General, Organic, and Improvised Chemistry PDF

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General, Organic, and Improvised Chemistry

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1. Synthesis of Potassium Nitrate KNO3 (5 replies)

2. Epsom Salt -> Sulfuric Acid? (6 replies)
3. Question about decomposing ammonium nitrate (1 replies)
4. Extraction of hexamine from Esbit? (2 replies)
5. Manufacture of sodium hydroxide (12 replies)
6. Ethyl Centralite Synthesis (1 replies)
7. Bismuth Trisulfide Scarcity (4 replies)
8. Is it possible to separate toluene from gasoline? (4 replies)
9. Salicylic acid synthesis by hydrolysis of asprin (19 replies)
10. Chlorine gas storage/methods of use (1 replies)
11. Hexamine Synthesis step by step w/ pics (29 replies)
12. Iodine production (39 replies)
13. Sodium hydroxyde purity (10 replies)
14. Industrial Solvents Handbook (0 replies)
15. Oxygen Balance (8 replies)
16. Sodium dithionite (1 replies)
17. creative solution needed: seperate silver from palladium (9 replies)
18. Excel molecular formula subscript help (5 replies)
19. Barium Nitrate (6 replies)
20. Cobalt Oxide Coated Anodes (10 replies)
21. Electrophoretic Coatings (2 replies)
22. KNO3 solution gone wrong (0 replies)
23. Partial nitrations? (5 replies)
24. Looking for some solubility info... (12 replies)
25. Atmospheric Pressure? (0 replies)
26. Why KNO3 sucks for nitrations (15 replies)
27. Isopropyl Nitrite synth gone WTF (24 replies)
28. chemistry books (10 replies)
29. Acids, Equations & other basic questions (5 replies)
30. Polyhydrocarbon (7 replies)
31. Call for Papers. (0 replies)
32. Ignition Temperatures (4 replies)
33. Nitrowool? (10 replies)
34. H2O2 help (2 replies)
35. H2O2 out of a new fuel-cell? (1 replies)
36. DDT, The Pesticide (21 replies)
37. Peroxidization of Naphthalene (3 replies)
38. Chlorine gas from KMnO4 and HCl? (4 replies)
39. More powerful Chlorates? (7 replies)
40. Home Production of Bases (3 replies)
41. Sodium Perborate (1 replies)
42. Chemical Information On Solutions (1 replies)
43. Fertilizer ---->phosphorus pentoxide (12 replies)
44. Sulfuric Acid (3 replies)
45. Unforseen Happening With nitration of cellulose (8 replies)
46. Quick way of making Copper (II) Oxide (23 replies)
47. Best ways to synthesize Copper Sulfate (24 replies)
48. Sufuric Acid turned black! (29 replies)
49. VP racing fuel (7 replies)
50. Civil War Chemistry (8 replies)
51. Phloroglucinol Synthesis (5 replies)
52. Alpha-Hydrogen Chlorination (2 replies)
53. Condensation of nitromethane (3 replies)
54. quick, how can I get a hold of some cesium :D (35 replies)
55. N-methylpyridine synthesis (17 replies)
56. Tetrahydrofuran via dehydration of 1,4-butanediol (4 replies)
57. Would this work to make Sulfuric Acid? (7 replies)
58. Condone Providone? (5 replies)
59. Synthetic Cocaine (9 replies)
60. sodium azide synthesis (4 replies)
61. Kurt Saxons Method.... (21 replies)
62. The Road to Furazans (3 replies)
63. A review of chromium compound synthesis (38 replies)
64. Protecting a Double-Bond (4 replies)
65. Gammabutyrolactone (GBL) (35 replies)
66. Synthesis of Amines (16 replies)
67. Making ammonium persulfate (11 replies)
68. tetranitromethane synth??? (2 replies)
69. Destruction of Aluminum via Mercury Amalgamation (0 replies)
70.
71.
68.
69.
70. Explosives fromTerephthalic acid ? (9 replies)
71. Hydrazine preparation: anhydrous processes (36 replies)
72. Making AN. (1 replies)
73. Freebase Nicotine (14 replies)
74. On-line chemistry courses (2 replies)
75. Benzaldehyde (missing thread) (7 replies)
76. Lithium from Batteries (4 replies)
77. Thorium and Uranium (1 replies)
78. Increasing fuel power. (3 replies)
79. Red Iron Oxide -> Black (1 replies)
80. Sodiumtripolyphosphate (Na5P3O10) as a dehydrator (5 replies)
81. Household Film as Polymeric Binder (0 replies)
82. pH indicator (17 replies)
83. White Smoke Produced by AN (2 replies)
84. AP dimer-trimer conversion? (7 replies)
85. Condensing Oxygen out of Air (3 replies)
86. Phenole (16 replies)
87. Iodic acid & iodates (1 replies)
88. Purification, stabilizatin and storage of explosives (1 replies)
89. Ion exchange and acids (1 replies)
90. Detonator Capsule Materials & Reactivities (15 replies)
91. OT - Malonic Acid synthesis (4 replies)
92. Setting up a lab (108 replies)
93. urea as a substiute? (6 replies)
94. Ammonium Nitrate Solubility in Methanol (3 replies)
95. OTC pyridine production (14 replies)
96. The theory of OTC tetrahydrofuran (THF) synthesis (21 replies)
97. DNA chemistry (1 replies)
98. alternatives to chloroform (30 replies)
99. solubility of potassium perchlorate (25 replies)
100. Chlorinated aspirin (1 replies)
101. Mercury Thermometer (18 replies)
102. HCl + nitrate (20 replies)
103. sillicon tetrachloride (3 replies)
104. Chemistry Reference? (2 replies)
105. Medical Treatment (24 replies)
106. Purification of OTC Paraformaldehyde (14 replies)
107. Another method of KClO3 preparation (20 replies)
108. how to guess the reaction will be cool or hot? (13 replies)
109. Extraction of Nitroglycerin from DBSP (6 replies)
110. Ice Baths (14 replies)
111. NH3 gas (12 replies)
112. Toluene to Benzene? - Archive File (5 replies)
113. Ammonium Hydroxide/various nitrates/sulfates - Archive File (0 replies)
114. Nitrating mixtures - Archive File (1 replies)
115. Potassium picrate - Archive File (1 replies)
116. Easy O2 - Archive File (9 replies)
117. methenamine/hexamine manufacture? - Archive File (0 replies)
118. making K2CO3 - Archive File (5 replies)
119. mannitol = sorbitol? - Archive File (0 replies)
120. Hydogen Iodine - Archive File (0 replies)
121. Weird nitration process - Archive File (0 replies)
122. Di-(2-ethylhexy)sebacate - Archive File (1 replies)
123. peroxysulfuric acid - Archive File (2 replies)
124. formaldehyde toxicity - Archive File (0 replies)
125. Acetic Acid - Archive File (0 replies)
126. Polyvynyl alcohol (13 replies)
127. DDNP: Mega's procedure: Production of Picramic Acid? - Archive File (6 replies)
128. chlorate or perchlorate? - Archive File (0 replies)
129. chemicially destroying explosives (0 replies)
130. more concentrated H2SO4 from car batteries - Archive File (9 replies)
131. RDX/PETN precursors - Archive File (0 replies)
132. Chlorine by HCl and MnO2 - Archive File (0 replies)
133. Refluxing - Archive File (1 replies)
134. potassium to potassium nitrate - Archive File (1 replies)
135. NH4ClO3 - Archive File (8 replies)
136. eed help identifying acid. - Archive File (6 replies)
137. storage codes - Archive File (1 replies)
138. questions about vacuum distillations - Archive File (0 replies)
139. would this work to get hydrochloric acid - Archive File (5 replies)
140. filtering - Archive File (2 replies)
141. NH4NO3 + KCl -> NH4Cl + KNO3 ? - Archive File (0 replies)
142. Potassium-Kalium - Archive File (0 replies)
143. I haven't been able to make hexamine - Archive File (5 replies)
144. White fumes? - Archive File (0 replies)
145. generating chlorine gas - Archive File (2 replies)
146. Iron oxide problems - Archive File (8 replies)
147.
148.
145.
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147. NC FROM PAINT LACQUER - Archive File (0 replies)
148. Extracting KNO3 from Sucrose/KNO3 mixture? - Archive File (0 replies)
149. Chloroacetone: warm or cold? - Archive File (0 replies)
150. ammonia and bleach - Archive File (0 replies)
151. White Phosphorus - Archive File (7 replies)
152. Fe2O3 (0 replies)
153. Freezing water out of weak H202 solutions - Archive File (1 replies)
154. A Crazy Idea... (Reactions with NX3) (6 replies)
155. NO acetic anhydride - Archive File (0 replies)
156. Methylamine. (6 replies)
157. Methods of extracting NM - Archive File (2 replies)
158. How to solve a stoichiometric ratio (0 replies)
159. Phosgene a substitute for PCl3 in CH3COCl production? (18 replies)
160. dextrin from starch - Archive File (4 replies)
161. Ethylchloride - Archive File (0 replies)
162. Prep. of Benzoyl Chloride - Archive File (0 replies)
163. Silane gas. - Archive File (0 replies)
164. Questions on lead azide precursors. - Archive File (0 replies)
165. Calcium Carbide - Archive File (0 replies)
166. Heating H2O2 - Archive File (1 replies)
167. Ammonium Perchlorate - Archive File (0 replies)
168. Extracting Potasium Nitrate - Archive File (3 replies)
169. hydrosilicons (or silicon hydrogen chemistry) (5 replies)
170. Water aspirator for vacuum? - Archive File (0 replies)
171. vacuum distilling? - Archive File (0 replies)
172. propylene glycol? - Archive File (1 replies)
173. No nitric acid - Archive File (2 replies)
174. making K2CO3 - Archive File (0 replies)
175. Hydogen Iodine - Archive File (0 replies)
176. Weird nitration process - Archive File (0 replies)
177. Simple questions about dichlorobenzenes.. (13 replies)
178. preperation of formaledhyde (46 replies)
179. electrolosis of organic salts (11 replies)
180. Manganese Heptoxide's halogen cousin :) (0 replies)
181. Would this work? (sodium chloroacetate) (5 replies)
182. Sodium Party (29 replies)
183. Making Anhydrous Ethanol... (13 replies)
184. Trying to make OTC trimethylsilyl chloride (9 replies)
185. Reduction of Styphnic acid (1 replies)
186. Reaction rate... (12 replies)
187. NaClO3 from Calciumhypochlorite - Archive File (0 replies)
188. oxidation of potassium chlorate to perchlorate - Archive File (7 replies)
189. New Oxidizer - Archive file (0 replies)
190. Help - NaCl03 from bleach - Archive file (0 replies)
191. nitration - Archive file (0 replies)
192. An+sulfuric for nitro esters - Archive file (3 replies)
193. Making X% Y(sol) from >X% Y(sol) ? (15 replies)
194. Nitromethane Synthesis - Archive Thread (31 replies)
195. Making AN - Archive Thread (0 replies)
196. Ammonium Chloride Synthesis (8 replies)
197. Benzophenone (destillation) (10 replies)
198. Products of Detonation Effecting Soil (9 replies)
199. Attempt to plasticize PETN (16 replies)
200. weird white precipitate (12 replies)
201. Boric acid (15 replies)
202. Ethyleneurea (3 replies)
203. Isotopic Explosives (11 replies)
204. Sodium Sulfide (20 replies)
205. Tables weights and measures (5 replies)
206. Hydrogen Peroxide decomposition data (2 replies)
207. Boron - only useful for ignitors? (11 replies)
208. phosphorus production (22 replies)
209. Nitration without the use of acid?!?! (5 replies)
210. Color of Fe2O3 (3 replies)
211. Nitration of Acetone (13 replies)
212. chemistry question, reactivity stuff.. maybe.. (5 replies)
213. Carbon Foam (11 replies)
214. Acid recycling/recovering (13 replies)
215. Making H2SO4 from HNO3 (27 replies)
216. Cyalume glowsticks \ liquid glow comppound (4 replies)
217. Benzofuroxan and derivatives (4 replies)
218. Hygroscopicity, problems, solutions and thoughts (4 replies)
219. chlorites from chlorates (4 replies)
220. phenol (8 replies)
221. A couple of misc. questions.,.. (3 replies)
222. How much lemon juice for the AP? - archive file (0 replies)
223. HC is just a catalyst right? - archive file (0 replies)
224.
225.
222.
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224. Styrene-Butadiene Rubber (10 replies)
225. Ammonium Picramate for DDNP (13 replies)
226. Chlorate, Perchlorate production cells -archive file (0 replies)
227. Acetic Acid ------> Acetic Anhydride -archive file (24 replies)
228. Liquid Oxygen Synth (23 replies)
229. potassium nitrate from ammonium nitrate -Archive File (2 replies)
230. acid for nitration -Archive File (0 replies)
231. Calculating Oxygen Balance -Archive File (0 replies)
232. Hydrazine (41 replies)
233. accident (effects) (6 replies)
234. Types of Diesel Fuel (13 replies)
235. The Hunt for Decalin (22 replies)
236. My Curious Electrolysis (2 replies)
237. potassium permanganate synthesis (24 replies)
238. Recycling Calcium Sulfate, is it Possible? (9 replies)
239. 5-Aminotetrazole (5-ATZ) synth. (15 replies)
240. Nitrogen fullerenes (8 replies)
241. Copper liner (7 replies)
242. potassium nitrite synthesis (79 replies)
243. Homemade alcohol (103 replies)
244. pentaerithrytol reaction. (3 replies)
245. Looking for info on ammonium azide... (8 replies)
246. Catalysts for carbonyl + amine condensation reactions? (1 replies)
247. Security products cheap (2 replies)
248. Concentrating and purifying Sulfuric acid (16 replies)
249. De-polymerizing Teflon (15 replies)
250. Alcohol Fermentation (23 replies)

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Pages : 1 [2] 3
251. What is this? (14 replies)

252. Nitrous Oxide (39 replies)
253. Small test (6 replies)
254. Laboratory Technique Videos (1 replies)
255. ChemOffice 2002 7,01 Ultra (31 replies)
256. Balancing AN+NM => ???? formula (12 replies)
257. oxidation from H2O2 (15 replies)
258. Maybe OT- Hash Oil (15 replies)
259. tin tetracloride (1 replies)
260. tin tetracloride (17 replies)
261. carbon monoxide (11 replies)
262. Preparation of benzoic acid (15 replies)
263. concentrating nitromethane? (20 replies)
264. Blu-Tack (75 replies)
265. sulfuric acid from sulfur flour (10 replies)
266. anhydre acetic (13 replies)
267. Perchlorate section on Megalomania's site (2 replies)
268. Other Pages... (12 replies)
269. impact sensitive flash target....any ideas? (7 replies)
270. Burning a Friend Alive...(safely) (49 replies)
271. .,-_:Stink Bombs:_-,. (29 replies)
272. Explosive Situations (13 replies)
273. Fun with biometric devices (4 replies)
274. Does Mercury mess up speed radars readings? (8 replies)
275. strange (useful) plastic? (3 replies)
276. sinking a paddleboat (21 replies)
277. Is there a contractor in the house? (15 replies)
278. Chemical Reactions (12 replies)
279. Tits on a fish (3 replies)
280. Improvised Sodium Azide (15 replies)
281. Acetone volatility (7 replies)
282. Poor Man's James Bond 5 (2 replies)
283. Nitric Acid (2 replies)
284. Car-Fire ??????? (7 replies)
285. OLD TOPIC - CELL FONE RUNS HOME LINE (10 replies)
286. Accidents and Legal Incidents (50 replies)
287. mega-low non explosive (13 replies)
288. The steps for explosive synthesis (15 replies)
289. Heterogenic Catalyst (AP) (2 replies)
290. Cutting Tools (54 replies)
291. breaking glass (22 replies)
292. A few things... (2 replies)
293. Responce to "Group purchases for the forum" (4 replies)
294. Economical Source of Zinc (8 replies)
295. Zink powder. (5 replies)
296. buying AN in bulk (9 replies)
297. United Nuclear? (33 replies)
298. Tranquilisers (4 replies)
299. denatured alcohol (29 replies)
300. Milori Blue (2 replies)
301. "The Tech of A Bomb Squad" (0 replies)
302. Techniques and Supplies for Filtration (5 replies)
303. Cop Cars Locator's (12 replies)
304. flask warmer (9 replies)
305. Spiked "jacks (?)" (4 replies)
306. new adventures in cyanide (85 replies)
307. polyisobutalene distributor (1 replies)
308. HTPB/PIB (2 replies)
309. Radar detectors (14 replies)
310. Safety precautions when making nitric acid.... (6 replies)
311. Need links for my links page (2 replies)
312. Anyone know how to make polyepichlorohydrin? (3 replies)
313. Exothermic Crystallization (6 replies)
314. Video Software (7 replies)
315. How's this lockpicking "guide" ? (1 replies)
316. Sodium Chlorate Production (222 replies)
317. Crystaline AN. (24 replies)
318. Bits And Pieces From OZ (9 replies)
319. Obtaining Al in Australia... (49 replies)
320.
321.
318.
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320. Apology (2 replies)
321. Got Valves? (11 replies)
322. Converting Problems (1 replies)
323. Other species of K3wlz (12 replies)
324. Selling my tools/equipment (3 replies)
325. Nitric acid article from PDF (12 replies)
326. Telco Hand Phone set (6 replies)
327. Hand Flares and Parachute Rockets (9 replies)
328. NaN3 From Airbag (29 replies)
329. o my god.. (20 replies)
330. Kewl chemistry corner April 6, 2002 (7 replies)
331. KIFE, online source? (11 replies)
332. little question about vacuum pump (4 replies)
333. Jobs (74 replies)
334. Smoke movement (8 replies)
335. Clandestine lab (131 replies)
336. WWII bomb in my neighbourhood (34 replies)
337. Pentaerythritol anybody? (27 replies)
338. cupric nitrate (4 replies)
339. Merck Index 13th edition now available. (5 replies)
340. Anybody save The Journal of Propellants, Explosives, and Pyrotechnics website? (1 replies)
341. Improvised distillation apparatus (52 replies)
342. hexamine manufacturing (41 replies)
343. Ball Mill (78 replies)
344. Caffeine. (3 replies)
345. Chemistry Question (14 replies)
346. This site is way cheap vs. firequest! (11 replies)
347. Beautiful metal nitrates (40 replies)
348. grappling hook (24 replies)
349. napathalene (11 replies)
350. Ordering chems. (10 replies)
351. AN availability in the UK? (4 replies)
352. Binder ? (5 replies)
353. If anyone wants AgNO3, look on eBay. (18 replies)
354. Pics! (53 replies)
355. My PDF (3 replies)
356. Eagle Layout Editor 4.08r2 (4 replies)
357. Nuclear testing videos (2 replies)
358. tripwires (6 replies)
359. An excuse for buying acids (9 replies)
360. Chemicals from batteries (56 replies)
361. explosives-sound(?) (20 replies)
362. Improvised Acid Rain.. HELP! (6 replies)
363. E-books worth a read (3 replies)
364. one second plumer (15 replies)
365. REALLY good books on Xplosives? (34 replies)
366. Organic chemistry (7 replies)
367. Proxy (20 replies)
368. IMH (T&T)? (1 replies)
369. Poison (112 replies)
370. HCL (8 replies)
371. improvised GSM autodialer (18 replies)
372. Most useful 'tool'? (20 replies)
373. Why don't we.. (5 replies)
374. Download My PDF! (6 replies)
375. I got a site with some cool pics on it (34 replies)
376. Improvised fan (16 replies)
377. Good reading materials... (5 replies)
378. improvised Linear Shaped Charge (24 replies)
379. free respirators with filters (14 replies)
380. project avalanche (55 replies)
381. Suggestions for remote detonator? (11 replies)
382. Opening sprung latch locks - product found (3 replies)
383. browns gas(hydroxy)?!? (11 replies)
384. crazy shit w/ napthalene (13 replies)
385. Sulfur from a sulfate..? (10 replies)
386. YC Shooting Range (20 replies)
387. I have a problem (5 replies)
388. Making Iron Oxide (25 replies)
389. WTF happened to my H2SO4? (18 replies)
390. suggestion for money (1 replies)
391. Perfect Toy (0 replies)
392. AIM/ICQ ? (1 replies)
393. ssaerospace.com (3 replies)
394. UPGRADE SHUTDOWN!!! (0 replies)
395. The perfect x-mas present... (13 replies)
396. First explosive? (60 replies)
397.
398.
395.
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397. Merry Christmas (33 replies)
398. Free Batteries for Christmas (17 replies)
399. Det Cord Construction (21 replies)
400. RTPB/Video Editing (38 replies)
401. new site (29 replies)
402. KNO3 and Fertilizer (23 replies)
403. I need some help!!! (15 replies)
404. heart beat sensor (2 replies)
405. Your favorite anime/cartoon? (40 replies)
406. Crocodile chemistry (9 replies)
407. WHOLESALE SOURCES (2 replies)
408. Potassium Chlorate (21 replies)
409. good video/pic source? (2 replies)
410. Eating up concrete (15 replies)
411. Passing the polygraph (22 replies)
412. phosphate (0 replies)
413. New Smilies (2 replies)
414. Volcano Demonstration Chemical (7 replies)
415. Getting Free Internet Service (1 replies)
416. lithium (20 replies)
417. Iodine (26 replies)
418. Rubber-Like Stuff, HELP! (6 replies)
419. Distilling HNO3 from H2SO4+KNO3 (5 replies)
420. Trioxane (2 replies)
421. Phosphorescent Compounds (8 replies)
422. acetaldehyde from bleach? (9 replies)
423. The limit between high and low explosives? (35 replies)
424. Fool Proof Guide to making HNO3 (21 replies)
425. High yield aromatic nitration with KNO3/H2SO4 in DCM (2 replies)
426. Tomorrows world uk (8 replies)
427. elite fighting force (10 replies)
428. Phosphor: white --> red ? (3 replies)
429. Whats everyone planning for this new year? (37 replies)
430. Best Mix For oxygen+acetylene devices (for a friend) (13 replies)
431. Thermite Mix in PMJB vol.1 (11 replies)
432. Instructions on How to use chinese celebration crakers (8 replies)
433. Rifle/Hand Grenades (0 replies)
434. What is in Liquid Fire? (9 replies)
435. Nitration catalysts (0 replies)
436. inflammable (12 replies)
437. lead nitrate (2 replies)
438. Liquid Carbonic (8 replies)
439. Red P (13 replies)
440. What did you do during the crash? (75 replies)
441. does any one have plans from plans & kits site? (8 replies)
442. 70 virgins? (3 replies)
443. What to do when a cop moves in? (16 replies)
444. 13-0-46 fertiliser is it good? (2 replies)
445. How to get Bin Laden (30 replies)
446. the rag head (2 replies)
447. To Jumala... (9 replies)
448. WebCam (8 replies)
449. Wing Chun Wooden Man (4 replies)
450. Buying potassium permaganate in uk (10 replies)
451. Common sense (2 replies)
452. armored car kit! (1 replies)
453. Nitration with polyphosphoric acid and KNO3? (2 replies)
454. snitched. (15 replies)
455. Distilling condenser types (13 replies)
456. mac-11 (25 replies)
457. favorite explosives. (1 replies)
458. Bank Safes (25 replies)
459. Advice (8 replies)
460. school sanctioned explosives demo....schweet! (28 replies)
461. Shockwave reducing foamed concrete. (1 replies)
462. Stun gun (14 replies)
463. emp (4 replies)
464. 50 stupid things to do with matches (31 replies)
465. Phosphorous Pentoxide (13 replies)
466. homebuilt missile (30 replies)
467. Sodiumazide (5 replies)
468. Bullet proof glass (25 replies)
469. Safety measures (12 replies)
470. Exploding Car's.. (3 replies)
471. Why my life become sucked too! (30 replies)
472. LSD (1 replies)
473. pyro-page (1 replies)
474.
475.
472.
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474. What to do if the worst thing happends? (19 replies)
475. MY LIFE BECOME SUCKED (13 replies)
476. ethylene urea (4 replies)
477. Chlorate Cell power supplies (17 replies)
478. Induction coils- help needed badly! (14 replies)
479. Rust (1 replies)
480. NO2 (8 replies)
481. Azido Binder EGBAA (2 replies)
482. Cop Killer ??? (27 replies)
483. Hydrazine Hydrate 26 % (2 replies)
484. looking for dielectric fluid (7 replies)
485. HNO3 by desiccation (27 replies)
486. Safe Breaking and alarms etc. (12 replies)
487. door sensors (25 replies)
488. AN used as a desiccant? (7 replies)
489. Tony Montana got a scanner!!!! (19 replies)
490. Pernitric acid (5 replies)
491. Everyday chemicals for HE (38 replies)
492. polynitroalkyl amines (1 replies)
493. How are permanganates made? (3 replies)
494. ethanolamines (4 replies)
495. How to bug the wife (3 replies)
496. seperating Fuel Oil from Anfo (2 replies)
497. Dirty blood (4 replies)
498. VoD of NU? (3 replies)
499. Separating KNO3 and NH4NO3 (4 replies)
500. Telling the difference between Ammonium Nitrate and Potasium Nitrate. (6 replies)

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Pages : 1 2 [3]
501. extracting iodene (11 replies)

502. Methylene Chloride (15 replies)
503. picric acid problem... (6 replies)
504. Nitrate fertilizer question (16 replies)
505. Sulphuric Acid Synthesis (57 replies)
506. Chlorobutanol info (3 replies)
507. H2O2 ways to concentrate 3% ? (131 replies)
508. Liar Exposed! (formerly P.E 4 And A Car) (85 replies)
509. paraformaldehyde (37 replies)
510. A quick question on nitronapthalenes: (9 replies)
511. Whats hexamine called in Norway? (7 replies)
512. Megalomania, please help! (3 replies)
513. Various Questions. (1 replies)
514. Urea manufacture (16 replies)
515. concentrations (7 replies)
516. Re: The list (10 replies)
517. Drying ammonium nitrate, dessicator (0 replies)
518. Ammonia chemistry questions. (1 replies)
519. superpowerful explosive (23 replies)
520. Density Table (15 replies)
521. H2O2 from OxyClean? (17 replies)
522. improvised blinding powder/grenades? (34 replies)
523. fun with N2 (16 replies)
524. CrO3 (25 replies)
525. Luminous solution... (25 replies)
526. Small Blasting Machine from Will (7 replies)
527. The most powerful explosive?? (15 replies)
528. hydrazine!! (30 replies)
529. Obtaining/producing oleum, how to make SO2 (19 replies)
530. Other peroxides. (52 replies)
531. Ammonium Chloride (3 replies)

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The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Attempt to plasticize
PETN
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View Full Version : Attempt to plasticize PETN
stanfield February 21st, 2003, 04:32 PM

I tried to plasticize 50g of my PETN with lecithin and mineral oil. This method is usually used with RDX but PETN and RDX are very similar so, I substitued RDX with PETN
So, I mixed 50g of PETN, 0,3g of lecithin and 7,3mL of mineral oil in a plastic bag and I DIDN'T obtained a "modelable" material, it's still powder !!! Why ?
==> <a href="http://stanfield.150m.com/plastic.htm" target="_blank">Photograpy of the experiment</a>

EDIT : HEAVY pictures ! ADSL or Cable recommanded...
see ya !
[ February 21, 2003, 03:34 PM: Message edited by: stanfield ]
rikkitikkitavi February 21st, 2003, 05:14 PM

just a thought, but the PETN didnt look so very fine? Shouldnt the powder be very very fine to make a good emulsion?
/rickard
Mr Cool February 21st, 2003, 06:19 PM

A very fine powder is needed to get a mouldable product, also I theorise that more rounded HE grains would be better than sharp/angular HE grains.
I personally find RDX to be much easier to plasticise than PETN, because it's much finer after recrystalisation from acetone. PETN forms quite coarse "sugary" crystals, RDX is
much finer, more like flour.
A tip which 10fingers suggested to me a while ago is to add some detergent, just a drop of washing-up liquid, to the water into which the PETN soln in acetone is dumped. This
seems to help keep the particle size small.
I've never had very good luck with oil-based mixtures though. I've made ones which work, but they were never as good as ones based on blu-tack binder with a bit of oil/
parrafin to keep it soft. Such polymer-based plastiques are much more resiliant, and do not fall apart as easily.
stanfield February 21st, 2003, 06:52 PM

I ordered some SBR rubber but I didn't received it yet ! Then I'll try to make some Semtex...
How can I "grind" my PETN into fine powder ? is a mixer recommanded ?

Furthermore, this PETN on picture didn't dissolved totally in acetone (not enough solvent), maybe it's a problem...
see ya !
rikkitikkitavi February 21st, 2003, 07:33 PM

dissolve it in acetone(saturation) , dump into water so the PETN preciptates again instantly.
Doing so doesnt give the PETN time to slowly grow crystals, but instead a maximum amount of fine crystals can be formed, since this process is faster than crystal growth due
to a high supersaturation.
I m not sure if it still small enough crystals though. But you wont loose any PETN, since it is almost insoluble in water.
/rickard
Microtek February 22nd, 2003, 09:25 AM

I think you should look to the mineral oil rather than crystal size of the PETN. I have experimented quite a bit with plasticizing PETN myself and while the Blu-tack binder is
unmatched, I did manage to make some good formulations with oil, wax and grease even though the crystals were more coarse than yours. I suggest you use the most
viscous oil you can find, preferably that used for lubricating the chain on a chainsaw; it is designed to be able to cling to the chain even as it spins. I can't see what kind of oil
you are using because I can't open the fourth picture.
stanfield February 22nd, 2003, 01:49 PM

this is "standard" mineral oil, nothing more. Density = 0.8/0.9
I have 15W40 motor oil, maybe it's better ?
Microtek February 23rd, 2003, 05:45 AM

It should be as thick as syrup or thin honey.
bonnsgeo February 23rd, 2003, 06:29 AM

to obtain a very fine petn i think its maybe better to do it in hot acetone and add slowly some water (hot too).
and after let it cool in a fridge.
i think if u "precipitate" it slowly, u will obtain very small crystals.
Microtek, i remember (not very well) your way to plasticize petn with blu-tack.
u dissolve blu-tack, extract the binder and replace it with petn ? am i right ?
do u have pictures to show how u do that ?
bye
Mr Cool February 23rd, 2003, 06:47 AM

That's right. Just leave blu-tack sitting in unleaded petrol until all that remains is a layer of sediment on the bottom. Pour the petrol off the top, and dump it into acetone. Stir it
around for a while, and the precipitated binder will collect together in a sticky lump. Take it out of the petrol/acetone mixture, and allow it to dry.
To make a plastique, add a few mL of petrol to 1 part of the binder, and mix in 8 or 9 parts of a very fine HE. Spread it out thinly to allow the petrol to evapourate.
I found that very slowly the plastique will harden and go more rubbery. Adding a small amount of oil, such as paraffin, will help to prevent this. It should be used instead of a
portion of the binder, not additionally.
kingspaz February 23rd, 2003, 08:55 AM

bonnsgeo, small crystals are obtained by FAST cooling not slow cooling. slow cooling causes big crystals.

I do a variation of Mr Cool's method:
I add about 10 g Blu-tack or a similar product to about 60 mL unleaded gasoline and heat/boil the mix to dissolve all except the filler. This is done with stirring and once only
the powdery filler remains, the beaker is allowed to sit until the supernatant liquid has become clear. The liquid is then filtered, taking care to get most of the gasoline through
the filter before any of the filler is poured into it; otherwise it will clog up the filter and make the process excruciatingly slow.
Most of the gasoline is then evaporated and the remaining viscous solution of plasticizer in gasoline is poured out onto a dish. A suitable amount of finely crystalline HE is added
and the slurry is mixed thoroughly with a spoon while blowing air over the mass. When the mix is almost dry, it is spread out in a thin sheet and left to dry until no gasoline
smell remains. It can then be pressed to increase density and cut into shape.
How much HE is needed per gram Tack depends on the actual product and the efficiency of your extraction procedure. Experimentation will be needed.
Observer February 23rd, 2003, 10:20 AM

That way you don't know how many % binder you are using.
When I made PBHMTD I used a process similar to that of Mr Cool's. Only I didn't precipate the binder, but left the gasoline to evaporate. I would recomend using sufficient
gasoline to get the whole mass of crystals damp, that way you ensure that all of them are coated with a thin layer of binder. The smaller crystals you use, the better it will
stick together. Using the minimum amount of hot acetone to dissolve your PETN and large amounts of almost freezing water should give you very fine PETN.
[ February 23, 2003, 09:29 AM: Message edited by: Observer ]
Microtek February 24th, 2003, 03:16 AM

That was my point in saying that experimentation would be needed; once it has been established ( by experiment ) how much binder/plasticizer is extracted by a given
amount of boiling acetone ( edit: gasoline, not acetone ), the entire isolation step can be skipped and thus save both time and solvent.
[ March 09, 2003, 07:05 AM: Message edited by: Microtek ]
Observer March 8th, 2003, 03:49 PM

I noted one thing today when I tried the method of precipating the binder in acetone. When the rubber had dried, it was harder than normal, it used to be sticky.
I checked the bottom of the container of the acetone/gasoline mixture, and small dropletts was lying on the bottom(might be residual rubber and it may in be in or partly in
solution).
The softner(sp?) agent?
Sorry Microtek.
[ March 08, 2003, 05:24 PM: Message edited by: Observer ]
andreas March 17th, 2003, 01:55 PM

<a href="http://www.straightshooters.com/target/btputty.html" target="_blank">http://www.straightshooters.com/target/btputty.html</a>
Maybe this is a rather cheap source for PIB.

Worthwhile to check out.
Mr Cool March 17th, 2003, 04:43 PM

The trouble with the blu-tack binder is you can't stretch it well, it ends up going fluffy and falling apart in my experience. The same is true if you press a ball of it hard, the
edges of the formed disc can split and go fluffy. For most applications it works well if you take care when handling it, but it would be nice to have a more plastic plastique.
Microtek, was it you who was using liquid latex a while back? Does this have the same flaw?
If you're using a plastique just to keep the HE in place, I personally prefer simple PBX-like compositions, formed from HE and two-part epoxy. You may need a simple mould
while the epoxy cures, and it takes longer since you can't just squish the HE into place and fire it, but it's generally a lot less messy and the charge is more resistant to handling
before firing.

The Explosives and W eapons Forum > Chemistry for Am ateur Expe rimenters and C itizen Scientists > General, O rganic,
a n d I m provised C hemistry > Products of Detonation Effe cting Soil
Log in
View Full Version : Products of Detonation Effecting Soil
CyclonitePyro February 24th, 2003, 12:10 AM

S o m e o n e I k n o w h a s a p l a n t o b o r e h o l e s i n t h e ground, place charges in the holes and create sm all crators which will be
refilled with soil of a higher quality in order for certain plants to grow nicely.
A p o s s i b l e p r o b l e m being that the explosive used will create products upon detonation that would hinder the growth or pollute
the plants. Acidity in the soil can seriously affect plant g rowth and m any explosives release acidic substances when they
d e t o n a t e . I t h i n k a m m onium n i t r a t e b a s e d e x p l o s i v e s a r e o u t . M a y b e n o t .
So the question is, what explosive could be used that upon deto nation would not leave chem icals in the surrounding soil that
would harm plants. The roots will eventually grow out far enough to absorb the tainted dirt.
The dirt does not nessecerily need to be thrown from the site, it could just be loosened to aid digging, but it would m a k e t h e
job easier if it was blown out. If the dirt doesn't need to be blown out of the crator this would allow use of less powerfull
e x p l o s i v e s t h a t m ight have no toxic detonation products.
Perhaps an O2/H2 mixture could be used which would only create water. Maybe expoding C02 canisters? Non-detonating
e x p l o s i v e s s e e m like they lack the power needed thoug h.
A-BOMB February 24th, 2003, 12:45 AM

AN it the only one I could think of its a explosive and a fertilizer, so if it all doesn 't detonate you a lready got som e fertilizer in
the hole.
spydamonkee February 24th, 2003, 01:14 AM

APAN seems like a good choice, simple to make too
EP February 24th, 2003, 01:47 AM

Explosives are often used for loosening soil for planting crops/fruit trees so I don't think there is anything to worry about.
Nihilist February 24th, 2003, 02:09 AM

I know AP would work however handling that m uch AP m i g h t b e a b i t d a n g e r o u s

I'm virtually certain that nitroglycerine in the form of dynam ite would produce no toxic products if a djusted to O B with NC or
s o m e other fuel. Of course you could sim ply use EGDN as that has perfect OB all by itself.
xyz February 24th, 2003, 04:54 AM

If you are worried about acidity, just put a small amount of limestone into the hole after it has been m ade. I don't think the re
is anything to worry about though.
0EZ0 February 24th, 2003, 05:51 AM

As Microtek has said. To produce non-toxic detonation products, all you need to do is select an explosive com position with the
OB as close to, or hig h e r t h a n t h e b a l a n c e d 0 % a s p o s s i b l e .
If m e m o r y s e r v e s , t h e p r o d u c t s y i e l d e d a r e o x i d e s o f C a r b o n ( C O < s u b > 2 < / s u b > ) , H y d r o g e n ( H < s u b > 2 < / s u b > O ) a n d o x i d e s o f
any metals that exist in the explosive if at all(eg.Al2O 3). Any Nitrogen forms into it's natural state
as N2.
If th e r e i s a n o v e r b a l a n c e o f o x y g e n ( t o o m u c h o x y g e n ) , t h e n t h e o n l y p r o b l e m with detonation products is free O 2 being form ed. Which isn 't m uch of a prob lem .
As you can see, all products from a balanced O B are gaseous, even in th e case of (vapourised)water and are rather non-toxic.
T h e r e s h o u l d n ' t b e m uch of a problem using explosives in this situation. As others have said, blasting has been used to ditch
hole s for fruit trees. Just be careful with the size of the charges <img border="0" title="" alt="[W ink]" src="wink.gif" /> . It can
surp rise som e people just how m uch earth can be displaced by blasting, especially if you have to fill in the hole aga in :D .
Good luck with the project.
<sm all>[ February 24, 2003, 04:55 AM: Message edited by: 0EZ0 ]
CyclonitePyro February 24th, 2003, 07:36 PM

Alrig h t s o u n d s g o o d . T h a n k s f o r t h e h e l p e v e r y o n e .
I know am m o n i u m n i t r a t e i s a g o o d f e rtilizer I was just worried about what compo unds it might form after detonating. I've
actually read that using lots high nitrogen fertilizer really lowers the pH of the soil, and you will need to use a lot of lim e s t o n e
to counteract it.
How does regular ANNM sound ? I thought ANNM at oxygen balance was unpractical.
<a href="http://www.globalsecurity.org/m ilitary/systems/m u n i t i o n s / m 3 0 0 .htm" target="_blank">http://www.globalse curity.org/

m ilitary/system s/m unitions/m 300.htm</a>
this link Arkangel posted recently has what I need. I just can't find that kind of auger in any stores.
I t h i n k a r o u n d 5 0 - 1 0 0 g o f A N N M m a k e s a crato r of the desired size for m y, err, m y friends use.
I guess I got a little carried away worrying about this, but I'll be dam ned if a whole year's crop is ruined because I b l a s t e d t h e
hole s!
I guess I could post pictures of the whole project, maybe even o f the final payoff :D
Everyone contrbuting to this thread gets a free plant m atter treat <im g border="0 " title="" alt="[Wink]" src="wink.gif" />
Anthony February 24th, 2003, 10:25 PM

1 0 0 g m of ANNM sounds good, although it would depend a lot on the soil type/structure.
You can get auger drill bits up to 1.5"-2" for drilling woo d from m ost DIY places. They should work in soil if you attach an
extension bar to get to the required depth. They're about $30-$40 new though, so an old knackered second hand one would
be ideal.
E x a m ple Pic:
<img src="http://www.longchengtools.com/1006c.jpg" alt=" - " />
Of course this is what you really want :)
<img src="http://www.fs.fed.us/r4/boise/m gmt/watershed/SilverCreek/media/dscn5503.jpg" alt=" - " />

a n d I m provised C hemistry > B e n z o p h e n o n e ( d e s t i l l a t i o n )
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View Full Version : Benzophenone (destillation)
frogfot February 25th, 2003, 12:19 PM

T h i s c a m e u p a t x i n v e n t i o n s , b u t m o r e p e o p l e m ust see this.
B e n z o p h e n o n e i s a n o t h e r k e t o n e w h i c h p r o b a b l y c a n b e peroxidised (pro bably). This would theoretically yie ld a very stable
peroxide, because there would be alot of electron rich benzene rings nea r peroxide bondings, wich would donate som e e l
dencity to pe roxide bondings. But thats just theory.
T h e r e a r e a " s i m ple" way to produce benzophenone, by destillation of calcium b e n z o a t e . I h a v e m a d e s o m e e x p e r i m e n t s o n

s m a ll scale and got n ice results. Heating small amm ount of calcium benzoate in a quarz pipe (28X1 cm ) c l o s e d a t o n e e n d ,
p r o d u c e d d e n c e h e a v y o r a n g e fumes that fell directly on the ground, it could be easily collected in a beaker, it condensed after
a while.
Orange product sm e l l e d s o m ething between roses and cherry.
W e l l , b e n z o p h e n o n e s h o u l d s m ell roses (pdf on web) and cherry sm ell is probably an impurity of an aldehyde. This is what i
got:
<a href="http://www.geocities.com /frogfot/stuff/benzophenone.jpg" target="_blank">www.geocities.com/frogfot/stuff/
benzophenone.jpg</a> (50ml baker)
W hile trying to upscale this procidure it filed in every way. I used an iron pipe (35X4,5cm), clutched in one end and filled with
~10g calcium b e n z o a t e . O p e n end was directed into a b aker in icebath. Heated pipe with a torch, fum es filled baker but they
condenced at very slow rate.
Another prob lem was incompleate decom position. It seem s that a m ore powerfull torch is required, or, som e t h i n g h a v e t o b e
d o n e a b o u t c h a m b e r / c a l c i u m benzoate. To raise efficiency of heat from torch or to lower d ecom position tem perature.
Can anybody solve those problem s or give an addvice, please?

E v e n i f b e n z o p h e n o n e c a n n o t b e p e r o x i d i s e d , i t w o u l d b e f u n t o p r o d u c e s o m e , f o r u s e i n o t h e r e x periments.
Heres differe n t p h y s i c a l p r o p e r t i e s o f b e n z o p h e n o n e :
MP 49oC; BP 306oC; insoluble in water; 13g soluble in alcohol
H a v e n o d e c o m position tem perature of calcium b e n z o a t e , i t s e e m s that it's m uch higher than 300oC.
[Editted to change "<>" to "[]", to m ake superscrip ts work]
<sm all>[ February 25, 2003, 01:09 PM: Message edited by: Mr Cool ]</sm all>
IPN February 25th, 2003, 12:33 PM

S o u n d s l i k e s o m ething very interesting to try. Have you tried to m ake it into pero xide yet?
W hat king of torch do you have? Because m y torch can reach 1500C easily. I have also access to a oxy-acetylene torch
reaching tem perature s u p t o 3 0 0 0 C .
I wo uld test this but I d o n t have any calcium b e n z o a t e .

Or could it be made by m i x i n g s o l u t i o n s o f s o d i u m b e n z o a t e a n d c a l c i u m chloride?
Btw. that product looks like oily phorone...
Found this with a little search:

<a href="http://www.orgsyn.org/orgsyn/prep.asp?prep=cv1p0095" target="_blank">http://www.orgsyn.org/orgsyn/prep.asp?
prep=cv1p00 95</a>
<sm all>[ February 25, 2003, 12:07 PM: Message edited by: IPN ]

Calcium benzoate can be producet like you said, if hot saturated solutions are m ixed and then cooled down. Solubility of Ca
benzoate is 2,67g at 0oC and 8,3g at 80oC in 100ml water. I never thought of this way, will use it
in the future.
I u s e d t o m ake it another way, maybe it's good to post for those that do n't have CaCl<su b>2</su b > . M a k e s a t u r a t e d s o l u t i o n
o f s o d i u m b e n z o a t e ( f o u n d a s s p i c e f o r c a n n i n g ) a n d a d d ~ 2 0 m l 30% HCl for every 22g.
Benzoic acid precipitates, filter and wash with cold water, then ad d e x c e s s o f C aCO3 and leave for a day. It rea cts
very slowly, then it's just to evaporate.
EDIT: Forgot, havn't tryed to peroxidise it, need bigger am m o u n t a n d a d vice. Im p u r i t i e s h a v e t o b e r e m o v e d s o m e h o w , a n d

because its not soluble in water how could one react it with H2O2? Maby dissolving it in alcohol, b ut
m aby alcohol will react too?
My torch can probably do 1500oC too, it's usual propane.
[Editted for same reason as above]
Mr Cool February 25th, 2003, 02:14 PM

As well as the water solubility problem (which m ay be overcom e with a load of alcohol), O B is really going to suck. It m a y b e
possible to n itrate it though, you would get a m ax of two -NO2's per benzene ring I think because -C O-Ph will be
m eta directing, but also deactivating so nitratio n m ight be hard, you could end up with just one -NO2 per ring.
Edit:
A good rule of thumb for working out directing orientation on aromatics is thus:
If th e substituting group contains double bonds, it will b e m eta directing and deactivating.
If th e substituting group contains all single bonds, it will be ortho/para directing a nd activating.
Halogens are ortho/para directing, but deactiva ting because of their high electronegativity.
So, -NH2, -O H, -CnH2 n+1</su b> etc are all activating o/p- directors, -CHO , -NO2</
s u b > , - C O O H etc are all deactivating m - directors.

T h a n x f o r a d ress, IPN. I got those synthesises in organic chem book, but they require some rare chems.
Mr C ool, I don't wanna sound ignorant but what is OB? May i guess, is it m a s s r a t i o b e t w e e n p e r o x i d e b o n d ings and the rest of
m olecule?
Maby this peroxide will suck as you said, but it could also be very unsencitive com pared to other peroxides, which should
proove the theory, that benzene rings can stabilize peroxide bondings. O ne could take acetophenone, which is smaller than
b e n z o p h e n o n e a n d i t ' s p r e p a r e d n e a r l y s a m e w a y . ( t h e r m . d e c o m p. of C a b e n z o a t e + C a a c e t a t e )
I r e a l i s e d t h a t b e n z o p h e n o n e h a v e n o p r o b l e m to condence, it condences directly in conta ct with surrounding air, bu t it rema ins

as "fog". I m ean, it rem a i n s a s s m all drops in air, which take som e time to settle down. If one would let this fog go through a
thin 10 m long pipe this would settle it down on walls. Gonna by copper p ipe and test this. (i planned to by it anyway)
I was a bit la te :rolleyes:
<sm all>[ February 27, 2003, 12:30 PM: Message edited by: frogfot ]</sm all>
Stoic February 27th, 2003, 01:32 PM

O B = O x y g e n B a l a n c e , I I R C.
megalomania February 27th, 2003, 10:59 PM

If I were doing this I would set the pipe up in such a m anner as to direct a gentle flow of air through it while the pipe is being
heated. The air flow will push any benzophenone out. You can bubble this exit ga s into water in wh i c h b e n z o p h e n o n e i s
insoluble. Th e b e n z o p h e n o n e s h o u l d c o n d e n s e right away and can be collected by filtration. Vaporized calcium b e n z o a t e f o r
e x a m ple will be soluble in water, and hopefully so will any other byproducts.
You may wish to consider laying your reaction pipe in a bed of coals. This is an effective m eans of directing the heat where you
need it. A torch m ay have a flam e of 1500 degrees, but that doesnt mean your pipes core will get that hot conside ring a torch
can only heat a sm all point at any one tim e.

T e s t e d s a m e procidure with 7,6 m copper pipe, it worked ok on sm all scale, fume s settled down. Actually it took about 15
m inutes to fill the pip e. But if one would go bigger, whole device m ust be closed airtight.
Heres used setup:

<a href="http://www.geocities.com /frogfot/stuff/benz2.png" target="_blank">http://www.geocities.com/frogfot/stuff/
benz2.png</a>
This would be perfect setup:

<a href="http://www.geocities.com /frogfot/stuff/benz1.png" target="_blank">http://www.geocities.com/frogfot/stuff/
benz1.png</a>
Dropping acetone have 2 reasons. First, wash down product from walls, because it's thick. Second, i beliave benzophenone
particles "stick" better to acetone than to any o ther dry surface.
Bed of coals is nice idea, it wo uld be hard to accom plish at hom e b u t o n e c o u l d m ake it next tim e i go cam ping.
Experim e n t s k i n d a s t o p p e d , i ' m searching for suitable parts..
EDIT:
Oh, would those peroxides be something possible? (dont laugh.. :rolleyes: )
<a href="http://www.geocities.com / f r o g f o t / s t u f f / b e n z o p h e n o n e . p n g " t a r g et="_blank">http ://www.geocities.com/frogfot/stuff/
benzophenone.png</a>
Calculated their O B just for fun:
(1)d i- -266
(2)d i- -234
tri- -234
Yp, thats low, but AP is also a bit low (-151).
<sm all>[ February 28, 2003, 04:55 PM: Message edited by: frogfot ]</sm all>
frogfot April 30th, 2003, 04:29 AM

It was long time, but finally got m uch better results. I fount suitable reaction cham ber
that is nearly airtight. Heres pic on it, ive combined steel body with brass adapter.
http://www.geocities.com/frogfot/stuff/vessel.jp g
Ive tested it in production of acetone with success, heres more details on vessel:
(http://www.geocities.com /frogfot/synthesis.htm l#aceton)
After som e tests i realised that setups from post above totally sucked they canno t settle down the product and passing fum e s
through wate r didn't worked eather.
But another way worked great. I let the pipe from reaction chamber into an outlet of filtering
flask that was closed in top with a filter from a v a c u u m c l e a n e r ( t h e o n e t h a t s u p p o s e t o r e move really sm all particles from air).
And it worked great! The fum es remained in flask and settled down after a while. There was sm all am m ounts of water too
(Probably crystall water).
D e c o m p o s i n g 3 0 g b e n z o a t e ( p a r t i a l l y ) g a v e 5 m l p r o d u c t a n d a b o u t 2 m l water. Though i will mak e a bit m ore precise tests on
larger scale.
O n e g o o d t h i n g t o m ention is that reaction m ust be pushed to the end, this will ensure that remaining cake in reaction vessel
will be porous and easy to rem ove (which wasn't in my case).
And another great thing happened some weeks ago in m y dream (in case) :) My dad helped to
draw a mass spectra of product, and it showed to be above 80% benzophenone! I should mention that tested sam ple have
b e e n s t a n d i n g f o r s o m e m onth and any volatiles would dissapear. This will be tested another time with fresh product. I will a lso
add further results in this
post on yield s. And m aby write the whole procidure as for aceton e destillation on m y p a g e .
John A shcroft May 4th, 2003, 12:44 AM

Your benzophenone is definitely very im p u r e . B e n z o p h e n o n e i s c o l o r l e s s .
Such high tem peratures shouldn't be necessary for decomposing calcium benzoate into ca lcium c a r b o n a t e a n d b e n z o p h e n o n e .
Calcium acetate, for exam ple, begins decom posing around 160C.
How was your calcium benzoate acquired/prepared?
A cyclic peroxide of benzophenone is going to be very weakly ex plosive. Nitrating the benzophenone prior to peroxidation will
resu lt in a dangerous peroxide product. Firstly, the im proved oxygen balance will m a k e d e c o m position m o r e e x o t h e rm ic,
m e a n i n g t h a t a r a n d o m d e c o m p o s i t i o n e v e n t o f a single (or several) molecules (not especially uncomm on with organic
p e r o x i d e s ) i s m ore likely to propagate into detonation of the entire crystal. Secondly, the nitro groups are electron
*withdrawing*, m eaning that electrons will be withdrawn from the aromatic ring, thus withdrawing electrons from t h e o x y g e n s o f
the peroxide bonds, which will dram atically weaken the peroxide bonds - a dangerous situation ind e e d .
frogfot May 7th, 2003, 01:09 PM

M a d e s a m e e x p e r i m ent on larger scale, 50 g benzoate. This gave totally 20 ml liquid, from which 13-15 m l was red-brown goo
and rest was water.
I described this on page too:
http://www.geocities.com/frogfot/synthesis.html#benzophenone
John, it would take alot of time if tem perature was near decomposition of salt..
I have tryed the peroxidation and failed, Mr Co ol was right about loads o f alcohol. I dissolved sma l l s a m p l e o f u b t a i n e d
" b e n z o p h e n o n e " i n 5 t i m e s m e t h a n o l e a n d a d d e d o n e a m m o u n t of 30% H2O2 after what
benzophenone separated.. failure :(
Anyway, som e drops of 30% HCl was a l s o a d d e d and this stayed over night... nothing hap p e n e d .
W ell, it probably got som e other uses (nonexplosive), now its only to purify the product, d unno how...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Ammonium Chloride
Synthesis
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stanfield February 28th, 2003, 04:00 PM

I tried to make some ammonium chloride (for smoke bomb) using HCl and NH3, go to :
<a href="http://stanfield.150m.com/ammoniumchloride/ammoniumchloride.htm" target="_blank">this web page</a> and give me your opinions to solve my problem...
thanx !
Polverone February 28th, 2003, 04:29 PM

Does your NH4Cl stink like HCl? Is that how you know it's full of acid? If so, the smell and the problem should go away once the crystals completely dry. NH4Cl is acidic in
aqueous solution so testing with pH paper/meter won't help.
There's another way of making NH4Cl that can be faster if it doesn't need to be high purity (should work fine for smoke bombs): mix hydrochloric acid and a concentrated
solution (or even pure prills) of NH4NO3. The NH4Cl isn't as soluble and you will obtain a considerable precipitate if the temperature isn't high.

Solubility of NH4Cl in 20oC is 37,4g/100ml and 87,3g/100ml at 116oC. So, by described procidure (if you chilled it to 20oC) you lost 43% of NH4Cl.
You just could boil off as much water as possible, to make it thick, and then pour on a plate in oven. Holding it at about 150oC for some hour would remove the
rest of water. Excess of HCl would probably evaporate away too (but this have already been answered).
stanfield March 1st, 2003, 03:54 PM

I boiled down most of the water then filtered out the product...
But I think the yield won't be famous, I didn't weighted it out yet but I fell it's not very good...
rikkitikkitavi March 1st, 2003, 05:51 PM

When I have made NH4 salts, I have always used a slight excess of ammonia. This way I can boil down the solution to dryness with a common stainless steel pot (for cooking
:) , since many NH4 salts are very soluble at high temperatures, meaning trowing away the mother liquor (the solution in equlibrium with solids) lowers your yield.
It is only in the very beginning it smells of ammonia, it evaporates quickly when the solution is boiling. However, doing it inside is not recommended! With a tighter pH control
of course you need less NH3 excess, thus less fumes.
I add the NH3 to the acid until the solution smells weakly of NH3. ( I start with measuring out the liquids aproxmemately )
However, most NH4 salts are very soluble, which means that at the end, you will have a sticky mess boiling and sputtering everywhere. So the last step , drying/boiling down
a 50/50 mixture I usually do in a pyrex bowl in a oven.
Today I made 350 grams of (NH4)2SO4 from some polluted sulfuric with this method.
/rickard
spydamonkee March 1st, 2003, 05:52 PM

hmmm seems like NH4CL has a few uses that intrest me so i might just aqquire one of the 40kg bags i have seen laying around on a factory floor
nothing like having chems in bulk :D
Will sit next to my 10 Ltr's of 98% H2SO4 that i aqquired from the same place, free of course <img border="0" title="" alt="[Wink]" src="wink.gif" />
Wow that was real informative. :rolleyes:

Alen.
[ March 01, 2003, 05:15 PM: Message edited by: ALENGOSVIG1 ]
megalomania March 2nd, 2003, 03:15 AM

Some may remember my recent problems in boiling down ammonium chloride in the kitchen. That's what I get for trying to save my heating mantle from extended heating
operations. Once I moved the works back into the lab I had no trouble. Mine had an excess of HCl which did stink; I would prefer an excess of ammonia myself. I boiled the
liquid nearly dry using a flask to minimize spattering (quite minimal with a small neck) and poured it out into a crystallization dish to finish the job with low heating.
stanfield March 4th, 2003, 12:52 PM

yeah, this stuff smell like hell when you're boiling down the solution...
NH4Cl with NH4NO3 and HCl ? interresting but what's the equation ?
HCl + NH4NO3 = NH4Cl + HNO3 ? right ?
see ya !
Mendeleev March 8th, 2004, 04:06 PM

Sort of old thread I stumbled upon, sorry, but your mix looked like white goo, stanfield, when I mix mine it looks like water, and just gives off lots of white fumes, I seem to
get okay yields, why the disrepancies?

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Making AN - Archive
Thread
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Anthony March 5th, 2003, 05:51 PM

Detonator
Frequent Poster
Posts: 132
From:
Registered: NOV 2000
posted February 01, 2001 03:16 AM
--------------------------------------------------------------------------------
When i can't buy AN, i do it :
NH4HCO3+HNO3
It's available widly and very cheap...1KG is about 2$
Microtek
Frequent Poster
Posts: 194
From:
Registered: JAN 2001
--------------------------------------------------------------------------------
But what about the nitric acid ? If you can get decent concentrations ( 65% or more ) and H2SO4 95%, you could be making NG or EGDN and shouldn't waste time on AN.
In fact almost any HE is better than AN in its pure form, only ANNM will make it worth your while, so the question is: Can you get nitromethane? well can you.. punk? ( no
offense )
Detonator
Frequent Poster
Posts: 132
From:
--------------------------------------------------------------------------------
mmm who would like to make NG??? someone wants to die?
You can make alot of AN cheaply...it'snt dangerous...
BTW you can make RDX or Picric Acid without using NA.
And use a better language (punk)!!
no_name_available
A new voice
Posts: 25
From: germany (?)
posted February 01, 2001 04:33 PM
--------------------------------------------------------------------------------
1st.: why do you make it with NH4HCO3 ? just use household common ammonia: NH3 + HNO3 -> NH4NO3
2nd.: why to make it and not to buy it as fertilizer ? i made some by pouring ammonia 30% to 65% HNO3 - it take a lot of time to drop it slowly in, and i had it to do with my
gasmask because of the ammonia gas was getting free by the heat of the nitration. my PH testing paper was getting blue just by liing open in the air !
ALENGOSVIG1
Moderator
Posts: 766
From: Vancouver, Canada
--------------------------------------------------------------------------------
detonator: nitro is less sensitive than AP .
------------------
Explosives Archive
PYRO500
Moderator
Posts: 1474
From: somewhere in florida
Registered: SEP 2000
--------------------------------------------------------------------------------
well that may be true for commercial stuff, but homemade NG is dangerousl beacuse it can poision you with vapors, drip off unnnoticed and go boom! and in production it
makes nasty fumes!
ALENGOSVIG1
Moderator
Posts: 766
--------------------------------------------------------------------------------
well, thats easy. Use a fume hood, or fume absorber, and use gloves and a mask when messin witth it. It sensitivity is less than ap if properly washed
------------------
Explosives Archive
Microtek
Frequent Poster
Posts: 194
From:
--------------------------------------------------------------------------------
I have just begun using NG in my experiments.
I don't make a lot of it at one time, at least not until I have tested it thoroughly, but until now my results are promising.
While trying to make a good plastique from HMTD or AP, I constructed a drop-hammer to test the impact sensitivity. As I was working with primary explosives I only made it
with a 35 cm drop and a 335 gram hammer, however, I used my lathe to cut the impacting surface of the hammer to micrometer precision. The hammer is made from
ordinary medium grade steel, while the anvil is a hardened steel plate and the hammer is cut in such a way that it impacts on exactly 1 square centimeter. This setup will
detonate AP with as little as a 10 cm
drop, HMTD a little more, but in 20 tries from 35 cm, I was unable to set off NG. With the NG, I had to use a manual hammer and hit it with considerable force lying on an
anvil. In another test, I used epoxy-putty to make a small "bowl" on a board ( to test the breaching power ). This bowl could hold maybe 0.5 cc, and using this little NG, I
figured I'd only use a small cap, so the cap explosion wouldn't obscure the effect of the NG. In the end I used a coloumn of AP 2mm in diameter and 9mm long, pressed with
about 40 lbs ( thats about 8000 psi ).
No detonation.
I made several other tests both with NG and EGDN ( and I'm still making tests ), and at this point, I think NG is really much safer than AP or HMTD. EGDN is somewhat more
stable than NG, but NG is stable enough if you are used to the safety precautions that go with AP.
Hint: NG mixes with nitromethane. The addition of NM makes it more stable, and with a mixture of 8.2% NM and 91.8% NG you have a perfect oxygen balance....
blackadder
Frequent Poster
Posts: 313
From: London
Registered: DEC 2000
--------------------------------------------------------------------------------
When NH4N03 is mixed with H20, an endothermic reaction takes place, what is the resulting chemical and how would one extract the NH4N03 from it?
PHILOU Zrealone
Frequent Poster
Posts: 479
From: Brussels,Belgium,Europe
--------------------------------------------------------------------------------
Simply by heating the solution to 100C and allowing the water to come out. Then cool down in an enclosed vessel with some dessicant (in another recipient) like CaCl2 or
anhydrous CuSO4 or MgSO4. add a little ethanol to ensure taking all the water away.
It should cristallise as white clouds on the walls. take them en put them in the sun on a black surface or in an open oven at medium temp!
------------------
"Life that deadly disease sexually transmitted".
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o )"
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Thanks, PHILOU.
I'm trying to extract all of the NH4NO3 out of those used instant cold packs that I have lying around.
They work by puncturing a bag of NH4NO3, which is inside a bag of water, the two substances mix, the reaction takes place, and the water becomes cold.
[This message has been edited by blackadder (edited February 02, 2001).]
Detonator
Frequent Poster
Posts: 132
From:
--------------------------------------------------------------------------------
PHILLO I have problems getting all the water out from AN, any suggestions?
Mr Cool
Frequent Poster
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From: None of your bloody business!
--------------------------------------------------------------------------------
No reaction takes place when you dissolve AN in water. It's a minor point, but I thought I'd point it out anyway.
EGDN is more stable than NG at slighlty elevated temperatures, so I make it instead of NG if I ever need a liquid explosive. Mix it with acetone, 75% EGDN : 25% acetone to
make it less sensitive.
To dry AN, just powder it and put it in an oven at 105*C for a few hours, and store it in an airtight container.
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
P.S. - don't bother making AN. If you look around, you're bound to find an agricultural supplier that will sell you 55lb for about $40. I can get 55lb for 27.50. Not a bad price.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Making X% Y(sol)
from >X% Y(sol) ?
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gatecrasher March 5th, 2003, 11:01 PM

Lets say I wanted to make 15 grams of 10% solution of HNO3 from 70% Nitric Acid.
How many grams would I need to put in of the 70% HNO3 to H2O????
Meaning how many grams of H2O and how many grams of the 70% HNO3????
(Obviously this question can be relevant to any other solution, so I changed the title to make it more general...)
[ March 07, 2003, 02:22 PM: Message edited by: Mr Cool ]
PEROMAN March 6th, 2003, 07:02 AM

You need 2.14g of 70%HNO3 + 12.86g wasser :D
Arthis March 6th, 2003, 12:18 PM

How does the moderating system work then ? Other mods can't ban or so ? (hell I know it pretty off-topic question but since the topic is dumb... )

Arthis, the moderating system works thusly:
Lamer posts, lamer is seen, lamer is gone :D . That's all you need to know.
As it happens, I think we're experimenting with being nice at the moment. I can't say that I'm a fan of all this kewl-hugging, but we'll see how it goes. Therefore I won't do
anything about this topic.
It is actually quite a useful question, syntheses will often ask for X% of Y(sol), when you have >X%.
What you need to do is work out how much Y is in 100g of your solution, then divide this by the % needed, multiply the number by 100, then subtract 100 (if you started by
working with 100g). This will give you the mass of solvent you need to add to 100g of your starting solution to get a given percentage.
eg, you have 70% HNO3, you need 10%.
100g of 70% HNO3 contains 70g of HNO3.

70/10 = 7.
7*100 = 700.
700 - 100 = 600.
Therefore 600g of dH2O must be added. This will give you 700g of solution, containing 70g of HNO3, therefore it will be 10% w/w.
gatecrasher March 6th, 2003, 11:26 PM

MR COOL,
THANKS FOR THE REPLY.
BUT I AM A LAMER, I NEED IT MORE SIMPLER!!
AND WHAT DID I DO WRONG? DO I HAVE MY HEAD UP MY ASS?
PEROMAN March 7th, 2003, 02:53 AM

Gatecrasher ! Why do you ask 1 question several times???
I have already answered it (look my previous reply)
you need 2.14g of 70%HNO3 + 12.86g water !!!
You can count it easily :

As Mr.Cool said , you need 1 weight part of 70%HNO3 per 6 weight parts of water , and you get 7 weight parts of 10%HNO3
7x = 15
x = 2.14
6x = 12.86
Learn mathematics !
frogfot March 7th, 2003, 08:45 AM

Since this topic is still on I thoat to ask if anybody is interested in dencity data of aqueus HNO3 (and H2SO4)?
"Handbook of chemistry and physics" got nice tables on this (1% resolution 5 digits accuracy), I can scan this, again, if anybody is interested.
gatecrasher March 7th, 2003, 11:43 AM

Fine, I'll just boot MYSELF out!!! This is a Communist forum and who needs it GOOD BYE!!!!
--------------------------------
hehe, he's not going to find any better! so long butt sucker!
[ March 07, 2003, 05:33 PM: Message edited by: kingspaz ]

NBK isn't the only one with banning powers you know. He just likes to make a spectacle out of it, other times the lamers are gone before most people are even aware of their
existence. No fuss, they just vanish. But like I said, I think we're being nice at the moment...
<blockquote>quote:<hr />Simply add 600 mL H2O to 100
mL of 70% HNO3 and then measure up 15g of the solution and use it for whatever you are doing. That is 10% HNO3.<hr /></blockquote>No, this won't work! 100mL of 70% HNO3 is 142g, therefore containing 99.4g of HNO3. The final solution will
weigh 742g, with 99.4g of HNO3, therefore it will be 13.4%!
Frogfot, that table would be a nice thing for what is currently the "Nitric Acid" section, please do scan it, host it somewhere and provide us a link. Or, you could scan it, e-mail
the scan to me and I will host it and post a link.
I still think this is a potentially useful topic, so I'll just clean it up a bit and let it carry on.
See ya later gatecrasher, we'll miss you I'm sure :rolleyes: :p .

The funny thing was, he had his question answered three times and then stomped off in a huff because no one would help him! :D
I don't like his kewl-hugging either, but some people insist that we're too harsh :rolleyes:
I'd close this thread, but frogfot has a decent question he needs answering.

There, that's better. I just got rid of the posts that were (quite rightly <img border="0" title="" alt="[Wink]" src="wink.gif" /> ) ridiculing gatecrasher, so if anyone seems to
be replying to a post which doesn't exist, that is why...
Incidentally, the Staff are being nice. But if the members take the mickey out of an idiot and he decides to leave, well, that's not our fault :) .
Hehe, obviously three answers were just not enough to satisfy his enormous brain, he wanted more!
rikkitikkitavi March 7th, 2003, 03:53 PM

is this the so called three-strike-law, and you are out ? :)
/rickard
frogfot March 7th, 2003, 06:24 PM

Heres HNO3
<a href="http://www.geocities.com/frogfot/stuff/hno3.png" target="_blank">http://www.geocities.com/frogfot/stuff/hno3.png</a>
And here's it recognized, in .xls (had nothing to do :rolleyes: )
<a href="http://www.geocities.com/frogfot/stuff/hno3.xls" target="_blank">http://www.geocities.com/frogfot/stuff/hno3.xls</a>
Also specific gravity for H2SO4, tryed to recognize, but it sucked (somebody have spilled some crap on those two pages)
<a href="http://www.geocities.com/frogfot/stuff/h2so4.png" target="_blank">http://www.geocities.com/frogfot/stuff/h2so4.png</a>
Mr Cool, can you download them, maby change extension or resize.. i dont know if .png is optimal for such things.
vulture June 1st, 2003, 05:58 PM

The key to correctly calculating concentrations in liquids is the density. Try mixing ethanol and water and you'll see what I mean.
Once you know the density of your starting and you final concentration there should be nothing left to stop you.
Arthis June 2nd, 2003, 07:58 AM

I was wondering if the density function of the concentration of HNO3 was a line, or a curv ? It would be easy, since d(H2O)=1...
Anyway the approximation should not be too big, and this method should work (for approximated ratios needed...); d(HNO3 pure)=1.51
metafractal June 2nd, 2003, 11:01 AM

Hmm... now lets see:
Density : % HNO3 By Weight
1.0 : 0.3
1.1 : 17.6
1.2 : 32.9
1.3 : 48.4
1.4 : 67.0
1.5 : 96.7
At first it looks like a linear relationship ('line'), but it develops a slight exponential incline ('curv') in the higher Density/%HNO3s. Its neither really, there are multiple factors
affecting it. One could probably get away with treating it as a linear function (line of best fit) for most practical purposes, but its probably best to look up the tables for any
serious procedures :) .

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic,
and Improvised Chemistry > Nitromethane Synthesis - Archive Thread
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Mammut
A new voice
Posts: 39
From: Essen,NRW,Germany
--------------------------------------------------------------------------------
hi,
do i get nitromethane if i mix
CH3OH with H2SO4/HNO3?
Can someone tell me the reaction
CH3OH + H2SO4/HNO3 ---> ???? + ????
thanks
[This message has been edited by ALENGOSVIG1 (edited February 13, 2001).]
atropine
Frequent Poster
Posts: 129
From: wales
Registered: OCT 2000
--------------------------------------------------------------------------------
i would edit that post b4 any one sees it. you will be flamed.
wantsomfet
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Posts: 233
From: EU
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The reaction for nitromethane needs several hundred degree C, if i remeber correct, and a platinum catalyst. Nothing for the
hobbychemist.
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Cricket
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Posts: 160
From: USA
--------------------------------------------------------------------------------
In KIPE2 (or was is it 1?) it tells the industrial procedure for making Nitromethane. It is very expensive to get the equiptment
to make it. When I saw the diagram I just said "Fuck this.". I dont think their is an easy to make it. It is just too usefull for it
to be easy to make.
MacCleod
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Posts: 215
From:
--------------------------------------------------------------------------------
I beleive I read recently that only 2 chemical plants currently make nitromethane,that's one of the reasons it's so
expensive.There was a supplier in South Carolina called F H S Supply,Inc. that sold NM racing fuel (for model cars,planes,etc.)
with up to 65% NM in it.At that time the price was $30.48 per (single) gallon,or $21.34 per gal. when buying a case or more (4
gallons per case).This info is a few years old,but if you call them they'll send you a new price sheet;thier toll-free # was:
1-800-742-8484.
The toll # was:
1-803-222-7488.
megalomania
Administrator
Posts: 651
From: USA
--------------------------------------------------------------------------------
The industrial rxn uses methane gas at about 450 C and several ATM's of pressure. Nitric acid (100%) is sprayed in through
atomizer nozzels. I have thought about trying this by heating up an air pressure tank, but unless you have a good way to
drain off the product, which I do not. yield will be crappy and time consuming.
Of course I do have a method of synthesizing nitromethane using laboratory equip/chems at my website if your interested.
------------------
For the most comprehensive and informative web site on explosives and related topics, go to Megalomania's Explosives and
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DarkAngel
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From: ?
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Finally i found a source in Holland that sells 99,6%Nitro Methane for 18 USD
I convert it with this site: <a href="http://www.xe.net/ucc/full.shtml" target="_blank">http://www.xe.net/ucc/full.shtml</a>
------------------
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atropine
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Posts: 129
From: wales
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Well, sorrey bout that, it would appear that you didn't. In the Uk nitromethane is commanly available in most model shops.
And if they don't have it they will usualy get it for you at 14 a litre.
xyz March 7th, 2003, 06:13 AM

Shouldn't this be in chemistry related?
Does anyone know a supplier of nitromethane in Australia?
0EZ0 March 7th, 2003, 06:37 AM

Nitromethane can be had for those who keep their eyes and ears open, as with almost all chems. A local RC model aircraft/
car/etc. club would be a good place to start asking around. All you have to show is that you are a keen model aircraft/etc.
enthusiast and you are looking to formulate some of your own fuel. Which could be quite true, as in my case <img border="0"
title="" alt="[Wink]" src="wink.gif" /> . A bit of small talk, and there you have it :) .
[ March 07, 2003, 06:18 AM: Message edited by: 0EZ0 ]

I think an OTC nitromethane synthesis will be in my plans for the coming weeks, it all seems easy enough. Vinegar, pool
hypochlorite, a strong acid (HCl masonry cleaner, for example), nitrite from nitrate. It should be a nice experiment to try.
Has anyone here tried it before, and if so, do you have any tips which might help? At the moment I think I'll concentrate the
vinegar using distillation from CaSO4, Ca(NO3)2 etc a few times since I'm worried
about side-reactions if using, for example, sodium ethanoate and sulphuric acid.
VX March 8th, 2003, 07:58 PM

I have tried concentrating vinegar, and also making ethanoic acid from meths (denatured alcohol). I would suggest making it
from alcohol any day; it's so much easier! All it takes is to reflux ethanol with a strong oxidiser, (e.g. potassium
permanganate) for about an hour, and there you are, pure(ish) ethanoic acid!
Polverone March 8th, 2003, 08:43 PM

I don't think you should have any real worries about side-reactions between sodium acetate and H2SO4. But if you don't want
to use H2SO4, you could use H3PO4 instead, as it is a weaker acid and dehydrating agent. However, since it is weaker, I would
think you would surely want to use anhydrous sodium acetate. And it is somewhat tricky to completely dry sodium acetate
without scorching it.
For the chlorination are you using phosphorus, sulfur, iodine, or a mixture as your chlorination aid?
knowledgehungry March 8th, 2003, 09:55 PM

I read megas synth and was wondering if there was a way to make chloroacetic acid(besides using red phosphorous) or an otc
source for it.
Thanks.
megalomania March 9th, 2003, 01:46 AM

Chloroacetic acid is not the kind of thing you would find in the stores. I know of no product that uses it. It is pretty much
limited to use in some organic synthesis setups and industrial operations.
It took me a few years to find the synth I have on my website. Since then I have seen no other method of producing it but the
one I found. I think even the industrial method chloronates acetic acid like this IIRC. Modern processes use artifical sun lamps
to get the reaction along, but those are specialized, and expensive, bits of equipment.
I am moving this thread to Chemistry Related.
[ March 09, 2003, 01:24 AM: Message edited by: megalomania ]
Mr Cool March 9th, 2003, 06:54 AM

Good, I'm glad you think I can use sodium acetate and sulphuric acid, Polverone. That should hopefully speed it up a lot. And
if it does fuck up, then I'll try distilling from a dehydrating agent or fractional distillation.
Although, actually I think I might make it from ethanol instead. Originally I was going to try this synthesis using the most
basic chemicals, but this wouldn't make it easier for everyone to make since it still needs some good glasswear. Ah, damn,
but I don't have any permanganates or dichromates ATM. So I'll start experimenting with vinegar, and move on to making it
from ethanol when I get more of a suitable oxidiser. I may have to order more calcium hypochlorite too, the stuff I have is
quite old.
For the chlorination I'll use sulphur with iodine. I have a 750W filament lamp that I hope will give enough UV, if not this could
take a long time!
Al Koholic March 9th, 2003, 08:36 AM

Mega, there is another reaction that does not utilize PCl3 (which is good because I really don't like the thought of conducting a
reaction between P and Cl in my room). Rather it utilizes S2Cl2, SOCl2, or SCl2, and I think you can use things like S4Cl4 and
whatnot. The one I am going to do uses S2Cl2 which can be easily prepared by bubbling a stream of Cl2 gas into molten
sulfur at 295C. I have synths for all these if you want them. BTW, did you get the email I sent you a while back?
megalomania March 9th, 2003, 07:18 PM

Do you happen to have a ref for that procedure Al Koholic
? I have a synth for S2Cl2, but I don't know about the others off the top of my head. I turn down
no offers of syntheses :) I most likely did not or do not have your email as mine has been quite buggy this past few months.
Go ahead and send it again to [email protected] until I get a real address.

If UV ye need, would a UV lamp not be more effective?

I do believe the reaction requires visible light photons, not UV light to do the job.
Tuatara March 11th, 2003, 03:52 AM

Your bog standard, OTC quartz halide lamp will give you plenty of both!

Ah, but both of those options are fatally flawed - I have neither a UV lamp nor a quartz halogen one :) .
I wonder... would generating Cl2 in situ be better (would it still work as I am about to outline?)? It would be
easier for me. It would mean I could have some MnO2 in with the acetic acid and just drop in conc HCl through
the top of the reflux condenser. Otherwise I'd need to use more glasswear and also make something to bubble Cl2 in from one reaction flask into the other down the condenser. I have a feeling that making it in situ would be more
efficient, even if slower, but I'm not sure why really... purifying the resulting chloroacetic acid would be just the same, it
requires distillation anyway.
I'll try to find out more about making CAA.
Or maybe... oxidise ethylene glycol to 2-hydroxyethanoic acid, and reflux this with I2 with FeI2,
AlI3 etc as a catalyst? Maybe. Like I said, I'll try to find out more, including any other methods out there.
Edit: Or refluxing 2-hydroxyethanoic acid with H2SO4 and NaCl? I'm sure there are loads of
problems with these last two methods, I'm just brainstorming and haven't thought them through yet.
Alchemist March 11th, 2003, 07:00 PM

Hello all,
if you check out Rhodium's sight ,http://www.rhodium.ws/chemistry/chloroacetic.html, it says you can use Sulfur instead of
Phosphorus but the yeilds are lower!
Later!!!
Also found that Wohler's organic chemisty says that Iodine can be used as a catalyst. Sorry no yeilds stated.
P.S., Al Koholic please do post your synth's for all of use. Thanks!
[ March 11, 2003, 10:35 PM: Message edited by: Alchemist ]

Grrr! Didn't read MY website did we? I gave the procedure I wrote on CAA to Rhodium to use on his website :) Mine originates
from Praxis Des Organischem Chemikers (Practical Methods of Organic Chemistry), which itself comes from some Chemishe
Beristsche article of 120 years ago.
I would be wary of adding too many additional chemical to the reaction mix as possible side reactions can ruin everything.
Besides I think you need to completly saturate the acetic acid with chlorine to get this to work.
Also I feel I should mention that the best light of all is sunlight, better yet in the summertime. Better get some mirrors this
time of year. Without the proper amount of light the reaction will take longer, days longer, and all the while you need to be
forcing vast amounts of chlorine into the flask.
Einsteinium April 2nd, 2003, 05:03 PM

Troubles with Nitromethane? There's a lot of synth to achieve this in a clandestine lab setting...
Chlorination of acetone may be achieve with Cl2 in a refluxing acidic media but this is tricky as polychlorination
may well occur (chloroacetone is more reactive towards chlorination than acetone itself). I did it once and got a 32% yield,
which isn't a bad yield since the reaction's nature. Chloroacetone reacts with nitrites and yield *both* nitrite and nitro
coumpound (fortunatly the nitrite rearanges readily into the nitro at his bp). Nitroacetone is finally cleaved with NaOH to yield
nitromethane and sodium acetate. I don't really like the first part of this synth so...
You can oxidize methylamine with 3 molar equivalent of any peracids to yield the acid, water and nitromethane :
CH3NH2 + 3RCO3H -> CH3NO2 + 3RCO2H + H2O
This reactions gives ~60% yield based on the methylamine used.
Nitromethane may also be prepared from :
Methyl Iodine and Sodium/Potassium Nitrite (high yielding)
Methanol + H2SO4 (or conc. HCl) and Sodium/Potassium Nitrite (~60% yield)
I think all above synths and a couple other can be found at <a href="http://rhodium.ws" target="_blank">rhodium</a>
I believe industrialists used to reacts methanol with nitric acid and then rearanges the methyl nitrate to nitromethane in the 'ol
times but I guess we'll leave this method to the industrialist bastards :)
And please, don't use your 6 foot tall bong to relax while preparing this stuff... :D
knowledgehungry April 2nd, 2003, 10:17 PM

Hmmm... The reaction using H2SO4 methanol and KNO2 would be the easiest i think, I dont have any KNO2 right now but i'm
sure to get some sooner or later. I shall try and post back with results.
Einsteinium April 2nd, 2003, 10:54 PM

I actually I never tried it out (I get nitromethane by distillation of some high-performance racing fuel @ my local hobby shop).
For higher nitroalkanes I use the indirect alkyl halide/metal nitrite way. Some advices :
Never allow your vessel to reach reflux (MeOH/conc H2SO4 has significantly higher bp than MeOH
alone) because you will be driving a side reactions that produces dimethylether! (gas!).. I would rather keep the temp @ at
conservative room temp for a first attempt.. Might take a lot of time for the reaction to proceed but I would rather die of
boringness than be knocked off by (CH3)2O :D
Also, I haven't played much with HONO (which is produced as H2SO4 reacts with NaNO2) but I know it dismutates into HNO3 with water at high pH and high temp. Another good reason to keep a
low temp (you don't want nitric acid there in any noticeable concentration).
Adding Zinc Sulfate to the reaction will greatly helps the reaction has it complex the alcohol function into a better leaving group
than water (you remove water with the simple synth).
If you can get your hand on NaI/KI (I heard it could be "easily derived from salt licks" but I don't have a clue about what are
salt licks) I would rather produce CH3I in situ :
CH3OH + NaI + H2SO4 + NaNO2 -> CH3NO2 + NaHSO4 + H2O + NaI
1 - H2SO4 reacts with both NaI and NaNO2 producing HI and HONO
2 - CH3OH reacts with HI producing CH3I and water
3 - CH3I reacts with ONO- (dissolved HONO) to produce nitromethane and NaI
As you might has understood, NaI acts as a catalyst here, you only need to add a small amount to get this reaction working
properly.
Well, good luck with any synth you might choose but it is my opinion that you should consider fuel distillation instead. It's
easier, quicker and cheaper!
[ April 02, 2003, 09:57 PM: Message edited by: Einsteinium ]
Energy84 April 3rd, 2003, 01:46 AM

The only 'salt licks' I've ever heard of are a sort of animal mineral block. The ones that we get are big 30 pound blue blocks.
And yes they are salty... <img border="0" title="" alt="[Wink]" src="wink.gif" /> They can be purchased at almost any
agriculture store. Just ask for salt blocks. You can get it in granulated form (for mixing into feed) and the block form. I'm not
sure what the exact difference is but you can get them in blue or brown. I'd guess that the blue ones have more salt in them
though because they are alot harder. (Dropping them on a concrete floor will chip them.)
Marvin April 4th, 2003, 05:40 PM

Some very nice ideas there. The chloroacetone idea I likw a lot, but the yeild is a bit poor, based on chlorine? Were you
chlorinating the liquid (why was this acidic?) or the vapour above it under reflux, I understood yeilds were normally better this
way.
The synthesis from methanol bothers me. A lot. Aside from anything else it looks too easy, this always bothers me. With
dilute acid Id expect methyl nitrite gas to be the majority product with virtually no nitro product formed, the nitrite is explosive
by itself even if you dont get an explosive mixture forming with dimethyl ether and air. HCl I cant see as working at all, and Id
be worried that this would liberate large amounts of methyl nitrite and hydrogen chloride gasses when heated, with maybe
some NOCl and NOx thrown in for good measure. If this was done stepwise through formation of methyl sulphate, I could see
this working and giving overall the same result, but methyl sulphate is a tad on the toxic side for my liking. Sodium methyl
sulphate looks rather safer if this method will work.
The catalyctic method with iodide looks more like a work in progress than a finished method, for example whats to stop the
liberated nitrous acid from oxidising the liberated HI like youd expect it to, and this grinding the reaction to a halt?
Einsteinium April 4th, 2003, 09:41 PM

It was acidic because I wanted the reaction to proceed through the ionic mechanism (ketone -> enol -> chloroketone)
directly bubbling the liquid instead of the free radical mechanism (ketone -> ketone free radical -> chloroketone) in the
vapour phase. The reason why I don't do it anymore is because the first time I tried it, it went out of control and that was quite
freaky to see acetone/chloroacetones splashing out of my damn ice-cold 30-cm condenser.
Methyl nitrite decomposes before it's boiling point, you won't ever get it as a gas at room temp. With dry ice you can get a
decent yield of nitrite, but I don't think the methanol method is appropriate as it proceeds so slow at theses temps...
I have never heard of nitrous acid reacting with HI at usual temperatures, and truly don't think it does. Do you have reference
about this?
Mr Cool April 5th, 2003, 08:46 AM

Well, I can say that 50% H2SO4 in water with an equal volume of 90% ethanol added and a
spatula measure of KI will turn brown and deposit iodine crystals when NaNO2 is added at room temperature.
Also produced was a significant amount of acetaldehyde, and there was a slightly chloroform-like smell present. There was
vigorous bubbling each time the NaNO2 was added.
I didn't use any zinc sulphate.
But this does not mean it can't be done, more likely it means I should've found a procedure to follow first...
The haloketone route seems a good one, and today/tomorrow I will try making chloroethane and then reacting with
NaNO2 to yield nitroethane after fractional distilation to remove the ester.
I'll have to find my chem notes to get a synth for chloroethane, IIRC it's roughly the stoichiometric ratios of 50% H2SO4 with NaCl, with a ZnCl2, AlCl3, FeCl3 etc catalyst?

You can do it trough chloroethane but since chloroethane is a gas @ room temp and chlorine a somewhat cheap leaving group,
I do it through bromoethane, which is a liquid @ room temp. Yields are usually high (~85%) with bromoethane and you
usually don't need Lewis acids (Zn, Fe etc...) catalyst to get the reaction done. KBr can be found a photographic supply shop
for ~10$ US/500g, reacted in situ with sulfuric acid to give HBr which then reacts with Ethanol to generates ethyl bromide. Ethyl
bromide gives ~80% yield nitroethane with sodium nitrite, I've done it several times, the procedure can be found at rhodium.
Sorry for the HI crap, didn't know it could be oxidized to iodine by nitrites (iodine reacts with ethanol to form acetaldehyde...)
Mr Cool April 5th, 2003, 04:14 PM

I haven't found a good source for KBr yet, but will keep looking...
Thanks for the advice.

Dont be sorry, just put more difference between the ideas, particually untested ones, and information from reliable sources,
like books.
Methyl and ethyl nitrite are stable as gasses, I think you must be taking a generalisation out of context here, becuase none
of my information suggests they arnt stable. PAS Smith simply states they are gasses adding only that the alkyl nitrites
decompose slowly at room temperature but can be kept almost indefinatly in a fridge. An encyclopedia states that ethyl nitrite
solutions can be distilled at atmospheric pressure, as in the production of sweet spirits of nitre and that if heated too much the
gas can explode, but that ethyl nitrite decomposes only slowly as a gas at room temp (no info on methyl nitrite). Sidgewick
points out that in the victor meyer synthesis, the nitro and the nitrous esters of methyl, ethyl, etc have such different boiling
points that separation is fairly trivial, and that the nitrous ester gasses decompose rapidly at 200C (he also talks about things
like hydrogenation at lower temps). Theres no information in Sidgewick about isomerisation to nitro compounds, only the
production of nitrous gasses and aldehyde. If this information comes from a patent, please remeber that these are very
heavily biased and unrelaible sources of information on their own.
While I'm spreading misery mindlessly, I'll add a personal theory I have for why the catalyctic iodide method wouldnt work
even if nitrous acid and HI didnt react. The theory is that formation of the nitroparrafin occurs becuase the poor solubility of
silver or alkali halide in the reaction mixture. More obviosly becuase of the very low solubility of silver halides and the higher
yeilds this method generally produces. In the catalyctic method, you are expecting the KI to be soluable for the conversion to
iodide, and insoluable for the conversion to nitroparrafin. Sidgewick does talk about change in yeilds of silver over alkali and
also the relative change in yeilds for primary to tertiary, and for different chains. I think the synths in which alkly nitrites might
form need to be reevaluated in terms of safety at least, if not in terms of validity.
I dont like the acetone+acid method. I have the sneaking feeling that the reason it went out of control, was that the chlorine
was reacting mainly with aldol products, which I see no way of preventing under these conditions. I dont have any way of
checking the free radical method by lituriture, but chlorination in bright light of the vapour above reflux seems to me like the
way to do it. The higher boiling point of the chloro products should mean that much less of these are present in the vapour
than in the liquid, with less di chloro compounds being formed, and an acid absorber of some sort (calcium carbonate?) in
solution to prevent acid build up and aldol equilibriums screwing things up.
Lastly, if you still need convincing about methyl nitrite existing in gas phase at room temp, check out organic synthesis. While
often not the best way, and occationally downright dangerous, the synths do always work and methyl nitrite is generated at or
neer room temperture and bubbles into a reaction from the generating flask in the "ISONITROSOPROPIOPHENONE"
synthesis.
Ok, that wasnt the last, this is, PAS Smith lists a ref that states alkyl chlorides dont work at all in the victor meyer synthesis. Id
call a cheap leaving group one they went really easily (!), but I know exactly what you meant:- chlorides are cheap and they
are crappy leaving groups. The specific ref for this is Kornblum, B Taub and H.E, Ungnade, J Am Chem soc. 76, 3209 (1954)

Well, actually if I don't give any litterature to check I assume that you will before trying anything I may post unless you too,
assume it may well work. The theory behing theses reactions is called bimolecular substitution (SN2) and dosen't
stand at all over solubility in the solvent you are using. Next, acetone dosen't undergo self-aldolisation unless a very strong
base is used, it went out of control because way too much chlorine was passed in the acetone creating a temperature increase
I couldn't prevent quickly enough. Free-radicals formed with halogens dosen't undergo aldols condensation at all. Methyl and
Ethyl nitrite aren't stable, they decompose as you say at room temp. Slowly maybe, but quite quickly in such heated acidic
media. Silver nitrite is known to reacts faster in this synth because silver acts is a lewis acid (just as Zn or Fe, mentionned by
Mr. Cool) which complex the alcohol creating a better leaving group and because silver nitrite isn't an ambivalent nucleophile,
the reaction works better with tertiary halides because they can form stable carbocations and react through monomolecular
substituion instead (SN1). Yes organic synth use gaseous methyl nitrite @ near room temp, but they do use it
immediatly and they dosen't produce it from acidic media. I said that if you want the nitro coumpound with the methanol synth
the only way would be a very low temp where the nitrite is stable even in acidic condition, but this reaction is worthless. Do a
simple search about bimolecular substitution on any decent site and you will find out how this synth work. Any decent organic
chemistry book has a complete chapter about it too, might be informative.
[Edit : Here's a good theoretical reference : <a href="http://www.ch.ic.ac.uk/widdowson/teach_files/nitrogen/dw1.html"

target="_blank">http://www.ch.ic.ac.uk/widdowson/teach_files/nitrogen/dw1.html</a>

"Well, actually if I don't give any litterature to check I assume that you will before trying anything I may post "
If you truly believe this, I think you are the only one. Giving references, or suggestions of books that cover the specific subject
is a good idea if you want people to go out of their way to double check suggestions.
Ive read what I have on the subject, come to some conclusions, and feel happy making the following suggestions......
"The theory behing theses reactions is called bimolecular substitution (SN2) and dosen't stand at all over solubility in the
solvent you are using"
For primary haloalkanes, it is indeed SN2 as shown by kinetics studies, but choice of solvents and the solubility of the reagents
is critically important, for example, DMF over DMSO generally requires nitrite scavangers to prevent nitrosation reactions that
occur because of the increase in reaction time due to lower solubility of the sodium nitrite. More importantly, the fact the
reaction is clearly SN2 from the kinetics overlooks an important feature, the reactants get used up and the products taken
together form almost quantativly. Your making this an unvoiced assumption, and then wondering where my argument applies.
If we look at the production of haloalkanes,
ROH + HBr <=> RBr + H2O
Although SN1 or 2 tells you what can happen kinetically, and thus some information about the products, it doesnt tell you if
the reaction will go forwards or backwards. In the case of a simple mixture, this reaction goes mostly where its driven, a
secondary or tertiary haloakane mixed with water will rapidly hydrolyse, primary haloalkanes being SN2 would do also, but are
kinetically limited by the availability of OH- so although it wont be destroyed under these conditions, it wont be formed either.
To make haloalkanes the reaction conditions are changed and you have 2 powerful factors favouring formation of product
rather than reactant, you add strong acids/dessicating agents like sulphuric (slightly oxidising, so a problem with HI) or
phosphoric acid, and you remove the low bp haloalkane from the reaction mixture by distillation.
I'm arguing that formation of NaX or AgX in particular is a strong incentive for the reaction to proceed to completion. I also
think that the use of haloalkanes in this reaction isnt 'catalyctic' as such, just a way of seperating the conditions required for
facile and neer complete nucleophilic substitution of the alcohol, from the reagents these conditions are incompatable with. In
order words, if you can stabilise this, and void competeing reactions kinetically or thermodyanically (if possible, the nitroalkane
is the better themodynamic product over the ester), I think direct nucleophilic substitution would be facile on its own, and
would not by improved by iodide ions, which you are expecting to jump in and out under the same conditions.
"acetone dosen't undergo self-aldolisation unless a very strong base is used"

This simply isnt true. It doesnt go to completetion with dilute acid because the products arnt favoured, unlike strong base,
which tends to produce insoluable polymers. If you make acetone moderatly acid you get a solution of mostly acetone, with a
few percent of aldol products, diacetone alcohol, metsylene oxide etc. I'm bothered that these would react with chlorine far
more readily than acetone itself, reduce the yeild, and make the chlorination less easy to control.
If you go furthur with acetone, by saturating it with HCl gas the reaction goes much furthur, as dehydration sets in. Left for a
day and then neutralised, treatment with water produces an oil which is mostly metsyl oxide and phorone, which can be
seperated by distillation.
"Free-radicals formed with halogens dosen't undergo aldols condensation at all"

Free radicals do a lot of very weird unpredictable stuff. My suggestion though was to prevent buildup of large amounts of HCl
in the mixture that would cause high amounts of aldol products, and dehydration products of these to be produced all of which
would be much easier targets for chlorination. The synthesis book by MB Smith deals mainly with bromination of ketones in
this area, but gives an interesting twist. KClO3 is added to the ketone mixture and any HBr formed is oxidised right back to
Br2. This prevents large amounts of HBr from building up in the mixture, and also potentially halves the amount of Br2
required for the reaction.
"Methyl and Ethyl nitrite aren't stable, they decompose as you say at room temp"
They are stable enough to provide a very serious hazard to people attempting these reactions. They are also stable enough
as products of the primary reactions to put formation of nitroalkanes from the alcohol in some considerable doubt. This
particulaly as they dont decompose to the nitro compound, but to the aldehyde and NO. Acid media isnt likley to be relavent,
as with any setup anyone might be able to try at home the nitrite esters will go straight out of solution, being gasses and
leave.
"Silver nitrite is known to reacts faster in this synth because silver acts is a lewis acid (just as Zn or Fe, mentionned by Mr.
Cool) which complex the alcohol creating a better leaving group and because silver nitrite isn't an ambivalent nucleophile"
I dont like the term ambident nucleophile, but this is certainly the main reason for the increase in yeild of nitro compound
over nitrous ester. In these reactions the shorter reaction time the more product, so I also consider the formation of AgX to be
a factor kinetially as well as thermodyanically, and the ability to produce more concentrated solutions of the nitrite nucleophile,
much more of a issue with sodium nitrite reactions. I dont buy the lewis acid complex argument in this situation for reasons I
mention later. Theres no alcohol involved, and the leaving group is the halide, so I dont see what you are getting at here.
"the reaction works better with tertiary halides because they can form stable carbocations and react through monomolecular
substituion instead (SN1)"
This simply isnt true, yeilds are worse with victor meyer with secondary and tertiary halides than with primary. With primary
halides silver gives typically 80%, sodium 60%. With secondary halides silver gives less than 15% , sodium gives much better
yeilds, up to 60% but generally less than with primary, more problems with competeing reactions, nitrosation products, the
expected nitrous esters 'low temperature' nitrate ester formation and large amounts of dehydrohalogenation which form
olefins and then go on to react furthur, usually with nitrogen oxides. Getting these fairly high yeilds with secondary halides is
usually a matter of choosing a solvent sodium nitrite is very soluable in, and adding nitrous ester scavingers such as
phloroglucinol to hinder nitrosation by the resulting alkyl nitrites. Tertiary halides with silver typically give 5% yeilds at best and
the nitro product can usually not be isolated from the reaction mixture, they instead form high yeilds of nitrous esters, olefin
addition products etc. I dont have enough examples to be able to draw proper conclusions from sodium nitrite with tertiary
halides, but the general trend is that the only high yeild products are olefins, for example t-butyl bromide and chloride fail to
give nitro compounds, but form isobutylene instead. The only suggested practical route to tertiary nitro compounds here is the
oxidation of amines, with very satifactory yeilds, 60 to 90% by peroxyacetic acid, or permangante (permanganate doesnt give
great yeilds with primary amines).
I'm not totally sure you intended to state tertiary halides give better yeilds, but maybe you meant secondary halides give
better yeilds with sodium over silver nitrite, something quite often quoted. This is one of the principal reasons I dont put any
credit to the idea that silver acting as a lewis acid stabilises the complex, and just in case you want to say 'steric hindrence'
lithium, sodium and potassium nitrites all give similar yeilds.
"I said that if you want the nitro coumpound with the methanol synth the only way would be a very low temp "
Actually you said that dry ice would be the only way to get a good yeild of the nitrite, which was consistant with your idea that
methyl/ethyl nitrites did not exist in the gas phase. If side reactions can be stopped, particulaly oxidation, conversion of nitrite
to nitrate in the strong acid etc in conditions where nucleophilic substitution of the alcohol can occur then formation of some
nitro compound is possible, but in all normal home conditions it wont happen. Formation of the alkyl nitrite will occur which
does not require nucleophillic substitution, or the breaking of the alcohol C-O bond.
"Do a simple search about bimolecular substitution on any decent site and you will find out how this synth work"
I will do my best not to be insulted that youve just suggested I look up pre degree information. :p
"Any decent organic chemistry book has a complete chapter about it too, might be informative."
University level organic chemistry textbooks dont provide the detail needed to design a synthesis in the complete absense of
good chemical reasoning that this would form as a majority product, or in the absense of anything similar working practically.
Mechanism only gets you a 'maybe this could form', its usually existing high yeild syntheses for similar products that suggest
a high yeild synthesis is possible.
I'm currently limited to information I have at home, and the really detailed stuff ends around the mid 60's. University
textbooks dont go into neerly enough detail about this stuff dispite being technically 'up to date'. If anyone has some more
recent detailed information, Id like to see it particualaly if it disagrees with aspects of what Ive said. What is your reference for
the 60% yeild from methanol/H2SO4/nitrite, and what are the exact conditions used? Youve suggested dry ice, we know it cant
work at room temp, but if all the species can be stabilised removing kinetic limitations the nitro compound could form as the
thermodynamic product, given long enough.
[ April 12, 2003, 04:12 PM: Message edited by: Marvin ]

"If you truly believe this, I think you are the only one." I didn't gave any ratio of reactants, temperature and/or time in any
suggestion I made! Are people crazy enought to ignorantly mix chemicals in random amount just to see how it might goes?
This is damn crazy... Also, I told most of theses synths were on rhodium <a href="http://www.rhodium.ws"
target="_blank">www.rhodium.ws</a>, I cannot find the page "nitroalkanes directly from alcohols", which WAS there (I wish I
had backuped(sp?) the site) and the reference given was Fieser but I cannot remember from which book of Fieser. Maybe they
removed it as they knew it didn't work well...
"a secondary or tertiary haloakane mixed with water will rapidly hydrolyse" I wouldn't say "rapidly" here, as I did clean several
alkyl halides (more than 50 different, even tertiary halides) with water and lost nothing but a minime fraction of product. I
know what you meant though, refluxing (or heating over 50C) an alkyl halide with plain water will hydrolyse it quite quickly.
The solvent was simply an excess of alcohol so it's pointless to speak of DMF or DMSO as solvents.
"Although SN1 or 2 tells you what can happen kinetically, and thus some information about the products, it doesnt tell you if
the reaction will go forwards or backwards." That's true, and yes it's why one must add a lot of acid to drive this reaction in
favor of the alkyl halide. Removing the halide will definitivly drive the reaction this way too.
"I'm arguing that formation of NaX or AgX in particular is a strong incentive for the reaction to proceed to completion." We are
in solution here, thus we speaks of ions. In no way NaX or AgX are produced in this reaction Na+ or Ag+ comes from the nitrire, X- from the acid. Theses ions should stays dissolved as the reaction runs.
"which you are expecting to jump in and out under the same conditions." As I stated, I haven't played much with HONO (did a
diazonium salt once, that's it). The use of Iodide as a catalyst (jumping in and out) is a common artifice used to catalyze
many reactions such as : EtCl + AcONa -> AcOEt + NaCl. This reactions sucks as is, but adding some NaI catalyze it (look
for the Finkelstein reaction) since the iodide ion jumps in and out (I- is a better nucleophile AND better leaving
group than chloride, this is why it jumps in and out).
"My suggestion though was to prevent buildup of large amounts of HCl in the mixture that would cause high amounts of aldol
products, and dehydration products of these to be produced all of which would be much easier targets for chlorination" I
wouldn't say high amounts but overall you are right here too. However, what I did said is that the reaction didn't went out of
control because of this aspect, it went out because I chlorinated acetone way too strongly (the flux of Cl2 was way to high)
which resulted in a temperature build-up and lost of the reaction control.
"This particulaly as they dont decompose to the nitro compound, but to the aldehyde and NO." I should have said rearrange,
not decompose, a procedure to achieve this can be found in "Panchanan, Neogi and Tarinicharan Chowdhuri, [can't remeber
the journal] p.701-707 (1916)" This procedure can also found at rhodium's.
"I dont buy the lewis acid complex argument in this situation for reasons I mention later. Theres no alcohol involved, and the
leaving group is the halide, so I dont see what you are getting at here." There is alcool involved in the process of alcohols to
nitroalkanes! The first leaving group was water (from protonated alcohol) there is where Ag+ plays a major role.
Also, Ag+ does form complex with alkyl halides, also making them better leaving groups. Keep in mind this is
dissolved, there's no AgX in the media unless it's a precipitate of AgX.
"I'm not totally sure you intended to state tertiary halides give better yeilds, but maybe you meant secondary halides give
better yeilds with sodium over silver nitrite, something quite often quoted." Tertiary halides would give better yields, but
certainly not in solvents we are speaking of here (5% is a good yield in theses solvents IMO). One would be left with tertiary
alcools, and/or ethers, alkanes, alkenes...
"This is one of the principal reasons I dont put any credit to the idea that silver acting as a lewis acid stabilises the complex,
and just in case you want to say 'steric hindrence' lithium, sodium and potassium nitrites all give similar yeilds." I never said
the reaction would give a better yield since Ag+ complex the leaving group, I said it would proceed faster, this is
VERY different. Actually the yield would be inferior with most sustrate because the AgX+ leaving group is so good
that elimination take place in a greater extent, which lower the yield of nitroalkane. Does that help buy the Lewis complex
theory, it does lower the yield and accelerate all reactions where this leaving group is "called upon", this include elminations,
substitutions etc...
"Actually you said that dry ice would be the only way to get a good yeild of the nitrite, which was consistant with your idea that
methyl/ethyl nitrites did not exist in the gas phase." I am still a partisan of this theory, as long as we are speaking of good
yields (>75%).
"What is your reference for the 60% yeild from methanol/H2SO4/nitrite, and what are the exact conditions used?" as I said, it
was on rhodium (with HCl instead of H2SO4) and Fieser was quoted, I will do my best to dig out a similar procedure as I am
certain I saw it once (as I did consider it seriously). If my memory serves me well, the conditions were room temp, 18-24hrs
reaction time, excess of alcool (as solvent), conc HCl in twice the stochiometric amount and sodium nitrite in 1,25
stochiometric amount. I will try it if I can get my hand on some nitrite salts. BTW, I am not really fond of the procedure, as I
prefer alkyl halides all the way.
"I will do my best not to be insulted that youve just suggested I look up pre degree information." I am deeply sorry for that as
I do respect you and your ideas, please forgive me. While reading my posts I often find myself quite insulting, which isn't
really my intention, thus I'll put more effort in Engligh language diplomacy (my prime language is french, so please forgive
the pathetics grammar/spelling/syntax errors while we are here <img border="0" title="" alt="[Wink]" src="wink.gif" /> ).

"Are people crazy enought to ignorantly mix chemicals in random amount just to see how it might goes?"
Yes.
Most people are capable of working out rougly how much of each reagent is required for a hypothetical reaction, and most
people will automatically think experimentation is the way to solve the missing information problem. Since the answers are
usually in books they dont have access to, or know where to look for relavent material...
I speak a lot about DMF or DMSO because I have about 4 dozen tabulated yeilds of nitro compounds done in them. (Before
anyone asks, this stuff is on the to do list). Its stated these are used becuase of the high solubility of both the haloalkane,
and also of the metal nitrite used. The corrisponding alcohol is avoided becuase of the difficulty in removing it from the
reaction mixture. If yeilds are also lower, this would be another unstated reason. If the speed of victor meyer is greater in
alcohol than in DMSO, for example, with the same concentration of reactants, then Id buy that for a doller.
I'm aware of reactions like iodine catalysed hydrolysis, but I dont see this as jumping, more of a faster method to fall. Each
stage in the catalysis produces a more stable state than the previos one. Thus iodide will completly replace chloride, and both
will almost completely hydrolyse under the same conditions. The iodide is an intermediate state, and thus its the activation
energy of the attacking reactions that mostly matter. (SN1)
I did wonder briefly about iodine catalysed chloride reactions for nitro compounds, but the increased reaction time over pute
iodides would probably significatly affect the yeild fo the product, and couldnt be done with silver.
In the proposed iodine catalysed from alcohol reaction, since iodine is completely replaced in victor meyer reaction with nitrite,
you have a higher energy state as intermediate in the form of the alkyl iodide, and expecting the reaction to jump over this
additional hurdle, and be faster, While this doesnt totally rule out the net attacking complex of the iodide to the alcohol, being
less of an energy barrier than the attacking complex of the nitrite it does cast considerable doubt.
Ive read the conversion of alkyl nitrite paper. It doesnt give specific yeilds, and it only suggests the resulting solution tests
positive for nitroalkanes, but it seems likley the yeild is in the region of 5%. Presumably the main product of this reaction is
the aldehyde and NO with a small amount of unreacted alkyl nitrite. If you think a good yeild is 75%+, then the term for this
would have to be 'diabolical' given the nitro compound as the goal. Anyone setting up a flow reactor like this would be far
better using methane bubbled through nitric acid, not just becuase of the explosive nature of the alkyl nitrites.
"We are in solution here, thus we speaks of ions."

The situation I'm refering to is the classical victor meyer, in an organic solvent. Ionisation is a rare thing, and even the website
you referenced has the attacking species as the whole metal nitrite. In order to be a difference beteween them they have to
attack as a total group, and it seems likley AgX would leave as a single group too. Either way, the very low availability of X
atoms effectivly prevents the back reaction even if nothing else does, and this was my point.
Maybe Rhodium can jump in with the missing page and why it was removed.
DF90 July 2nd, 2007, 12:21 PM

I was thinking that it might be possible to react nitrogen dioxide with methanol to yeild nitric acid and a methyl radical... which
would then react with a nitrogen dioxide molecule (which is a radical) to form the nitromethane? What i would imagine to
happen is the nitrogen dioxide gives an electron to the oxygen atom in the hydroxyl group, which then bonds to the nitrogen
dioxide yielding nitric acid, and breaks away from the carbon atom (homolytic fission), leaving behind a radical :P This reaction
would be extremely useful as it cold possible be applied to synthesise other nitroalkanes and the nitric acid byproduct is very
useful also :D Just not sure if it would work... maybe someone could try experimenting with this concept?

a n d I m provised C hemistry > An+sulfuric for nitro esters - Archive file
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radar
Freq uent Poster
Posts: 63
From : R edding California
posted January 10, 2001 08:58 PM
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Do any of you know a m ethod in which i can do I can do a sim ple ester n itrification with just sulfuric acid plus am m o n i u m
nitrate and then add m y m aterial being nitrated? Like for exam p l e m eriol or nitro glycerine or EGDN? Thanks
sadsakjoel
Freq uent Poster
Posts: 170
From :
Registered: OC T 2000
posted January 14, 2001 06:05 AM
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hello, what is EGDN?
Mr C ool
Freq uent Poster
Posts: 991
From : None of your bloody business!
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EGDN = ethylene glycol dinitrate. It's like nitrog lycerin, but a bit m ore sto rage stable, a bit less sensitive, and a bit m ore tox ic.
I think the power is about the same.
The only time I use that sort of m etho d is when I m ake nitrocellulose, but I use KNO3 not NH4NO 3. If you're interested in that
recipe, say so and I'll type it out here. I think you need to do it at a slightly higher temperature, which m ight not be good fo r
NG or EGDN.
Mr C ool
Freq uent Poster
Posts: 991
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Did you mean to say metriol (= m ethyl nitrate)? Or is this a different thing I haven't heard of?
Mr C ool
Freq uent Poster
Posts: 991
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Sorry, I was confused in m y la st post. Myrol = methyl nitrate. I suppose you were talking about m a k i n g m e triol trinitrate?

Nitrating cotton with sulfuric acid/KNO3 (or other nitrate)?
W ouldn't there be problem s to make this nitrating mixture hom ogen, or will KNO 3 totally dissolve?
I'm asking this because i find it hard to cover cotton with nitratin g m ix even when using usuall m ethod (nitric/sulfuric acids).
I t s e e m s t h a t non-ho mogen mix can lead to partial nitration or even cau s e s o m e "hotspots".
Sparky June 2nd, 2003, 10:52 PM

Mr C ool, I am interested in yo ur procedure to m ake nitrocellulose with KNO3 and H2SO 4, could you type it out? I have read the
available threads on nitrocellu l o s e b u t h a v e n ' t f o u n d a n y satisfactory method using KNO3 which has been shown to work. SW I M
tried the Sam 's procedure but it doesn't seem to work. Maybe she screwed it up.
kingspaz June 3rd, 2003, 10:52 AM

procedure that will give a complete nitration of cellulose (using pure cotton wool p a d s ) :
0.5g cellulose
5g conc. H2SO4
2g of NH4NO3 or 2.5g KNO 3
1. add nitrate salt to sulphuric acid tak ing care to add it slowly in sm all am ounts and not letting the tem p e r a t u r e e x c e e d 5 0 * C .
2. add the cellulose to the acid and squash it d own under the su rface m aking sure it is all covered with the nitrating mix.
3. using a hot water bath and a cold water bath k e e p t h e t e m p e r a t u r e o f t h e m i x b e t w e e n 3 8 a n d 4 2 * C ( i d e a l l y 4 0 * C )
4. leave the m ixture to nitrate for 40 minutes at the temperature then pour the m ixture into cold water of atleast 3 times the
volum e o f t h e m ix.
to purify:
1. 3 washes with hot water each of 30 m inutes.
2. wash with hot bicarb solution for 30 m i n u t e s .
3. add to a fresh bica rb solution and leave to sit overnight (12hrs).
4. wash with hot water again.
5. wash with a hot 10% urea solution for 30 m inutes.
6. wash with hot water again for 30 minutes and then re move the NC and let it dry.
the above process should m ake the NC reasonably safe to store .
frogfot, yes hotspots are a problem but they can be avoided by using am m onium nitrate as the nitrate sou rce. even when the
m ixture tem perature is very low the amm onium sulphate will not crystalise out into solid crystals but just thicken the m ixture
m aking hotspots alot less likely to occur.

a n d I m provised C hemistry > nitration - Archive file
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atropine
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Posts: 129
From : wales
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I have recently bought 10 litres of H2SO4 from B&Q with no trouble. But i was wondering if it would be m ore usefull to by
s o d i u m or potassium nitrate, sodium nitrate bieng better as in nitration and potassium nitrate bieng better as an oxidiser. Oh
y e a h t h a n k s t o t h i s f o r u m I h a v e m a d e t h e b i g gest bang ever. A catering size can of beans, with a 2 inch hole drilled in top.
R e m oved beans, Filled it with ANNM an d u s e d a H M T D d etonator. And ignited it perfectly with a KNO3+sugar fuse cord.
------------------
# all wize m en have unwize fa ntasies <^
# >
Anthony
Moderator
Posts: 2304
From : England
--------------------------------------------------------------------------------
W hat conc was the NM you used and where did you get it?
Sodium nitrate is really quite useless as an oxidiser, ho w about getting both and using ea ch for different purposes?
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
Buying both would probably be best, but if you're getting them both from a garde n centre or somewhere that m ight get
suspicious, you could buy lots of NaNO3 and convert som e of it to KNO3 with "Lo-salt", which is 66% KCl and the rest is salt.
W hy am I the only one who can't get H2SO4 at m y local B&Q ?!?!?! I think it m ust be a curse of som e sort.
MacCleod
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Posts: 215
From :
--------------------------------------------------------------------------------
Mr C ool;are there any sm aller,non-cha in hardware store s around your area?.Many of these places(at least in the U.S.!)carry
better stuff than the big-nam e stores.My local Lowes(our equivalent to B&Q)carrie s 'blended' sulfuric(looks like jelled mud!),but
at a 'Mom and Pop'store a block away I bought a quart of clear,95% H2S04 for $6.50.Good luck,hope you find som ething!.
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
W ell, there is a small one near me, and I've just com e back from there! They did n't have H2SO4 either, but they did have 2 .5
L o f 3 5 % H C l f o r 3 . 5 9 , s o I b o u g h t s o m e o f t h a t f o r H M T D . I s u p p o s e t h e y m igh t be able to order som e H2SO4 for m e, so I'll
ask next time.
Sm artguy
A new voice
Posts: 11
From :
--------------------------------------------------------------------------------
Mr. Cool:
You use HCl to make HMTD??
I'm intereste d: would you tell me how?
(I know about citric acid...but HC l?)
atropine
Freq uent Poster
Posts: 129
From : wales
--------------------------------------------------------------------------------
The NM was 100% fro m a loca l model shop. 14 a quart. I tried HCL for HMTD and the yeild is vastly superior. And all this bull
a b o u t A P b i e n g e a s i e r t o m a k e t h a n H M T D . I v e b i n m a k i n g H M T D for around a year and have had only one batch fail m e .
Concider that.
P l a n ts
------------------
# all wize m en have unwize fa ntasies <^
# >
Mr C ool
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For every 14 gram s o f h e x a m i n e ( 1 4 g r a m s = 1 / 1 0 t h o f a m o l e ) , 3 . 4 g r a m s o f a m m o n i a i s m a d e , a n d t h i s m u s t b e
n e u t r a l i s e d . 1 m o l e o f a m m onia reacts with 1 mole of HCl, and 3.4 gram s of am m o n i a i s 1 / 5 t h o f a m o l e . T h e r e f o r e , y o u n e e d
1 / 5 t h o f a m o l e o f H C l , p l u s a bit extra. That is 7.3 gram s of pure HCl, so if you're using 35% w/w, you need 7.3/35 * 100
grams of it, or 20.8 g ram s.
So use about 25 grams of 35% HCl for every 14 gram s o f h e x a m i n e , a n d 4 0 g r a m s o f 3 0 % H 2 O 2 .
Cool it to 0*C or belo w during the reaction, but don't let it freeze. Yield is very high, usually about 70% of the theoretical yie ld,
so you get about 15 grams of HMTD for every 14 gram s of hexa mine.
Anthony
Moderator
Posts: 2304
From : England
--------------------------------------------------------------------------------
Thanks, I'll have to try another m o d e l s h o p , t h e l a s t o n e no longer stocked or could get 1 00% nitro.
Agent Blak
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Posts: 765
From : S k . C a n a d a
--------------------------------------------------------------------------------
70% of the Theoretical Yeild is about as high as you can Expect. It is alm ost Impossible to get 100% yield or the theoretical
Yeild(or very close to it, for that m atter).
------------------
A wise man once said :
"... As He W aits For T h e T i m e W h e n T h e L a s t B e c o m e First And,
The First Shall Becom e last"
--R ATM
Agent Blak-------OUT!!

a n d I m provised C hemistry > Help - NaCl03 from bleach - Archive file
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jacob d
A new voice
Posts: 13
From : d e n m a r k
--------------------------------------------------------------------------------
I've heard you can make KCl03 from bleach
( s o d i u m hypoclorite 4% solution) by he ating it
and then adding KCl to the boiling solution.
I thought that if I didn't added KCl I would get NaCl03 instead of KCl03 - is it right?
PHILOU Zrea lone

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Posts: 479
From : Brussels,Belgium,Europe
--------------------------------------------------------------------------------
Yes!
3Na-OCl-->Na-O -C lO2 + 2NaCl
Stone
Freq uent Poster
Posts: 140
From :
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A r e S o d i u m o r P o t a s s i u m Chlorate soluble in water? If so... how would yo u seperate NaCl from NaC lO3 or KClO3?
MacCleod
Freq uent Poster
Posts: 215
From :
--------------------------------------------------------------------------------
W ith the calcium hypochlorite/potassium chloride procedure,the KCl03 crystallizes out when the(filtered)solution cools(because
it's less soluble)and the salt stays in solution.
------------------
"There can be only one!"
PHILOU Zrea lone

Freq uent Poster
Posts: 479
--------------------------------------------------------------------------------
Solu bility is in the order:
NaCl>KCl>NaClO3>KC lO3
That m e a n s N a C l is m ore soluble than KClO3!W ater will dissolve m ore gram s of NaCl than NaClO3.
------------------
" L i f e t h a t d e a d l y d i s e a s e s e x u a l l y t r a n s m itted".
" C h e m istry is all what stinks a nd explode; Physic is all what never works! ;-p :-) :o )"

a n d I m provised C hemistry > New Oxidizer - Archive file
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Alchem ist
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From : W oodland hills,Ca.,L.A.
--------------------------------------------------------------------------------
Hello all,
I have been hearing that Dinitamides have been getting popular in the rocket, pyrotechnic, and explosive industries.
L i k e A m m o n i u m a n d P o t a s s i u m Dinitramide. Has anyone heard of these and can we all m a k e t h e m ?
------------------
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
P o t a s s i u m d i n i t r a m ide? Surely that m eans a nitram ide ion has a charge of -0.5?!?! O r is the ion called a dinitramide, and
there's no such thing as a nitram i d e ? T h a t ' d m a k e m o r e s e n s e .
I s u p p o s e t h e f o r m ula would be som ething like KN(NO2)2. Looks just a little bit u nstable! I certainly wouldn't want to make it,
but it might be possible (if that is the form ula, which it probably isn't) to make it by nitrating potassium am ide, KNH2, with a
H2SO 4/HNO 3 m ix, or maybe reacting it with nitrous acid .
Alchem ist
Freq uent Poster
Posts: 211
--------------------------------------------------------------------------------
Thanks for the reply Mr Cool,
this is what I found on the net. I can't rem ember the web sight,but I was doing a search for new explosives.
Dinitram i d e s a l t s ( P o t a s s i u m , Am m o n i u m , e t c ) a d d r e s s t h e n e e d for nontoxic oxidizers, because they conta in no chlorine or
m etals.
ADN contains no chlorine or metals. Th e m olecular formula is N4H4O4.

The ADN formulation looks like a solid form of highly hydrated, highly condensed air (O2, N2, 2H2O).
ADN's nom inal decom position products are the
n o n p o l l u t i n g g a s e s - n i t r o g e n , o x y g e n , a n d w a t e r.
ADN and the other dinitramide salts have potential as an oxidizer. Thus ADN is the oxygen source in solid propellants and
other munitions applications.
ADN is recognized as a potential revolutionary replacement for am m onium perchlorate in m issile system s.
ADN is calculated to g ive propellants with high specific impulse and is environmentally degradable and benign.
------------------

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > oxidation of
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the_wingman
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Posts: 48
From:
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Has anybody ever tried to produce potassium perchlorate from potassium chlorate and sodium persulfate (sodium peroxodisulfate)?
Does it worth trying? thanx
J
Moderator
Posts: 605
From: United Kingdom
--------------------------------------------------------------------------------
I have read that KClO3 may be converted to KClO4 by electrolysis of the solution. I think that the voltage must be maintained at 6.4v for hundreds of amp/hours.
J
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Correct me If I'm wrong, but I read somewhere that you can get the perchlorate of a metal by adding perchloric acid to the hydroxide of that metal. So, to get potassium
perchlorate, one would add perchloric acid to potassium hydroxide.
Mammut
A new voice
Posts: 39
--------------------------------------------------------------------------------
Hey
Im sorry i have no tip for u, but i have
80% Perchlorate-acid and i say if u do ca.
5ml on a paper and give fire to it, little
stars and smoke u can see [very cool]!!
firebreether
Frequent Poster
Posts: 108
From:
--------------------------------------------------------------------------------
Thats how perchlorates are formed - by adding X OH to HClO4
kingspaz
Frequent Poster
Posts: 348
From: UK
--------------------------------------------------------------------------------
yer i read somwhere that u can melt potassium chlorate and it will react with oxygen in the air to form the perchlorate. If this is possible it could be difficult to melt the chlorate
without it decomposing.
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Whoah, that sounds pretty simple. I'm guessing one would heat it over a low flame until it melts. Would there be any danger involved?
firebreether
Frequent Poster
Posts: 108
From:
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Are you really going to heat a chlorate over a flame???? Your crazy, most likely it would just bust out and burn away.
kingspaz
Frequent Poster
Posts: 348
From: UK
--------------------------------------------------------------------------------
well i haven't tried heating it and have no intention of trying to because chlorates decompose really easily. Pesonly to make pechlorates i would eletrolise sodium chlorate and
which would give me sodium pechlorate then i would convert this to potassium pechlorate by reacting with losalt.
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Hey, hey, calm down!
I'm not crazy, I didn't mean just shove it over a flame, if that's what you thought. Anyway, looks like that idea's going to the trash...
kingspaz
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From: UK
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sorry.....i never ment to sound mad!!!
wantsomfet
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Posts: 233
From: EU
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Potassiumchlorate will melt at ca. 356 deg. C and decompose at 400 and above. If molten it will take oxygen from the air and form KClO4. So if you have very, very pure
KClO3 you could heat it (no flame of course) to exact that temperature an probably obtain KClO4. Questionable is how pure the KClO4 will be or how long it takes for a specific
amount of KClO3 to convert to KClO4.
Note that the slightest impurities may cause decomposition = boom
I suggest only melting very little amounts...
Converting KClO3 electrolytically requires Pt-anode, Cu-cathode. 10V to 14V & 0,1 A/h per cm2 surface. For ~12g KClO3 in 200ml H2O it'll take ca. 3 hours, or set a higher
power.
Another method is KClO3 and H2SO4 (sulphuric acid)at low temperatures, i have the info somewhere, if i find it i'll post it.
------------------
catfood.tsx.org
Anthony
Moderator
Posts: 2312
From: England
--------------------------------------------------------------------------------
<a href="http://huizen.dds.nl/~wfvisser/EN/perchlorate_EN.html" target="_blank">http://huizen.dds.nl/~wfvisser/EN/perchlorate_EN.html</a>
You just have to hold it at it's melting temperature for a few hours.
The trouble with the electrolysis mehtod of forming perchlorates is making sure it has converted once it hasd formed, as it takes a long time.
The problem with using perchloric acid is that most human beings can't get it!
the_wingman
Frequent Poster
Posts: 48
From:
--------------------------------------------------------------------------------
But is there a possibility without the use of electrolysis cells or heating equipement?
I once read somewhere that mixing p. chlorate and sodium (or ammonium) persulfate with H2O and heating the solution would give potassium perchlorate.
I think it's because persulfate is a stronger oxidizer than perchlorate !?
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Forming KClO4 from KClO3 (or the sodium salt) is simply a auto oxydoreduction:
KCLO3 + 3KClO3--> KCl + 3 KClO4
Thus you should have if you do a 100% reaction (what is almost never the case) 3/4 of you starting KClO3 converted into KClO4; you willthen have 1/4 of KCl to take away
by recristallisation.
Perchloric acid can be done by adding HCl conc (max 37%) to NaClO3 (solid) and reflux boil it gently for hours.
HCl is very volatile!!!!!
HCl + NaClO3<===> HClO3 + NaCl (cristallises out)
HClO3 + 3 HClO3 + heat and air--> HCl + 3 HClO4.
Don't try mixing NaClO3 with a stronger acid like conc H2SO4 because HClO3 is an explosive acid when concentrated.
By distillation it is then possible to recover the HClO4 as a 79% solution (over the acid is explosive!!!!).
------------------
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
NH4ClO3 is very prompt to self autooxydoreduction into a weird mix of dangerous compounds like NH4NO2, NH4NO3, NH4ClO2,NH4ClO, Cl2O, ClO2, NH4ClO4, NCl3,... the mix
can decompose spontaneously even in solution and lead to ignition-explosions-detonations.
------------------
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Yeah, those compounds seem to be quite dangerous, chlorine dioxide explodes on formation, this can be seen if you put some conc. H2S04 onto some KClo3.
vurr April 28th, 2003, 06:47 PM

NH4ClO3explodes @ 102C,when dry. and maybe in extremly concentrated solutions.
when metal_ClO3 is low and ammonia(salts) is added slowly @ 105 C or up to perchlorate solution ,it should be not too dangerous to get rid of chlorate contamination..??
John Ashcroft May 4th, 2003, 12:55 AM

It's not chlorine dioxide which explodes on formation; it's chlorine heptoxide (Cl2O5).
Marvin May 5th, 2003, 08:39 PM

Ammonium chlorate has the same sort of autocatalyctic problem as sulphur chlorate mixtures. It can go off when it feels like it, but its much more likley on prolonged storage.
All the chlorine oxides can go off when they feel like it, or fairly reliably on contact with sulphuric acid/heat/light/organic compounds. Adding sulphuric acid to chlorates doesnt
produce the heptoxide, you need perchlorates for that.
John Ashcroft May 5th, 2003, 10:25 PM

Oops. "Heptoxide" should have been "pentoxide."

Chlorine doesnt have a pentoxide, the yellow explosive gas that forms when you add sulphuric acid to chlorates is the dioxide, though I forget what else forms to balence the
redox. You are thinking of nitrogen chemistry possibly regarding the pentoxide, and the numbers would balence.

It's not chlorine dioxide which explodes on formation; it's chlorine heptoxide (Cl2O5).
I corrected that to say "pentoxide." With the correction, what I said agrees with your statement - chlorine pentoxide isn't stable enough to exist (hence explodes on formation).

I dont think its fair to say something you cant make 'explodes on formation' simply becuase you cant make it. Or for that matter, why its relavent to the thread unless you are
contradicting blackadders post, as I assumed.
What is exploding on formation in blackadders post is ClO2 as he stated, not the pentoxide.

a n d I m provised C hemistry > NaC lO3 from Calcium hypochlorite - Archive File
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the freshm a k e r
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Posts: 171
From : Heave n
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I know how to make KCl03 fro m Calciu mhypoclorite, but I want to m a k e N a C l 0 3 . H o w m u c h N a C l s h o u l d I u s e ?

thanks
------------------
You can't survive the life!
Anthony
Moderator
Posts: 2312
From : England
--------------------------------------------------------------------------------
W hy? KClO3 is far m ore preferable to NaClO3.
the freshm a k e r
Freq uent Poster
Posts: 171
From : Heave n
--------------------------------------------------------------------------------
I can't get hold of any KCl
Does anyone know how much NaCl I should use?
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wantsomfet
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Posts: 233
From : EU
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Read this and you'll know...
<a href="http://huizen.dds.nl/~wfvisser/EN/chlorate_EN.htm l#thermal" ta rget="_b lank">http://huizen.dds.nl/~wfvisser/EN/
chlorate_EN.htm l#thermal</a>
Oh sorry, i ju st realised that you asked for NaCl...

For the procedure shown at wissers page you'll need 53,29g NaC l instead of 68g KCl.
(68g = 0.91 m ol KCl --> 0.91 mol NaCl = 53 .29g)
------------------
catfood.tsx.org
[This message has been edited by wantsomfet (edited February 08, 2001).]
Anthony
Moderator
Posts: 2312
From : England
--------------------------------------------------------------------------------
KCl is easy to get! As a salt substitute, or cheaper as water softener refill salt.
nbk2000
Moderator
Posts: 1103
From : G u e s s
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I c a n b u y a 5 0 p o u n d bag of KCl water softner crystals for $9. But sodium free salt substitute (KCl)at the superm arket costs
$1.5 per 4 ounces.
Go figure.
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Go here to download the NBK2000 website PDF.
the freshm a k e r
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From : Heave n
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I don't live in U S and in my country you can't just walk in to a su perm arket and buy it
are there anyway to make it from othe r chem icals?
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J
Moderator
Posts: 605
From : U n i t e d K i n g d o m
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W hat country do you live in? I'm sure it's available somewhere, you just need to look hard. Supermarkets aren't very good
places to find 'useful' chemica ls. Try hardware stores, garden centers, DIY stores etc.
J
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"If the aquarium water has to be drunk don't waste the fish. In fact they'll probab ly be the easiest to eat even if you don't
need the water. The cat is next in the pot." - John 'Lofty' Wiseman

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Reaction rate...
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Al Koholic April 6th, 2003, 11:42 PM

Ok...this may sound a little weird at first and I may be off track totally here but bear with me.
By increasing the pressure of the environment in which a detonation/explosion takes place, shouldn't this decrease the reaction rate (gas production) of the compound (which is
a first order reaction) and shift the equilibrium position towards the reactant slightly? I know this effect if it exists would be unbelieveably slight and most of you may not care
at all...but from a theoretical standpoint shouldn't this be true? Also, increasing the temperature of the environment in which the explosion takes place ought to have a slight
effect as well if one treats heat as a product of the reaction. Simple LeChatliers here.
Now that I've posed this question (which also has other variations that I need not discuss because I think the point has been made), I wonder what would be any of these
potential effects? Would VoD be lower for instance? If you got thoughts or I'm just babbling again :) lemme know!
[ April 06, 2003, 10:43 PM: Message edited by: Al Koholic ]
Microtek April 7th, 2003, 02:59 AM

I think you are right but as you said the effect of pressure on HE must be exceedingly slight. Temperature on the other hand does make an appreciable amount of difference
which is why artillery crews must take the temp of the propellant into account when computing trajectories ( unless they can measure muzzle velocity directly, many modern
units do this instead ).
Tuatara April 7th, 2003, 04:47 AM

I see what you are driving at, and it is certainly true for deflagration processes (eg rocket fuel), but aren't detonations a shockwave process? This means the reaction rate
would depend primarily on the velocity of sound in the explosive - density, temperature, rigidity.

LeChtelier describes reversible processes, detonation ins't reversible: carbon dioxide, water, oxygen, nitrogen, nitrogen oxides etc... (common detonation products) dosen't
reacts together producing back the explosives (that would be nice though <img border="0" title="" alt="[Wink]" src="wink.gif" /> ). Also, LeChtelier dosen't care about
time, the principe is time-independant thus speaking of reaction "rates" isn't correct if it's based on this principe.
However, we can predict that the detonation wouldn't be as favorized as it would be at a lower pressure but when the bomb actually explodes, the pressure dramasticly drops
to atmospheric and the process then goes on normally. Another logic applies to temperature as it's known that temperature has an influence on explosions. This behavior is
predicted by thermodynamics : at high temperature the entropic factor is predominant (since the amount of gas produced) and this favors the reaction. That is, the higher the
temperature, the greater the explosion (this is easily understood as mostly all explosives detonates when heated under vacuum (without oxygen...)).
vulture April 7th, 2003, 04:04 PM

Do not confuse kinetics with thermodynamics!
Le chatelier is thermodynamics and only affects the position of the equilibrium.
Explosive substances equilibrium is usually FAR to the right, hence they are explosive, so the effect will be limited.
Le chatelier has no effect on reaction speed.
Reaction speed only says something about the speed at which a reactant forms, but nothing about it's concentration compared to others (atleast not directly).
<blockquote>quote:<hr />This means the reaction rate
would depend primarily on the velocity of sound in the explosive - density, temperature, rigidity <hr /></blockquote>True. This is essentially the main difference between detonation and deflagration;
Deflagration = reaction propagation through heat conductance
Detonation = reaction propagation through shockwave transmission and breaking of bonds

I'm aware that the detonation isn't typically thought of as reversible in the typical sense of something like a salt dissociation in solution but there will still be a reaction quotient
and equillibrium even though like vulture said...will be FAAAARRRRRRRR to the right hehe :) . What's been said is pretty much what I was thinking would be the case just
making sure. It's verrrrrry interesting that temperature has such a large effect on the position!!! I had no idea that one would be required to re-calculate trajectories due to
temp changes. I would have thought that both temp and pressures effects would have been very slight...
Interesting discussion going on at least!
[ April 07, 2003, 03:30 PM: Message edited by: Al Koholic ]

Temperature has a HUGE effect on the position of the equilibrium!
I won't go into detail here, but there's an integration formula for calculating enthalpy at a different temperature than standard conditions.
To make it even more difficult, the heat capacity, which is a component of the integral, is usually a temperature dependent function too, which means things can get really
nasty mathematically.
Also, the equilibrium constant is also function of the temperature, as is the Gibbs free energy and the entropy....
If you can actually understand my babbling, congrats! <img border="0" title="" alt="[Wink]" src="wink.gif" />

You shouldn't see equilibriums in all chemicals transformations. This is a reaction with equilibrium in most conditions is farrrrr to the right: NaOH + HCl <-> NaCl + H20
When a substance detonates, the change is irreversible as other products would be formed (instead of the original explosive) if the products of the detonation ever comes to
reacts together. There are many simpler organic reactions which aren't reversible, for example acid-catalyzed hydrolysis of an ester is reversible but base-catalyzed hydrolysis
isn't because the resulting acid further reacts with the base. That is, the final product cannot reverts back to the ester. You can't write a reaction quotient for this reaction, same
logic applies in detonations, N2 won't react with CO2 and O2 etc.. to produce back the original TNT.
Vulture: There are links between kinetics and thermodynamics! Look for Arrhenius equation and the activated complex theory. Arrhenius equations is thermodynamic since it
contains elemental properties as the Gibb's energy (enthalpy and entropy..) but contains k, the kinetic constant. It implies that the reaction rate grows up proportionally with
the temperature with any reactions.

I suppose this is why we're having this conversation! :)
I am still failing to see why one cannot write a reaction quotient for a detonation. Even in a detonation you will have some concentration of reactant that varies with time and a
proportional change in the concentration of the products over time. This should be all you need to write A --> B + C [B][C]/[A] = Q
I think this should be applicable to detonations...lead azide for example. Pb(N3)2 --> Pb + 3N2 [N2]^3[Pb]/[Pb(N3)2] = Q
The way I imagine lead azide detonating based on my current knowledge is an extremely rapid chemical reaction essentially. I have an idea that DURING the detonation there
could be any number of things going on such as the presence of one or more transition states, lead azide molecules that reach the activation energy and don't proceed on to
product but simply fall back to the reactant state, and the possibility that the mechanism of detonation allows slight decomposition of the explosive but a reversal of the process
before it proceeds too far. Things like this are observed in every enzyme kinetic known. A certain number of activated enzyme/substrate complexs, no matter how high the
molecular efficiency of the enzyme, will form and then even though reaction activation energy has been reached, fall back to the state of enzyme and substrate without
forming product. I know this is a far cry from the complexity of a detonation but I can't warrent the fact that something similiar to this is not occuring in the detonating aether.
Based on this model, I don't think it is statistically possible to ever achieve a completely, absolute 100% detonation where NO original explosive exists....not even a molecule.
Perhaps this clarify's my admittedly self generated and most likely inaccurate personal interpretation of a detonating explosive but thats why I posted the topic...to see
whatchyall think! :)
Marvin April 8th, 2003, 08:40 AM

Technically all reactions have an equilibrium. In the case of base catalysed hydrolysis you dont prevent the reversability, you simply provide a second much favoured
equilibrium that forms the salt, and pushes the primary reaction furthur to completion by the resulting low concentration of free acid.
There are links between thermodynamics and rate of reaction, as an example, the general rule of thumb at room temperature is an increase in temp by 10C will double the
rate of any reaction, this follows from the thermal population of the exited transition states. If the explosive isnt confined, its doing no work, and all the energy remains, if its
allowed to expand against the atmosphere, pressure is dropping, and thus concentration of reactants and products is dropping, its doing work against the air, temperature is
dropping and as a result of both the rate of reaction should fall.
Detonation certainly is an equilibrium, but the reformation of TNT isnt an issue simply becuase its such a complicated molecule, and the energy difference is large. What is very
much an issue however, is relative amounts of CO2, CO, O2, H2, NH3, CN, N2 etc produced in the reaction. The higher the temp of combustion, the less complete the
combustion. LeChatlier applies here very well simply as a result of forcing energy into a reaction thats producing it.

Well said Marvin...you sure have a way with explaining things very clearly on this board.
What I would like to hear you're input on would be something I alluded to above. Do you think that the issue of "the reformation of TNT" could actually be a present issue
during the detonation itself? I realize what you are saying about the relative abundancies of the products of the overall detonation but I am just trying to deduce what could be
happening in the actual detonation aether. I consider it at least a possibility that there could in fact be TNT being partially decomposed only to immediately reform again during
the detonation itself. I think it might even be possible for a number of molecules to exhibit this behavior due to what would be in all liklihood an extremely tansient event. I
don't want to speculate with unnecessary detail here but what I am thinking is along the lines of a TNT molecule reaching an energy state at which it begins to lose (for
examples sake) a hydrogen or something and then immediately recaptures that hydrogen or another one and goes back to being TNT for a very short time. I know that this
really wouldn't matter one bit for the effect of the explosion because it is a transient state but I wonder what people here think of that?

This is true from a theoretical point of view; all particles/chemicals are in equilibriums with other particles/chemicals therefore can be described with an appropriate reaction
quotien. However, thermodynamic isn't exact nor appropriate in many cases and detonation is one of them. Detonation involves simultaneous bond cleavage, there is a
probability that all bonds thus broken immediatly recovers but if that happens, the results is the same as if there have been no detonation at all. If the bonds does recovers
partially, new products are formed which decomposes ultimatly to elemental carbon, simple oxygen/nitrogen/carbon gases and water. When we take accounts of the amount
of products formed (CO2, CO, O2, H2, NH3, CN, N2 etc) we are taking of other equilibriums as N2 + O2 <-> 2NO which cannot be coupled with the first detonation for
obvious reason. Some of theses equilibriums would favors the detonation, some wouldn't. If you want to go further in theoretical arguments, I do know that there is an
equilibrium between the air I breathe and the very noxious coumpound palytoxin or with TNT (all are farrrrrrrr in the favors of air) but I wouldn't start applying LeChtelier
directly here as it is nonsense IMO. In no way pressure/heat changes would start a gas-phase chemical synthesis of TNT by itself, as it would rather form something else. The
probabilities are there though, it *could* happen, but I'd rather say that there is no equilibrium at all between TNT and air.
Al Koholic: I haven't thought about very simple detonating explosives such as Lead Azide, for which I do agree a reaction quotient is definitly appropriate, even in practice,
because the fragments has a way to recombine into Lead Azide without necessarly doing it *immediatly* after the bonds has been broken or having one chance over the
Avogadro's number, if you see what I mean.
Al Koholic April 10th, 2003, 12:24 AM

Oh I completely see what you mean. That's the primary reason I chose something so simple as an example there. :)
At the end of the reaction it doesn't really matter either way because all I am thinking about here is the intermediate mechanism. I wonder if there is a way to study the actual
mechanism of this reaction? Unfortunately there are probably 20 labs asking the same question and not coming up with answers either so we obviously can't come up with
definitive answers here but this is fun stuff to think about.

and Improvised Chemistry > Alcohol Fermentation
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megalomania July 9th, 2002, 03:50 AM

I have undertaken a research project to put my lawn to work. I am interested in producing ethyl alcohol from cellulose
containing materials for fuel use. While there is much information on fermentation for beer, wine, and even fuel alcohol, I am
surprised at the lack of detailed information for cellulose conversion.
To bring people up to speed, cellulose makes up the vast majority of plants. Such materials as grass, wood, and newspaper
would be valuable sources of fuel if only yeast could process the cellulose. Cellulose is polymerized sugar, and it must be
processed to depolymerize it so that yeast may ferment it. The sources I have that discuss using regular grass seem to resign
themselves to the fact that only about 7% is useful sugar, while writing off the other 93%. Theoretically you could use 100% of
all your yard waste if only you could process the cellulose.
There are 3 ways in which cellulose can be converted into sugar. You can use a high strength acid process, a low acid process,
or use an enzyme conversion process. It is these methods of conversion that I want hard data on. All I can find are references
that these methods exist and are used, but I dont have any information that tells me in no explicit terms how I can do it.
I am looking for companies that sell high alcohol yeast, cellulose converting enzymes or ways to culture/produce those
enzymes, or yeast that can ferment cellulose. I know of some recent research that has produced a type of yeast that can
directly ferment cellulose to alcohol (at Perdue University I think), and I want to know if I can get some of that yeast.
I would hate to rake up a ton of grass clippings only to have 140 pounds of sugar fermentable. I want to be able to raid the
town recycling dump and turn all that newspaper into fuel. I want that $15 spent on BATF license form 2110.74 (license to
distill alcohol for experimental and fuel purposes) to be worthwhile.
I am not looking for any beverage information. I am only concerned with getting the highest yield from cellulose materials. If
you have any relevant information, please post it. There are a few useful books that my library no longer carries (some dumb
fuck stole ALL of the alcohol fuel books damnit!) so I am out of luck in the literature department. If anybody knows of any
ebookz or websites that have a pirated copy, please post em. These books are usually out of print, so they cant exactly be
bought either.
The last time I tried this I just dumped some yeast in a bottle of grass clippings in water. I got some really smelly crap, but
no alcohol to my knowledge. Of course thats what you get for not knowing anything at all. Now I am trying to go about this
more systematically, but I am very disappointed at the lack of useful practical knowledge out there to get high yields from
common materials. Why arent more people doing this, and why dont the big companies publish more information? I have
seen the phrase proprietary information about some cellulose conversion techniques. GRR! I think that means classified
secrets, screw you if I guess right. Maybe this is too hard or perhaps nobody has done it yet. I hope some of you will be able
to point me in the right direction.
pyromaniac_guy July 9th, 2002, 03:59 AM

Mega,
I know this isnt what you were asking for, but to the best of my knowlege all attempts thus far to produce alcohol fuel from
biomass have resulted in a process that requires more energy to be expended than is provided by the generated fuel... if it
was as simple as throwing some stuff in a vat of lawn clipings, do you think we would really give a crap about middle eastern
oil????
Eliteforum July 9th, 2002, 06:31 AM

You have to have a license to distill alcohol?! That's outrageous!
PYRO500 July 9th, 2002, 06:32 AM

I think that for this to work you may need to bleach the paper somehow with a substance that leaves the cellulose intact, and
there should be some kind of enzyme that naturally breaks cellulose down into a simpler fermentable suger, does anyone
know what the enzyme in cow's stomach's is ? The one that lets them digest grass? I think that if you could get some sort of
enzyme juice running through your paper juice you could convert it to usable sugar. I tried making alccohol a few times with
store bought yeast, I found that some of the diffrent packets that were in diffrent batches would ferment faster and some
would stop quicker witch led me to believe the diffrent dates of yeast came from diffent batches of yeast causing some of
them to perform better than others. you could get a bunch of diffrent batches of yeast and try them out cultureing the one
that does best. I guess it's also possible to capture yeast from the air in a filter and randomly culture batches but I think
that's needless. I beleve brewing supply companys will sell various brewing yeasts including high alcohol resistant yeast
10fingers July 9th, 2002, 10:24 AM

I've seen methods of converting cellulose to methanol by destructive distillation. I think this would be the easiest way of
getting an alcohol from wood, cellulose, paper or other organic matter. If you're just going to use it for a fuel then methanol is
just as good as ethanol.
As for ethanol I was looking into ways of making it at one time but the costs of production are much higher than what you can
buy it for. The gas stations in my area are now selling 85% ethanol fuel for around $1.20 per gallon.
I do remember a process for ethanol though that used hydrochloric acid to break down the cellulose into sugars. I will have to
dig through all my piles of shit to see if I can find it.
Also, I do have some plans for a reflux still for concentrating alcohol.
Alchemist July 9th, 2002, 11:30 AM

Hello Mega,
If you have NOT seen this web sight check it out!

<a href="http://journeytoforever.org/biofuel_library/ethanol_manual/manual8-10.html" target="_blank">http://
journeytoforever.org/biofuel_library/ethanol_manual/manual8-10.html</a>
<a href="http://journeytoforever.org/ethanol_link.html#cellulose" target="_blank">http://journeytoforever.org/

ethanol_link.html#cellulose</a>
Take care!!!
[ July 09, 2002, 10:36 AM: Message edited by: Alchemist ]
xoo1246 July 9th, 2002, 01:37 PM

Good page actually. Thanks.
Mr Cool July 9th, 2002, 04:33 PM

Eliteforum: you need a licence to distil alcohol in the UK too. Where are you from?
megalomania July 9th, 2002, 05:22 PM

I am only interested in ethyl alcohol, not just for fuel, but mainly as a chemical feedstock, so methyl alcohol doesnt help me
much. I have the journeytoforever.com publication printed out, actually. It is that document that I was alluding to when I
mentioned they just give up when it comes to using cellulose from grass clippings.
I know the biomass conversion to fuel is not exactly economic, but I am not doing it on a large scale. My process assumes
ample supply of biomass right from the backyard, hence no transportation, harvesting, or storage costs. I also dont pay for
electricity or water, so there are no operational expenses. I would use chemical reactants from other processes that I already
do or plan to do, and I would do all of this from materials I already have, so there are no start up and equipment fees (for
now).
I am thinking of trying a dilute sulfuric acid process that cooks the cellulose. I have waste sulfuric acid from my electrolytic
production of magnesium hydroxide for magnesium metal. I have been pitching this acid because it is contaminated with
magnesium sulfate. In theory if I used a more dilute magnesium sulfate solution I could achieve exhaustive electrolysis
giving me a dilute but pure acid solution. I can use this acid as is for my cellulose hydrolysis.
I have an abstract that describes a general overview of what I want to do for now
<blockquote>quote:<hr />Dilute sulfuric acid treatment at elevated temperature is a method that can be used either as a pretreatment
preceding enzymatic hydrolysis or as the actual method of hydrolyzing lignocellulose to the sugars. The first established
dilute-acid hydrolysis process was probably the Scholler process. This was a batch process, in which the wood material was kept
in 0.5% sulfuric acid at 11-12 bar for approximately 45 minutes. The first commercial Scholler plant was built at Tornesch,
Germany, in 1931. Thereafter, several other plants were built in Germany, Russia, Italy and Korea in the 1930's to produce
ethanol, glycerol and fodder yeast from the provided sugar solution. The process was able to produce 0.17 g of ethanol per g
of dry wood. Almost all of the dilute-acid hydrolysis processes are performed in a batch mode with a retention time of a few
minutes. However, there have been some studies concerning continuous hydrolysis in plug flow reactors.
An our recent work contains data for one-stage dilute acid hydrolysis, where 0.5% sulfuric acid was used at temperature of
188-234 C and a retention time of 7 minutes. The results show that a major part of the hemicelluloses (more than 80%) can
be hydrolyzed by dilute acid hydrolysis at temperatures less than 200 C, but the maximum overall glucose yield occurred at a
hydrolysis temperature higher than 220 C. In no case was a better yield than 40% of the theoretical glucose yield from glucan
obtained. Dilute-acid hydrolysis in two stages is a better process alternative in terms of sugar yield. In the first stage, which
should be carried out at relatively mild conditions, hemicellulose is converted to sugar monomers. In the second stage, the
residual solid is hydrolyzed at more severe conditions allowing cellulose to be hydrolyzed. When dilute-acid hydrolysis is used
for pretreatment of lignocellulosic materials, the process is performed in milder condition than those mentioned above. In a
one-stage pretreatment, a temperature between 140 to 170 C can be used, but two treatments at about 120 C may also be
used.<hr /></blockquote>I am not too keen on the 12 bar pressure
(about 12 atm) which will require me to buy stuff. I could use some more detailed information than this. I will have to check
and see how much pressure glass can take, but the 12 atm, or ~180 psi, is most likely too much. If I have to go with a metal
system, that means I have to get large diameter stainless steel pipe to resist the acidic conditions. There is some stuff at the
Hive and at Rhodiums site about wine bottle hydrogenation (pressure rxns) that I will see.
For me, the amount of time spent on the reaction is not a factor. If I could get away with a few atms at 100 degrees, and just
do this over the period of a few hours that would be great. I want to know if there is any experimental data that supports this
before I make the investment to do the experiments myself. The above process only needs 7 minutes at 188-234 degrees,
but it did not mention a pressure. I want to know which factors (time, temperature, pressure, and acid concentration) influence
hydrolysis. There must be some graphs out there somewhere.
Alchemist July 9th, 2002, 06:35 PM

Hello again,
Mega is this what you have found so far? If NOT, here's what I have so far!
Fuel From Sawdust
CAUTION
This procedure uses hazardous materials and anyone who attempts it does so entirely at his or her own risk.
Sulfuric acid is an EXTREMELY DANGEROUS CHEMICAL. Take full safety precautions, wear safety
goggles, gloves and apron. Take the advice of your chemicals supplier on industrial-standard protective equipment
that meets the required safety specifications. Have running water nearby. Don't inhale fumes! The workspace must
be thoroughly ventilated. No children or pets allowed. Try small test-batches first to familiarize yourself with the
process.
The conversion of cellulose, such as sawdust, cornstalks, newspaper and other substances, to alcohol is a fairly
uncomplicated and straightforward process. At the moment, it is a bit expensive; but that is hardly a problem that
needs to be addressed here. Just a few years ago the idea of running a car engine on alcohol was preposterous --
it was too expensive. Of course, back then gasoline was less than 50 cents a gallon. What might be uneconomical
at this writing might be a bargain by the time you read this.
Let's say you want to make alcohol from sawdust. There are two types of alcohol you can obtain from wood --
methanol and ethanol. Methanol can be obtained from wood by high temperature destructive distillation. Methanol
is also known as wood alcohol. The other method used to obtain ethanol involves converting the sawdust to
simple sugars, the usual fermenting by yeast, and the usual distillation of the fermented solution. There are a couple
of other steps involved prior to distillation that are distinct from the standard processes almost everyone is familiar
with. To save you the trouble of trying to remember whose book you read last week or where in this one you
need to rummage around in for the supporting information, I will provide the usual cookbook instructions.
The first step involves obtaining our standard piece of chemical engineering equipment -- the discarded 55 gallon
drum. You will need more than one.
The substances you will need to conduct the chemical phase of this operation are sawdust (for example), sulfuric
acid, water, and possibly some sodium hydroxide, NaOH.
For the mechanical segment, you will need standard window screens you can buy at the hardware store, plumbing
pipes, elbows, couplings, nipples, flanges, and a welding outfit.
I will describe this just the way my partner and I did it in the lab with the exception of some of the plumbing
connections. This is necessary because you can't pick up a 55 gallon drum between your thumb and forefinger the
way we do a test tube or beaker in the lab.
Be sure that you read all the way to the end before you put your hands on the chemicals. You might be
unpleasantly surprised.
STEP-BY-STEP PROCEDURES
Pour the sawdust you intend to convert to alcohol into the drum. Don't fill the drum more than one-third full or you
will be taking a chance on part of the process slopping over the sides of the drum.
Next, pour what chemists refer to as 18 Molar H2SO4, sulfuric acid, over the sawdust. The commercial
designation, if you order it from a chemical supply house, would be 100% sulfuric acid. However, as low as 91%
will work. We tried 9.2 Molar, or 51%, in the lab and it simply didn't work. It just sat there and looked at us.
Make sure that you put the sawdust in first. If you don't, the sawdust will float on top of the acid -- unless you
pour in more sawdust than the acid can absorb. In that case, you will simply have to pour in more acid anyway.
It's easier to do it right the first time.
When you pour the sulfuric acid on the sawdust, the reaction is almost immediate. The sawdust and acid react in
such a fashion as to turn black almost immediately. It resembles an ugly collection of coal tar or oitch. Bubbles rise
up through the solution. The bubbling is primarily due to air pockets inside the sawdust. Even though the reaction
appears to be instantaneous, you should let the mixture sit for a day or two to allow whatever reaction doesn't
take place at once to proceed at its own leisure.
Once the reaction is complete, you can simply dump in yeast and expect the mixture to ferment. The pH of the
mixture is so low, that is the substance is so acidic, that any microorganism such as yeast that you dump in is
simply going to explode. Of course, they will be very tiny explosions.
The proper procedure here is to supply enough water to raise the pH to the proper level for fermenting or yeast
propagation -- 5.0 to 6.0. In Kentucky, where the water is lightly acidic, diluting the solution 50% by adding an
equal volume of water will raise the pH to about 3.0. In areas where the water tends toward alkalinity (or is basic,
in chemical terms) the pH will go higher. If you don't want to keep adding water, add some sodium hydroxide,
NaOH, to raise the pH up to optimum conditions.
The trick here is that this mixture must be poured into the water used to dilute it with. If you pour the water onto
the acid, a natural inclination, what you will get is a loud hissing sound followed by acid vapors rising up out of the
solution to attack you. If you add the acid to the water, the dilution factor is much greater. The same reaction will
take place but on a much smaller, safer scale.
What takes place is an exothermic reaction. That is, large quantities of heat are liberated. You can get a good idea
of how much heat is liberated by simply placing your hand on the container during various stages of the
proceedings. Briefly put your hands on the drum when the sulfuric acid is poured on the sawdust and you will
experience the same discomfort that you would if you placed your hand in the middle of a hot frying pan. You will
get burned.
Once the solution has been adjusted to the proper pH, it is time to pitch in your yeast. A small packet of
Fleischman's, available at the local supermarket, will do just fine. Watch for bubbles of carbon dioxide to appear.
They might be hard to recognize coming up through the black gunk; 72 hours, or 3 days should be enough to
allow it to ferment completely.
A word of caution. You might think that simply diluting the acid with half water before you pour it on the sawdust
would save a lot of trouble. In a way it does. You don't have to worry about distillation if you do it like that
because 50% sulfuric acid won't convert cellulose to sugar and the yeast won't ferment anything else. We tried it
in the lab and it simply doesn't work.
LIGNIN
Before you run your solution into your still, you need to get as much of the black gunk, big gobs of it, out of the
solution. Remove as much as possible. The material is lignin or the substance that bonds sugar molecules together
to make cellulose out of them. In a chemistry lab you use a buchner funnel and filter paper. A buchner funnel has
tiny holes in the base. The filter paper is placed on the bottom, covering the holes, allowing the liquid to pass and
trapping practically all the lignin. For a barnyard operation, you can punch nail holes in the bottom of a 55 gallon
drum and cover them with newspaper.
Given the fact that the chunks of lignin in an outdoor operation will be much larger than those in a lab, you will
probably want to install a series of wire mesh screens between your fermentor and the eventual, modified buchner
funnel. The screens toward the fermentor should increase in mesh size and those toward the funnel should
decrease in mesh size.
The fluid that gets past the newspaper should be yellow in color. The filter won't catch everything. In the lab, we
observed a ring of small, brown flakes that settled to the bottom of our distilling flask. This fluid contains ethanol
and it is ready to be distilled.
At this point go back and scrape the lignin off the screens and remove the lignin-saturated paper from your funnel.
This is the fuel to fire your still with. There won't be enough to get the whole job done, but it will help and it does
eliminate the problem of what to do with all that black gunk. Just be sure you give everything a chance to dry out
before you try to light it.
The alcohol you get from distilling the yellow fluid is identical to that obtained from sugar or starch. We obtained
190 proof ethanol the first time through a fractionating column. The yield-per-pound appeared to be quite good.
According to most of the chemical literature we read prior to conducting this experiment, the commercial yield of
cellulose is far inferior to that of corn or other common feedstocks. However, a ton of cellulose (saw dust) is free
for the asking
In place of the sodium hydroxide, NaOH, that we used in the lab, you can substitute common garden variety lye
to adjust your pH. If you spill sulfuric acid on yourself -- it is a strong acid and it will burn -- dilute it with water
and scrub with soap. However, the soap should be one that lathers very well because the acid is a very strong
acid and the soap is a very weak base, or neutralizer. Lather the soap up well and use a lot of it.
Once you have distilled the alcohol, you can raise the temperature under your column and boil off the water.
Because the sulfuric acid has a much higher boiling point than water, you are simply repeating the distillation
process to recover whatever unused sulfuric acid is available from the bottom of your still. You can't recover
much of it because H2SO4 loses the two hydrogen atoms, or protons, in the initial reaction and is no longer
sulfuric acid.
In a commercial plant, the elements involved in the reaction could be recovered in the following fashion. It is a
process too long and involved to go into in detail here:
S02 + H20 ---- H2S04
P.S., check this sight also!
<a href="http://www.ott.doe.gov/biofuels/newsearchdb.cgi" target="_blank">http://www.ott.doe.gov/biofuels/

newsearchdb.cgi</a>
[ July 09, 2002, 05:57 PM: Message edited by: Alchemist ]
Mr Cool July 10th, 2002, 10:04 AM

Mega: Is the increased pressure really necessary do you think? I can't see what it might achieve, other than stopping anything
from boiling away. It can't be affecting any equilibria to any significant degree because there shouldn't be much of a pressure
change during the reaction, there's no gas produced or anything.
IMHO, it could be done for longer, at a slightly lower temperature under reflux.
That thread about depolymerising teflon has got me thinking... I wonder if there's any way to depolymerise poly(ethene)
effectively? Then you could react the ethene with steam to make ethanol, and you'd be doing your bit for the environment by
getting rid of non-biodegradable plastic!

Thanks for that info, Alchemist, and no I did not have that one. That link you gave at the end is a big tease, none of those
publications are available except maybe for a price :( . That process strikes me as rather wasteful. If indeed most of the
sulfuric acid is destroyed, I wonder what kind of sulfate is made in its place? Acid recovery is a key to doing this right. I have
not yet found any data that deals with the acid recovery, although the above info is close when it mentions using the acid as a
pH reducer and then recovering it after fermentation. That makes good sense.
I wonder if that process could be improved by cranking up the heat. I have seen some data that says low temperatures (30
degrees) can be fine if a very high concentration of acid is used. If a lower concentration is employed, perhaps heating will do
the trick.
I suspect the high pressures are just for industrial scale procedures. They want to process things quick, and at great efficiency
with a minimum of energy. Pressure is an easy thing to do if you already have all the equipment. From what I gather it is
difficult to penetrate into the crystalline structure of cellulose. I hypothesize that the pressure helps the acid penetrate the
structure better, and of course minimizes the time required to complete the reaction.
I found that graph I wanted that compares temperature, acid concentration, and time. Its actually a data table, but I will be
graphing the data to extrapolate some optimal conditions. These experiments make no mention of pressure, but I assume
some is involved to achieve these kinds of temperatures. Anyway, to sum up the data they used sulfuric acid at 0.2 to 0.6%,
cooked it for 8-20 minutes, and had the temp at 160-180 degrees. They found that concentration resulted in the biggest gain,
with 0.4% being the best. The worst effect was temperature, the higher the temp got, the lower yields were if done for longer
periods of time. This is good news from my perspective. Their best trial was 0.04% acid cooked to 170 degrees for 14
minutes. This resulted in 16.42 g of sugars per 100 g of wood. The higher temperatures favor the production of harmful
byproducts like frufural alcohol, which can in turn hinder fermentation.
These experiments were geared to hemicellulose hydrolysis. Hemicellulose requires less harsh conditions to depolymerize.
The % of hemicellulose in grass is about 15-25% and in wood it is about 20-30%. At best you can get around 75-90% of the
hemicellulose converted into fermentable sugars. These experiments achieved 75% conversion. This may be a useful
temporary measure to boost sugar concentration. The amount of acid is quite low, so recovery is not a big deal. The
temperatures are reasonable, and the time is quite short. 15% more sugar is better than nothing. This would not help me if I
use paper, and of course still leaves the bulk of the good stuff unusable.
This method may be a good pretreatment for the concentrated process though. After hydrolyzing the hemicellulose you could
then subject the cellulose to more vigerous conditions. I did some more research and found that is exactly what they do
industrially. This is a pretreatment step for them. The conditions necessary to hydrolyze cellulose also destroys the
hemicellulose products, and turns them into harmful fermentation hindering byproducts.
I do wonder if the conversion of cellulose is really worth it. This is the big problem that faces industry, and why it costs so
much. Even under the best process they get about 50% conversion. Perhaps industry is only concerned with high yields, where
I would be satisfied with a lower level of conversion. One must remember that industrial and laboratory conditions are rarely
the same.

What about a biological approach? Get some cow dung, cultivate the bacteria from it on grass clippings, paper, sawdust etc (to
favour the ones that use cellulose), and use these to break down cellulose. I'm presuming, of course, that they do hydrolise
the cellulose into sugars. A mixture of these bacteria and yeast may produce alcohol, or immobilise the cellulose-converting
bacteria in some gel (I've forgotten the name of the gel used), and fill a tank with them. Fill it with cellulose-rich stuff, drip
water in at the top and let water drip out the bottom, hopefully with sugars. Add yeast to this, and get alcohol.
Obviously it needs more thought than I can give it at this time of night (or is it morning now?!), but it's another potential
option.
Sam July 10th, 2002, 11:08 PM

If my memory serves me correctly, disstillation of different things produces different flavours (obviously).
Vodka is from potatoes and grain.

Japanese rice wine from rice.
Mexican tequila is from (some) cactus.
and thats all i can remember at the moment.
I have a diagram that shows how to evaporate the alcohol but i dont know how to put it up here.
You need a condenser, a thermometer, a bunsen burner, a beaker, and thats all I can remember, if anyones interested I'll
look it up, but if not, then I wont bother.
cutefix July 10th, 2002, 11:31 PM

The chemistry involved is simple:from a biochemical point,
Reduce cellulose to sugars by means of cellulases.Then add another enzyme (from yeast or bacteria) to convert the sugars to
alcohol.There are other ways of doing this.
To convert cellulose to alcohol you must first convert these polysaccharides to simple fermentable sugars.Just as what
alchemist said lignin should preferably be removed first.
Then an infusion made of the cellulose fibers are treated with cellulase enzyme.
Once it is broken down into digestible sugars;then you can pitch in yeast(preferably the distiller type because it can produce
more alcohol than bakers or brewers yeast).
There are enzyme companies that are expert in these matter
See this one:
<a href="http://www.novozymes.com/cgi-bin/bvisapi.dll/portal.jsp" target="_blank">http://www.novozymes.com/cgi-bin/
bvisapi.dll/portal.jsp</a>
There are detailed ways to do it
These URL looks informative,please check it out:
<a href="http://www.fao.org/docrep/w7241e/w7241e0b.htm" target="_blank">http://www.fao.org/docrep/w7241e/
w7241e0b.htm</a>
James July 11th, 2002, 10:10 PM

I read in a book (don't remember the title it had a yellow cover with a breakdown of a still on the front) that there were a
couple of organisms that might be useful. Clostridium Thermocellum and Thermoanaerobactor Ethonaculus (the names are
probably spelled wrong).

I am looking for the e-book (actually a zipped pdf file) called The Home Distillation Handbook, by Ola Norrman. I went to the
website that is supposed to have it, <a href="http://partyman.se/HbBok/home_distilling_handbook.html"
target="_blank">http://partyman.se/HbBok/home_distilling_handbook.html</a> and for a moment there I thought they were
a bit nieve offering it for download first, and then asking for payment. But alas the file is not there, instead it is now on <a
href="http://www.home-distillation.com/" target="_blank">http://www.home-distillation.com/</a> . The first link will
automaticially transfer you after a minute or so (and quite sneakely you can't use your back button).
I of course want the english version. Does anyone have it?
blazter July 17th, 2002, 11:55 AM

while i dont have the specific book your looking for i do know of some web sites that probably have the same sort of
information on them.
<a href="http://www.moonshine-still.com/page2.htm" target="_blank">http://www.moonshine-still.com/page2.htm</a>
this site is pretty much all devoted to plans for building various reflux stills that would be fairly large scale (compared to lab
distillation aparatus). doenst get into theory of operation much but has some good practical advice.
<a href="http://www.homedistiller.org/" target="_blank">http://www.homedistiller.org/</a>
this is a fairly complete guide, which includes both information about fermenting and then distilling. also includes plans for
reflux stills and gets into some theory of operation. includes useful calculation tools to predict fermentation outcomes and
various things like that. this is probably the most complete guide to distilling that i've seen on the web
Jumala July 18th, 2002, 12:36 AM

Mega tryes to win the nobel price. lol
I believe this problem is an older one. Im certain that many scientists do research for a proceed to convert cellulose in a
single sugar or more convenient direkt into a kind of fuel.
The two possibilities are:
A method to do the job already exist,-
then it must be too inefficient otherwise it would be in use everywhere. (To make biodiesel from rapeseed must be efficient
because it is a little cheaper than
normal diesel in germany)
The method dont exist,-
then there are to much technical or biological/chemical problems.
In both cases , who will find the perfect method get the nobel price and will be rich from selling patent licences.
(Only when the large oilcompanies dont kill him)
And for everyone who wants to make a good fruit liquor or whiskey
this side and their links could be interesting.
<a href="http://www.turbo-yeast.com/intro.html" target="_blank">http://www.turbo-yeast.com/intro.html</a>
10fingers July 18th, 2002, 12:48 AM

Here are some patents related to this subject;
1. Pretreatment process for the conversion of cellulose to ethanol. Patent #6,090,595
2. Process for pretreating cellulosic substrates and for producing sugars therefrom. Patent #4,237,226
3. Method for increasing of cellulose in lignocellulosic materials, particularly hard woods, agricultural residues and the like.
Patent #4,461,648
4. Prehydrolysis of lignocellulose. Patent #5,424,417
5. Method of treating biomass material. Patents #5,221,357 #5,366,558 #5,536,325 #5,628,830
Jaxx July 18th, 2002, 03:34 AM

Hey Mega, if yer after a yeast that can with stand high ethanol concentrations i think you can get it from liquor home brew kits.
I have seen these kits in the UK and they claim to have a final alcohol percentage by volume of 20 or 21 % alc.
Good luck with this ambitious project of yours!
kingspaz July 18th, 2002, 07:40 PM

i think that yeast converts simple sugars like glucose, fructose and sucrose or even starch to alcohol. the problem is getting a
yeats that can process cellulose which has lots of cross linking between lengths of glucose chains.

I have found a few places that sell distillers turbo yeasts, but I am still looking for some speciality yeasts. After an initial
hemicellulose hydrolysis you end up with mostly pentose sugars. I was dissapointed to find out that regular yeasts either have
a hard time or simply can not use pentose sugars.
I keep finding research on special strains of yeasts and other microbes, but nobody seems to have them for sale. I may have
to do it the old 1980's way and write letters to the various government agencies asking for sources.
organikum January 15th, 2003, 10:44 PM

mega you might have a look at this page:
<a href="http://www.dsmz.de" target="_blank">http://www.dsmz.de</a>
They sell also to individuals if you ask the right way.

Hope it is not to late to get your boyscoutgroups project running.
ORG

a n d I m provised C hemistry > De-polymerizing Teflon
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Microtek July 10th, 20 02, 05:0 5 AM

The purpose of this topic is to establish whethe r it is at all possible to de-polym e r i z e t e f l o n u s i n g m a n a g e a ble chem icals and
conditions, and also whether any serious hazards such as liberated flourine would result.
I have seen teflon mentioned in several instances in the context of energetic materials, specifically as an oxidizer in
inciendiary m ixtures and as a binder/p lasticizer for a plastique containing 10 % teflon and 90 % HMX. I was thinking that
m aybe the teflon was funktioning as a semi-energetic plasticizer in this applicatio n due to the oxidizing properties of fluorine (
at least if you added Al or Mg to get a high-blast m ix ). At the very least, teflon would be a very stable binder that would be
unlikely to cause any chemical incompatibilities.
Now, the only teflon I have access to is teflon tape for sealing jo ints etc., but when I used it for sealing the stopper in a bottle
used for glacial acetic acid, it was found to become soft and m ouldable. It lost these properties as the "solvent" evaporated,
but it got m e thinking....
PYRO500 July 10th, 20 02, 05:4 9 AM

PFTE teflon, the m o s t c o m m on kind is mostlty inert to all you can throw at it. there are som e exceptions but I think they are
well out of th e q u e s t i o n ( m olten alkali m e t a l s , s o m e flu oro-chemicals etc)
Pu239 Stuchtiger July 10th, 20 02, 06:2 4 AM

Roasting teflon yields various toxic carbonaceous fluorides.
Mr Cool July 10th, 20 02, 09:5 4 AM

Hm m m ... it is going to be very hard. T eflon's m ain advantage over other com p o u n d s i n m any situations is its inertness, and
the fact that it won't easily depolym erise!
Do you actually want to depolymerise it, or just dissolve it? Dissolving it might be easier, depending on the chain length.
10fingers July 10th, 20 02, 09:5 7 AM

S o m e of the pyro suppliers lik e Skylighter or Pyrotek se ll PTFE powder.

De-polym erization wo uld be the goal, as I'm looking for a plasticizer, but of course dissolving it m ight have possibilities also.
I n f a c t I d o h a v e s o m e m etallic sodium but I'm loath to use it for this kind of thing. I'm g o i n g t o n e e d i t f o r m a k i n g s o d i u m
a m ide which is going to be converted to sodium a z i d e ( t h o u g h t h i s l o o k s a b i t u n s a f e , s o I ' m going for DDNP if I possible ).
kingspaz July 11th, 20 02, 06:0 8 PM

why is teflon your cho ice for a plasticiser? why not a different, cheaper, easily depolymerised plastic?

First of all because I want to try new ways of do i n g t h i n g s , s e c o n d b e c a u s e t e f l o n i s u s e d a s a n o x i d i z e r i n s o m e inciendiaries
and so could be considered an energetic plasticizer and third because it is usable a the 10 % level which is quite good.
Of course, if de-polymerizing it is very difficult I'll have to give it up as im practical, but I won't know if it is before investigating
so....

h m m....well to dissolve it...its basically a long chain halogenoalkane so maybe CCl4 would dissolve it...can't think of anythin g
else since overall its not polar...
nbk2000 July 13th, 20 02, 01:0 4 PM

The whole reason why teflon is so useful is the fact that nothing (short of m olten alkali) will affect it.
CCl4 won't do shit to it, and nothing you can buy or m ake will dissolve it without destroying it.
As for being an "energetic" plasticizer, that's a bit of a misnomer since it's not explosive. In incendiary com positions, it's both
fuel and oxidizer. The carbon and hydrogen portions provide fuel, and th e flourine acts as a powerful oxidizer. I KNOW it
doesn't contain oxygen (duh!) but it reacts in m uch the same way.
Once heated to its flashover point, the breakdown of teflon is self-sustaining. You also ge t some fun bypro ducts like
octylfluoride which opacifies th e cornea s of the eyes within a few minutes, effectively rendering exp o s e d p e r s o n n e l b l i n d a n d
u n a b l e t o d e f e n d t h e m selves against further weapons effects. (Got to love that MIL-SPEAK :D )
You could use PTFE powder to form cold flowed pellets or slugs of explosive. You'll need a 10+ ton press to d o s o t h o u g h .
xoo1246 July 13th, 20 02, 03:2 7 PM

Have you read the pdf about detonation like behavior in thermite/teflon m i x t u r e s ? V O D a r o u n d 3 0 0 0 m /s as I recall it.
Mr Cool July 13th, 20 02, 05:0 9 PM

Yes, Al/Mg etc m ixed with certian chloroalkanes can be detonate d. Mg/Teflon (which is, IIRC, used in those decoy flare thingies
to confuse heat-seakers) can spontaneously detonate, but if it's going to then it will do so within 11 m inutes of being m a d e o r
s o m ething...
nbk2000 July 14th, 20 02, 12:2 3 PM

It's basically acting like flashp owder.
vulture July 26th, 20 02, 12:1 5 PM

If m y information is correct, halogenated carbons make PTFE we a k a n d s o m e w h a t f l u i d . H a v e y o u n e v e r s e e n t e f l o n s p r a y i n
bike r shops for treating chain and gear?
nbk2000 July 26th, 20 02, 02:0 2 PM

Yes.
I also know it's actually microfine particles of Teflon suspended in a petroleum ca rrier, not dissolved teflon.
James July 28th, 20 02, 02:4 4 PM

M a y b e T e f l o n c o u l d b e c r a c k e d s i m ilar to petroleum. As many people have already said it's futile to try to crack the C-F bonds.
It's just a crazy idea I thought up while perusing Teflon sites. Ok, I say something about therm a l d e c o m p o sition of Teflon, but
I don't keep good notes.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Concentrating and
purifying Sulfuric acid
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View Full Version : Concentrating and purifying Sulfuric acid
Hvoroba July 10th, 2002, 12:52 PM

Concentration-Dilute sulfuric acid is heated at 100C normal atmospheric pressure until all moisture (water) is vaporized and condensed seperately.
Purification-The resulting sulfuric acid is boiled at 340C normal atmospheric pressure and condensed seperately.
All this is done in pyrex glassware using an oil bath to prevent steam explosions.
This is a summary of an industrial procedure for concentration and purification which I found somewhere on the internet. Is this correct? If so, what important details should I
not forget while operating such a process? Thank you.
mongo blongo July 10th, 2002, 02:41 PM

Yes it works. Just be careful not to inhale any sulfur trioxide which is driven off from H2SO4 decomposition at a high temp. I quite sure this has been many posts on this.
tom haggen December 11th, 2003, 09:06 PM

I'm on a massive search on this topic. Also does anyone have any material safety data sheet on sulfur trioxide.
-tom
blindreeper December 11th, 2003, 09:33 PM

Tom you have created mahem at sciencemaddness about this topic. You created so many useless posts. "Where can I find the MSDS for SO3"
Fucking search.
www.google.com
sulfur trioxide MSDS
God some people are ignorant, first hit on google:
Safety (MSDS) data for sulfur trioxide
--------------------------------------------------------------------------------
General
Synonyms: sulfan, sulfuric anhydride, sulphuric anhydride, sulphur trioxide
Molecular formula: SO3
CAS No: 7446-11-9
EC No: 231-197-3
Physical data
Appearance: Needles or polymer
Melting point: 16.8 C
Boiling point: 44.7 C
Vapour density: 2.8
Vapour pressure: 280 mm Hg at 20 C
Specific gravity: 1.97
Flash point:
Explosion limits:
Autoignition temperature:
Water solubility: reacts violently
Stability
Stable. Incompatible with organic materials, finely powdered metals, bases, water, cyanides and a wide variety of other chemicals. Reacts violently with water, oxygen and
other chemicals - read a full data sheet before use.
Toxicology
Highly toxic - may cause cancer. May be fatal if inhaled, swallowed or absorbed through skin.
Risk phrases
(The meaning of any risk phrases which appear in this section is given here.)
R8 R14 R23 R24 25 R34 R45.
Personal protection
Safety glasses or face mask, gloves. Good ventilation.
How hard was that, clicking twice and typing 32 charaters :mad:

okay dokay
ALENGOSVIG1 December 12th, 2003, 12:08 AM

What kind of oil do you plan on heating to 340 degrees centigrade?
vulture December 12th, 2003, 04:41 PM

For fucks sake you're getting really irritating tom. It's a classical kewl strategy to crosspost the same question at several boards to make sure you don't have to get off your
lazy ass.
Oil would be problematic, but there are labdesigned silicone oils that will handle those temperatures. But why bother using an oil bath? Just suspend in borosilicateglass above a
bunsenburner and SLOWLY heat up.
rikkitikkitavi December 14th, 2003, 05:29 PM

or use molten lead/tin alloys which melts at about 230-250 C, without the risk of any oil decomposing or creating flammable gases (always a risk with open flames nearby)
there are thermal oil capable of with standing up to 350-400 C but they are not easily accessible .
for the luxurious ones, purchase a fluidized sand bed heat bath , excellent heat transfer and only silica /air used as a media (or build one yourself)
/rickard
Tuatara December 14th, 2003, 06:23 PM
Or try a white metal alloy like the HAYESOL 70 here (http://www.hayesmetals.co.nz/white_metals.html) with a melting point of only 68C.
I'm sure you could find something similar in your part of the world
YayItGoBoom! December 16th, 2003, 09:45 PM

I have a few questions about the process, if you don't mind. What kind of temperatures will it take to start producing sulphur trioxide, and how much gas will it produce? I have
about 3 litres of battery acid in my possession which is basically it when it comes to acid right now (just building up my lab), and I want to conc. for use in reactions (the conc.
right now can't do didly shit, nor do I have litmus paper or scales to figure out the conc.) I would like to boil some down and get the concentrated stuff, but I don't want to end
up fumigating myself.
What kind of procedures do you guys use? I doubt my vent hood in the kitchen is going to cut it, it would have to be done outside. Which means campfire in the woods for me
;-). I don't have any good pyrex that I could heat like that, would regular bottle glass be able to take that kind of heat shock?
Bah, it would be so much easier to raid the Chem Lab...
Bert December 16th, 2003, 11:46 PM

YayItGoBoom!-
Read this (http://www.roguesci.org/theforum/showthread.php?s=&threadid=2660) A search will answer a question like that every time...
nuclearattack February 3rd, 2004, 06:57 AM

To YaYItGoBoom:
To boil the acid you must have a very good ventilation system, the vent hood in the kitchen is not able to do this work well. Safety is the most important thing! Boil the acid
outdoor and wear a mask, googles and gloves. The pyrex is not a problem, you can buy it in a supermarket, it is sold everywere!
About the procedure: i boil my acid a lot, this means that when white fumes appear i continue for about 30/45 minutes. It's very usefull to use a graduated pyrex so you can
control the right amount of concentrated acid you need.
For example: if you start boiling 500 ml of 50% H2SO4 you will have to boil it untill it reaches 250 ml to have about 98%-100% H2SO4. You have to calculate the right amount
of remaining acid after the boiling procedure. It's not difficult.
Concentrating H2SO4 is simple but stay sharp during the procedure because SO3 is noxius.
Rhadon February 3rd, 2004, 11:47 AM

For example: if you start boiling 500 ml of 50% H2SO4 you will have to boil it untill it reaches 250 ml to have about 98%-100% H2SO4 But that's only correct if the
concentration is given in volume percent. Usually mass percent are used.
vulture February 3rd, 2004, 12:25 PM

It's not even correct in volume percent. The density of sulfuric acid increases with the concentration, so you'll need to boil quite a bit past 250ml.
It seems a rather common mistake to forget about density changes and then people wonder why their nitrations with their "98%" acid don't work.
EDIT: Rhadon, you have been forgiven. Now go in peace and...nevermind...:p
Rhadon February 3rd, 2004, 01:06 PM

:eek: sure. Forgive me that mistake.
frogfot February 4th, 2004, 05:08 AM

Just want to point out that concentrated sulfuric acid expands on heating with more than 10% by volume (by observation..) so you have to keep this in mind also ;)
Mendeleev February 4th, 2004, 02:07 PM

Yeah, mine goes from 900 mL to past 1100 mL.

a n d I m provised C hemistry > Security products cheap
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View Full Version : Security products cheap
markkx July 10th, 20 02, 04:1 7 PM

X
<sm all>[ July 10, 2002, 04:29 PM: Me s s a g e e d i t e d b y : m e g a l o m ania ]</sm all>

This is not the right section.
Edit: In fact, I'm not sure that there is a section that this could belong in.
<sm all>[ July 10, 2002, 03:52 PM: Me s s a g e e d i t e d b y : M r C o o l ] < / s m all>
megalomania July 10th, 20 02, 05:2 8 PM

I hope that's not an advertism ent...

a n d I m provised C hemistry > C atalysts for carbo nyl + am ine condensation reactions?
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View Full Version : Catalysts for carbonyl + amine condensation reactions?

Does anyone know of any catalysts that can be used to speed up the reaction between a carbonyl com p o u n d a n d a n a m i n e ?
Specifically, I'm interested in m a k i n g g u a n i d i n e f r o m u r e a a n d a m m o n i a . S o m e o n e s a i d i t c o u l d b e d o n e b y heating urea with

a n a m m onium salt; they also said that they had heard that som eone tried it and it blew up. Perha ps I could try using
a m monium sulphate...
At the m o m ent I'm wondering about using urea, with excess amm o n i a a n d a g r e a t e r e x c e ss of sulphuric acid; som ething like 1
m ole of urea , 1 . 5 - 2 m o l e s o f a m m o n i a a n d 1 . 5 - 2 m oles of sulphuric acid. Any com m ents on this? The idea is to ha ve a large
e x c e s s o f a m m onia to help prevent condensation between two u r e a m o l e c u l e s , a n d e n o u g h H 2 S O 4 t o h a v e s o m e f r e e e v e n
after it has reacted with the am monia. Then the excess could catalyse the reaction...
S o , i f y o u h a v e a n y i n f o o n m a k i n g g u a n i d i n e f r o m urea, either with NH3/NH4+ and a cata lyst or NH3/NH4+ and heat (or a
catalyst and heat), please post it. I'm not really interested in the method with cyanamide, it seems labour intensive and
dangerous to m e.
It'd be nice if it'd work; urea and sources of am m o n i a a re very cheap and plentiful, and GN/NG can t h e n b e m ade with low conc.
HNO 3 (and H2SO4, if NG is m ade), and they're quite po werful.
PrimoPyro August 7th, 2002, 12:04 AM

Personally, m y opinio n is that acidic environments inhibit am inal form ation, which of course is directly responsible for
condensation here.
My reasoning is:
I n t h e a m m onium ion, the polar character favors the proton bea ring the charge, not the nitrogen like is so in tertiary amines.
That proton exhibits electrostatic attraction toward the =O atom , and this gets us nowhere. The two will never com b i n e b e c a u s e
this just sucks up energy to form a very unstab le com pound that regurgitates that proton in a couple nanoseconds to put us
b a c k a t s q u a re one.
However, consider a nonionic am monia such as in a basic anhydrous environm ent where a ctual NH3 is the main constituent
p h a s e o f t h e a m m o n i a m olecule, not NH4+.
T h e l o n e p a i r o n t h e a m m o n i a e x h i b i t s t h a t s a m e sort of electrostatic attraction toward the carbocation attached to the =O.

T h e y m e e t a n d f o r m a n a m inal, C=O + NH3 --> C(NH2)(O H) by proton shift from the am m o n i a t o t h e o x y g e n . T h i s a m inal
loses water to form the desired im ine, C=NH + H2O
Imine formation is of great im portance in "other" clandestine laboratories I have som e e x p e r i e n c e with, and is beaten like a
d e a d h o r s e . I m ine form ation is reversible, and anhydrous conditions favor imine formation, so do dehydratory cond itions.
Imine formation DOES proceed in acidic environments, but I personally think it works better using neutral NH3 species.
NH4+ + heat --> NH3 + H+
Am monium ions easily lose their proto ns when energy is added, such can be witnessed in an ocillating color phenolphthalein
solution with NH4OH --> NH3 + H2O.
So if acidic environm ents are to be used, don't perform it at cold temps where am m o n i u m i o n s p r e d o m i n a t e t h e s o l u t i o n .
Just my $.02 ......
Prim oPyro
<sm all>[ August 06, 2002, 11:09 PM: Message edited by: Prim oPyro ]

a n d I m provised C hemistry > Looking for info on am m onium azide...
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Mr Cool July 22nd, 2002, 11:05 AM

I have a synth for it in mind, but was wondering if anyone has data on im pact sensitivity, etc. for it? Please, if you know
anything about it, let me know here.
I'm thinking about mixing conc. aqueous solns. of NaN3 and NH4NO 3, and slowly stirring in plenty of ethanol. NaNO3 is soluble
in ethanol, NH3N3 is only slightly soluble in it (c. 1g/100mL of 80% ethanol at 20*C). Any comm ents on this?
Thanks.
mongo blongo July 22nd, 2002, 11:30 AM

I have never heard anything about this explosive but it sounds interesting. Is it a prim a r y e x p l o s i v e ?
After you add the ethanol it m a y b e a g o o d i d e a to cool the solution to p recipitate as m uch NH3N3 as possible. If this
explosive is very sensitive the n the particle size may be a problem when precipitating the NH3N3. Maybe dextrin could be used
to prevent large crystals from forming.
Fallout85 July 22nd, 2002, 12:02 PM

From Fedoroff:
Am monium Azide (formerly called Am m o n i u m

Trinitride or Am m o n i u m A z o i m ide), NH4N3,
m w 60.06, N 93.29%; CO 1, nonhygr, rhm b
plates; m p e xpl 160 (Ref 5), starts to sublim e
at 133-4, bp expl above temp limit for slow
decompn ca 300, d 1.346 at 20, Q P f 2 6 . O k c a l /
m ol (R efs 17&21) Qvf -19 kca l / m o l ( R e f 9 )
Qpcor v approx 98 kcal/mol (Ref 6) & Q e
31.2 kcal/m ol (Refs 6&9) sol in w, sl sol
in alc or NH40H, in so l in eth. It form s with
a m m o n i a a d i a m m onate NH4N3.2NH3, in clear,
C O 1 elongated plates, which is stable at
-33, unstable at 0 and unde rgoes transition
at -9 (Ref 7). O ne g liq NH3 dissolves 0.7g
Am m azide at -33 and lg at 0 (Ref 7),
form s a eute ctic with NH, at -8 7 0 a n d 7 6 %
NH3 concn (Ref 14). Addnl soly data and
other props given in Ref 7). Am m a z i d e w a s
first prepd in 1890 by Curtius (Ref 1) by the
action of NH3 on hydrazoic acid. Detailed
descrpns of m e t h o d s o f p r e p n c a n b e f o u n d
in Refs 4,10,11,13,15,16&18.
W hile it sublimes below 250 at press O
t o 1 5 0 m m Hg, it sho ws slow decompn between
250450 at 70 m m and betw 250-310 0 at
1 5 0 m m . Am m a z i d e i s o n e o f t h e m o r e s t a b l e
azides (Ref 20). According to Gray & W ad-
ding ton it vaporizes and disso ciates into
NH3 & HN3 and then the HN3 explodes. A hot
wire causes Amm azide to burn quietly in
air rather than detonate (Ref 20). This azide
detonates violently when properly initiated,
heated rapidly or hea ted, under confinem e n t
(Refs 2 & 10). Tem p of expln is 1400 and
specific energy 7102 kg/1 (Re f 9). It is con-
sidered a non-brisant expl as it decom poses
in an ideal m anner producing only innocuous
g a s e s ( 1 1 4 8 l / k g a t 0 a n d 7 6 0 m m ) (Ref 6).
The toxicity of Am m a z i d e i s u n k n o w n ( R e f
22). Ephraim (Ref 19) states that this salt
m a y b e r e g a r d e d a s a p o l y m er of im id e(NH)X.
Infrared spectra studies of solid Amm a z i d e
are presented by Dews et al (Ref 19a) and
the tryst structure detd by Frevel (Ref 17a)
By m i x i n g a m m onium a z i d e a nd hydro-
chloroplatinic acid and concg the soln by
evapn, a very expl residue was obtained
(Ref 10; p 355)
Hope this helps.
Mr Cool July 22nd, 2002, 03:21 PM

It does, thanks :)
Alchemist July 22nd, 2002, 11:22 PM

Hello all,
Mr. Cool! Wh ere did ya find Sodium Azide and is it NOT expensive, or is it home m a d e ? ? ?
mongo blongo July 22nd, 2002, 11:43 PM

You won't have much luck finding NaN3 unless you can order it from a chem supplier. It would be very suspicious though.
Another option is ope ning up an air ba g casing from a car. The NaN3 is u s e d a s a charge to inflate the air bag. It will be in the
form of sm all brown pellets. The m aterial also contains sand and iron oxide IIRC so it will have to be removed.I "obtained" m y
NaN3 from a lab.
Mr Cool July 23rd, 20 02, 09:3 3 AM

I got it from two airbags, 225g of pellets in total, roughly 80% pure (calculated by dissolving a known m ass of pellets, filtering
it, and making lead azide with excess Pb(NO3)2, then weighing this azide...). It's probably +/- quite a few % though.
PrimoPyro A ugus t 6t h, 2002, 11: 46 PM

I suppose you could exploit the selective solubility of th e a m m o n i u m i o n in water.
Consider the ancient m ethod for m a k i n g s o d i u m bicarbonate, with an am m o n i u m chloride "byproduct" (hah, today the
byproduct is worth m ore than the product) by dissolving sodium chloride in am m o nia water and bubbling carbon dioxide gas
through the solution.
T h e i n s o l u b l e s o d i u m bicarbonate slowly precipitates out of solution to a very larg e extent (the basic enviro n m e n t f r o m t h e
a m monia co-solute drastically lowers the solubility of the sodium bicarbonate to the point of precip itation) leaving am m onium
ions and chloride ions in solution.
Y o u c o u l d e x ploit this by replacing sodium chloride with sodium azide, giving the azide ion and the am m o n i u m i o n i n s o l u t i o n.
I would consider using solid carbon dio xide (Dry Ice) instead of gas though, and I would recomm e n d k e e p i n g t h e s o l u t i o n
basic by having at least a 1.2 molar excess of am monium ion to sodium ion, to as to prevent deionization of the azide ion to
hydrazoic acid.
Hydrazoic acid, as I'm certain you know, is an incredibly painful/m iserable way to die. It is readily absorbed through the skin
and lungs, and its effects are noticed alm ost im m ediately. I can provide an MSDS if desired. Very very nasty compound. Keep
that environment basic.
Prim oPyro
Mr Cool August 7th, 2002, 07:40 AM

T h a t ' s a g o o d i d e a , I n e v e r t h ought of that.
As a m atter of fact I m ight try this late r tonight, since I should b e getting som e d ry ice for m aking dinitram ides.
I realised the alcohol pptation m ethod won't work too well, since NaN3 is less solu ble in ethanol than NH4N3!
Yeah, I know HN3 is nasty. Lol, when I first got my NaN3 the Pb(N3)2 I was making was probably 2 5% Pb(O H)2!! I added far
too m uch NaO H because I was paranoid.
Thanks for the help.

a n d I m provised C hemistry > pentaerithrytol reaction.
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woo-jong July 25th, 20 02, 10:5 7 AM

I want to know the reaction between fo rm a l d e h y d e a n d a c e t i c a l d e h y d e
which form s pentaerithrytol.
H C H O + C H 3 CHO -----> C(CH2OH)4 + ???
form aldehyde + acetic aldehyde -------> pentaerithrytol +???
I want to know the com plete reaction. please help m e....

8 CH2O + 2 CH3CHO + Ca(O H)2 --> 2 C(CH2OH)4 + Ca(HCO O)2
or
4 C H 2 O + C H 3 C H O + H2O --> C (CH2OH)4 + HC O O H , b u t C a ( O H ) 2 i s a d d e d t o a i d i n t h e r e m oval of the form ic acid

produced. It may also be necessary to keep the pH above a certain level.
nbk2000 July 25th, 20 02, 04:2 7 PM

Use the search button at the top of every page, scroll down to the "Organic Synthesis" search field, and type in penta...you get
the idea. There's the synth for your ed ucation.

Actually, Mr. C ool, you are correct about the pH being a necessity. The re m o v a l o f t h e f o r m e d f o r m ic acid is trivial to the
reaction, and proceeds m erely by atom ic opportunism , so to speak. The base is not optional, it is com pletely necessary.
Ca(OH)2 is often used because it gives rise to the best results.
T h i s r e a c t i o n i s k n o w n a s t h e T o l l e n ' s C o n d e n s a t i o n , a n d this reaction is most classically known for producing our beloved
product here: pentaerythitol. It involve s two seperate m e c h a n i s m s k n o w n a s t h e M i x e d A l d o l C o n d e n s a t i o n , a n d t h e C r o s s e d
Cannizzaro Reaction as the last step. It really is a lovely sequence, and I can gladly illustrate the m echanics operating here if
you like. I'll even draw some pretty pictures for everyone. :D
The reaction schem e l o o k s l i k e t h i s o n paper:
C H 3 C H O + 4 H C H O - - & g t ; C ( C H 2 O H)4 + HCO O H
Due to the calcium hydroxide that facilitates this reaction, the actual products are:
2 C H 3 C H O + 8 H C H O + C a ( O H)2 --> 2C(CH2OH)4 + C a(O O C H ) 2 + 2 H 2 O
The first step that occurs is the Mixed Aldol Condensation, in a sort of runaway ch ain reaction that is often hard to stop, and so
it happens three tim es. This is good, because that's exactly wha t we need to happen to m ake pentaerythitol.
First, in solution our Ca(OH)2 dissociates to Ca+2 and 2OH-. This basic environment is of 'm e d i u m strength' and is exactly
what is needed. Acetaldehyde's alpha hydrogen extrudes a proton to neutralize the OH- in the environment, in the reaction
OH- + H+ --> H2O. This reaction is reversible, and is based o n an equilibrium factor that we are exploiting here.
You can see what's going on in this picture. The alpha proton ne utralizes the hydroxide, leaving the alpha carbon with a
negative charge. Due to electron resonance, we can see a proton shift back and forth called tautom erization. This is the enol
isom er of acetaldehyde. The form on the right is m ore stable in very basic solutions, and its the one we DO NT want here, an d
that is exactly why we don't use very strong bases, because then the equilibrium resides on the left, with th e carbon bearing
the negative charge and the carbonyl NOT being reduced to an alcohol.
<img src="http://www.m e t h i n f o . c o m / b o a r d s / g e n e r a l / b i n aries/18/18561.gif" alt=" - " />
So right now we got ourselves a (preferably) en olized acetaldehyde with an alpha carbon that keep s shuttling the negative
charge back and forth between itself and the oxygen a zillion tim e s a s e c o n d . W h a t h a p p e n s n e x t i s t h i s :
W hat the fuck is going on??? you say, right? Well, on the top left we got our form aldehyde. That oxygen is pretty
electronegative, a lot more than the carbon at least, and polarizes the m olecule to that th e o x y g e n i s s l i g h t l y n e g a t i v e a n d t h e
carbon is slightly positive. The positive carbon (carbocation) is attracted to the negative enol carbon (carbanion) of the
a c e t a l d e h y d e + b a s e , a n d t h e y couple. The oxygen on the formaldehyde retracts an electron from the carbon, giving the
o x y g e n a n e g a t i v e c h arge, and the two carbons that are charged m eet and are neutralized. The C-C bond is very to u g h . O n c e
you slap it together, it ain't gonna com e off so easily, so once it's m a d e , t h e r e ' s n o g o i n g b a c k .
Now rem e m b er the last step o f the pre vious picture, the hydroxide was neutralized to water, and I said this was reversible. This
is where it gets reversed. The negative oxygen on the com pound just m ade reacts with wa ter, neutralizing it's charge to
b e c o m e a n a l c o h o l , a nd regenerating the hydroxide. Yo u see now that the hydroxide is a catalyst, without it the reaction
cannot occur. Stronge r b a s e s s u c h a s - O C 2 H 5 ( e t h o x i d e ) a r e o f t e n t o o s t r o n g , b e cause they force the equilibrium far to the
right with the original enol having the oxygen carry the charge, and this does not produce the right product, at least in this
case. There are exceptions.
Now we have set the stage for the sam e reaction to occur again, two m ore times in fact. The same process occurs with the
hydroxide abstracting a proton from th e alpha carbon, same as before, and then the carbanion reacts with another m olecule of
form aldehyde. This alpha carbon has three alpha protons, so occordingly the reaction occurs three times, replacing all three to
get our final com pound in that picture, with the three methylol functions added to the structure and that blasted hydroxy that
wont fucking go away, seem ingly. Good for him , he's working hard for us.
Its really a good thing we W ANT this to happen three times, because its actually hard to STO P the reaction. The only reason it
stop s at all is because the carbon only has three proton s to lose . With each m eth ylol function added, the next formed
carbanion is that m uch m ore stable, m eaning it is m ore likely to be present, and therefore more reactions occur and it is
harder to sto p a t e a c h s t a g e .
Now the estute will realize that this nifty little compound is very very close to the pentaerythitol of our heart's desire, but is still
not quite the re. W e still need to reduce that aldehyde to the final alcohol group. Now that our Mixe d Aldol reaction is kaput,
what happens?
T h e C r o s s e d C a n n i z z a r o R eaction. This one is really weird, but h ey if it works dont bitch, right? Ok, stay with me, he re.
Notice we've used up three of the four formaldehyde m olecules in our chem ical fo rm ula. W e ' l l u s e o n e m ore here to reduce our
alde hyde to the last alcohol, and oxidize this last form aldehyde to a formic acid. The m e c h a n i s m o f t h e C r o s s e d C annizzaro is
a hydride ion shift, whereas in a n A l d o l C o n d e n sation, the mechanism involves a proton shift. A proton shift is a m o v e m e n t o f
H+, and a hydride shift is a m ovem ent of H-, a m uch m ore rare entity.
Alrig ht, the first m olecule on the top le ft is the last form aldehyde. That workhorse hydroxide ion is attracted to that carbon
a t o m b e c a u s e t h e o x y g e n o f t h e f o r m a l d e h y d e is pulling on the carbon's electron s , m a k i n g t h e o x ygen negatively polarized
and the carbon positively pola rized. The hydroxide attaches to the carbon, and th e carbon yields one electron to the oxygen,
m a k i n g a n e g a t i v e o x y g e n i o n . P a y a t t e n t i o n t o t h e h y d r o g e n i n the second picture of the form a l d e h y d e m o l e c u l e , t h e o n e I
circled. Notice I circled the H and also the bond with it. The bonds are the electrons. This hydrogen doesnt leave the
form a l d e h y d e a s a p r o t o n , i t l e a v e s a s a h y d r i d e i o n H - s o t h a t t h e n e g a tive oxygen atom can neutralize the charge to
become a carbonyl group like it was before that irritating hydroxy butted in. So H- leaves the form a l d e h y d e , a n d t h e d o u b l e
bond is restored. The product is a form ic acid m olecule.
In our "almost pentaerythitol" we still have that last carbonyl group (the aldehyde part, C=O) to make into an alcoh ol. W ell,
just like in form aldehyde, that oxygen is hoarding those damn carbon's electrons for itself, causing minor polarization. This
hydride ion is VER Y strongly attracted to this carbocation (positive carbon ion) and adds to it, and the oxygen of the aldehyd e
gets its electron, form i n g a f a m iliar negative charge. At last, we can see the light at the end of the tunnel. This is an alkoxide
i o n . R e m e m ber I said earlier that alko xides like ethoxide ions are VERY VER Y strong bases. And b ases rea ct with acids; in the
l a s t s t e p , t h e a l k o x i d e s t e a l s a p r o t o n f r o m the formic acid, becom ing a neutral alcohol: pentaerythitol, at last! :)
Our newly m a d e f o r m ate ion has replaced the original h ydroxide ion from the calcium hydroxide, a nd pairs up with it to form
calcium f o r m a t e .
T h e s e a r e t h e m echanics behind our equation:
2 C H 3 C H O ( a c e t a l d e h y d e ) + 8 H C H O ( f o r m aldehyde) + C a(O H)2(calcium hydroxide) --> C(CH2OH)4(penta erythitol) +

C a ( O O CH)2(calcium form ate)
So you see, base is not trivial at all, but the "neutralization of form ic acid" is. It is simply a coincidence.
I certainly hope everyone enjoyed this post, an d learned something. I tried to m ake it interesting and explain why it happens
this way. I put nearly two freaking hours into th is post, so I hope it was worth that to you guys.
I'm new here, and I look forward to wo rking out lots of chemistry stuff for all kinds of spiffy explosives. :D
F e e d b a c k i s a p p r e c i a t e d . C y a , I m o f f t o b e d t o d r e a m about oth er chem ical reactions and other nifty products I can tweak out
of shit under m y sink. Toodles! <img border="0" title="" alt="[W ink]" src="wink.gif" />
Prim oPyro
<sm all>[ August 06, 2002, 04:04 AM: Message edited by: Prim oPyro ]

and Improvised Chemistry > Homemade alcohol
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NoltaiR July 27th, 2002, 01:30 AM

First off I am going to have to say that I really have no clue where a topic such as this would go so the mods may move it as
they will.
Having that said, I have recently found interest in homemade alcohol; primarily speaking wine. Now here are a few decent
sites that I have pulled up:
<a href="http://www.geocities.com/NapaValley/Vineyard/1762/recipespage.html" target="_blank">http://www.geocities.com/

NapaValley/Vineyard/1762/recipespage.html</a>
<a href="http://www.recipes.fsnet.co.uk/" target="_blank">http://www.recipes.fsnet.co.uk/</a>
<a href="http://www.beer-wine.com/w_yeast.htm" target="_blank">http://www.beer-wine.com/w_yeast.htm</a>
Anyways I would like to know if any of you guys have personal experience/knowledge of making homemade wine and if you
could give tips that would be most helpful.
Also any comments on issues relating to homemade alcohol would be interesting as well (i.e. rules/legalities, history, etc.).
Thank you.
DBSP July 27th, 2002, 05:31 AM

check: <a href="http://www.homedistiller.org" target="_blank">www.homedistiller.org</a> a very good site vith lots of pics and
calculaters, it's got everything.
I've got a alcohol dest. I can give you some pics of it later today, it spits out 92% ethanol.
VX July 29th, 2002, 05:54 PM

I know that this is off topic slightly but it doesn't warrant it's own thread, and I think it fits in here better that anywhere else.
I have just returned from a holiday in Italy (Rome), where I realy began to appreciate what various chemicals are far more
easily available abroad than in the UK. I was able to buy 2 litre bottles of 96% ethanol, (used to home make spirits). In the
UK I only know of one drink that is over 40% Vol, and that's 'absenth', which is only sold in bars( About 90%), and each
person is only allowed two shots in any one night, anyway here's the good bit, each 2L bottle was 9 Euro, that 6. I remember
asking about the cost of ethanol in my chem suppliers once, it's something like 40 because of the tax. (With a customs and
excise licence it was very cheap) So I now have 4L of almost pure alcohol which I am very proud of.
Other things easily available were acetone from hardware shops for about 50p for a litre (I know this is not a big thing to most
people but here in the UK we dont have it in hardware shops). Both 11% HCl and ammonia for about 30p per litre and
trichloroethane for about 60p per 500ml bottle.
This post will probably interest people from the UK the most while the rest of you will probably be bored by it, sorry
J July 29th, 2002, 09:27 PM

You're not looking hard enough <img border="0" title="" alt="[Wink]" src="wink.gif" /> All those chemicals (apart from the
Trichloroethane) and more are readily available, you just have to look. Acetone is sold at the chemist in 50ml bottles. Just ask
the chemist to order you a bigger bottle, I recently bought 500ml for 3.50, no questions asked. HCl is available in some
hardware stores in 32% concentration for 2.50/500ml, and H2SO4 (91%) is available as a drain opener for 5/liter.
As for the Ethanol, that is a problem. Because the tax man wants to take his greedy share, it's bloody expensive and only sold
by chemical suppliers as far as I know. But you can distill your own, I'll post a picture of my (basic) still tomorrow.

It is necessary in just about every country to have a license to distill spirits. Emphasis on the distill part, you can ferment all
you want legally, although drinking just that will most likely kill you. In the US at least the license is rather cheap and they
have to give it to you.
VX July 31st, 2002, 03:50 PM

Ah, I know that all of the chemicals are available as you said, except for the alcohol. I was just surprised that they were far
more readily available there. They were all being sold in supermarkets, you could just walk in a store and buy all the things
you need for a years experimenting. Probably for less than a tenner. Just like they do on the films :D
I have access to all of the chemicals I mentioned, from various sources but they are far more expensive than they were there.
Incidentally the guy at my chem supply store knows I am a chemistry student because I once invited him to check, since it was
confirmed he no longer questions any of my purchases. Although I am very careful not to buy any suspicious chems from him,
or ever buy certain combinations of chemicals in one order.
Tyler_Durden July 31st, 2002, 04:34 PM

even though i dont drink, i have always wanted to try this...
<a href="http://www.misterridiculous.com/diy/jug_wine_large/" target="_blank">http://www.misterridiculous.com/diy/

jug_wine_large/</a>
...it seems so quick, easy, and efficient
NoltaiR August 1st, 2002, 11:11 AM

As stated by mega, fermenting is legal (at least in the US) so long as you do not sell it to anyone (for anything, it doesn't
necessarily have to be cash) without a liscence as well as letting the government get their cut for taxes. However as long as it
is given for free or for yourself then you may make all the wine or liquor that you want. Distilling it to extract the pure (or
nearly pure) ethanol is illegal; this is also known as moonshining. An easy way to test (and this may not always be a very
accurate way to do this) is that if you can hold a match to your wine and it does not catch fire, then it is diluted enough to
keep the law away. If, however, it catches and burns like fuel (the ethanol) than your spirits may be over the legal limit. There
is one way to get by this if caught--and this may be tricky--and that is by using the loophole in the 'homebrewing' laws that
allows you to make distilled spirits as long as it is for testing for 'alternate forms of fuel'. If you can convince authorities that
your spirits are for experimental fuel purposes only, than you can have you alcohol as stong as you want and there is nothing
they can say.
Anyways my hobby took effect last Saturday when after a little online research about homemade alcohol (and it is so much
easier than I had ever imagined) I made 3 batches of wine and 1 batch of rum (each a gallon). The first was grape, the
second and third were cherry. The rum is made similarly like the wine, except molasses was substitued for fruit and oak chips
were used for aging. It has been about 4 or 5 days since I made the mixes and they are nearing their fermentation period. I
will update you guys as the process continues.
Anthony August 1st, 2002, 06:32 PM

Just because you can make 5 gallons of wine for a few dollars doesn't mean it'll be fit to drink by any stretch of the
imagination!
Guiness costs about 9/gallon and even at that price is unfit for human consumption.
I didn't realise there was a loophole for alternative fuel research, interesting.
YTS August 1st, 2002, 08:15 PM

I used to make wine the strongest i used to make was rice & raisan you use 3lb rice 2lb raisans 6.5lb of sugar 3 tbl spoons
citric acid & 2 gallons of water put all ingredients in a bucket stir well add yeast put on lid loosely to let gas escape stir daily for
2 to 3 weeks then pour thru filter into demi johns :) put in air lock let finish fermenting then keep siphoning of the lees for a
few months till clear .Or use a wine filtering kit its strengh is usaully 17 to 20% alchol. J i bought 5ltrs of 32% hcl from hard
warestore for 7.95 a few days ago i thought that was pretty cheap the store i bought it from is usually dear
Jumala August 1st, 2002, 11:37 PM

4 weeks ago I have started a fermentation of 3,5 Kg malt syrup and 4 Kg sugar with water. Aprox. 28l at all.
I used a sherry yeast, able to reach 16% alcohol. But it is a slow yeast. It needs 4-6 weeks. A few days ago I got the new
swedish pot distillers Yeast which is able to produce 20% in 7-10 days.I will use it for the next batch after Ill distilled the
malt-wine.
I hope it will be a acceptable wiskey.
Does anyone made wiskey with a good result?
DBSP August 4th, 2002, 09:37 PM

I've got the pics of my dest, I took them the last time I ran it.
Something wierd happened, it normaly stayes around 92% this time it ended up at ~93,5% great! :D
<a href="http://w1.478.telia.com/~u47804009/E&W/DBSPs_dest.JPG" target="_blank">http://w1.478.telia.com/~u47804009/

E&W/DBSPs_dest.JPG</a>
<a href="http://w1.478.telia.com/~u47804009/E&W/ethanol.JPG" target="_blank">http://w1.478.telia.com/~u47804009/E&W/
ethanol.JPG</a>
<a href="http://w1.478.telia.com/~u47804009/E&W/ethanol2.JPG" target="_blank">http://w1.478.telia.com/~u47804009/
E&W/ethanol2.JPG</a>
Jumala August 5th, 2002, 09:44 PM

to DBSP
I dont understand why you concentrate the alcohol up to 92%.

If you use only normal sugar for fermentation it should give nearby no foreshot (methanol, acetaldehyde) and less volatiles,
only tasteless alcohol.
The usual drinking strengh is 30-50%. I know a Koskenkorva wodka with 60%. But the 92% ethanol must dilute again.
So why all the expense?
zaibatsu August 5th, 2002, 10:34 PM

Maybe the ethanol is for a use other than drinking?
firebreether August 5th, 2002, 11:20 PM

You have to distill the mash to get it up to a higher alcohol % then the 10 - 20 % coming strait from fermentation. If his still
gets up to 90+ %, all the better, he'll just dilute accordingly. If its for fuel, you need it high, so you'll need to design the still
to give out high percentage alcohol, so youd need a reflux still.
DBSP - What height is your reflux column - 1 m, or higher? and what do you use for the media? How exactly did you measure
alcohol % - density, or other?
Jumala August 7th, 2002, 12:43 AM

o.k. for use as fuel it must have 92% or better 96%.
But DBSP comes from sweden, a country with the highest taxes on liquors.
So I think his alcohol is for making drinks.
I have only a simple still which gives me 60-70% alcohol from a 15-20% mash. But it is faster and needs less energy than a
reflux still.
Anthony August 7th, 2002, 08:21 PM

I'd be weary of drinking home distilled alcohol, because take off the wrong fraction and you've got methanol... How do you
ensure you avoid this DBSP?
DBSP August 10th, 2002, 06:48 AM

The usual procedure for removing the methonaol tnat might be formed is to throw the first 50ml away. this is what you can
read at evry every place, some even say that you don't need to remove anything.
Have you ever tried tasting mash srtaight out of the fermenting vessel? don't it tastes so bad you simply cant face drinking it.
And the hangovers you get from the mash is massive, due to all the shit thats present in it.
my column has 80cm of packing(SS steel scrubbers) and now puts out 94% meassured by volume with a standard alcohol
densimeter.
The diluted alcohol from the 94% tastes shit thats why you purify it with avtive carbon, I wouldn't even think of drinking
finished alcohol from a 70% crude alcohol even if it was purified 5 times.
Moonshine is very common in sweden since the taxes on ethanol is so fucking high, allmost everyone has tasted it. I allmost
never drink anything else, except for some beer but the swedish beer isn't what I would call good so I only drink it when I get
some danish beer(much better).
photonic August 11th, 2002, 02:36 AM

I have all the copper piping for building a pot still in my garage waiting to be assembled, but would like to build a reflux still if
possible. HOwever, I am unsure if I am capable of doing so. Despite all my reading, I'm am unsure about the preparation of
the mash. All recipes I have seen reccomend using "yeast nutrients" then they give a list of chemicals I have never seen. Are
there any common "yeast nutrients" readily available at the grocery store? Any information relating to the building of reflux
stills and preparing of the mash would be greatly appreciated.
Secondly, I bought mostly lengths of 1" and 1/2" copper piping. I was planning to use the 1" piping as the jacket and the 1/2"
as the condensing core, will the be too much area for it to condense properly?
[ August 11, 2002, 02:03 AM: Message edited by: photonic ]
mr.evil August 11th, 2002, 06:20 AM

f you are planning to make your own destillation/reflux still, maybe you should read this pdf(link):
<a href="http://www.rhodium.ws/pdf/still.pdf" target="_blank">http://www.rhodium.ws/pdf/still.pdf</a>
Maybe it's usefull for you :)
photonic August 13th, 2002, 02:20 PM

HEy, dbsp, I've completed my still and am ready to pack the reflux column with stainless steel wool. How tightly did you pack
the pads in there? Did you like tear the pads apart and fill it or just shove whole pads in? ANy help would be greatly
appreciated.
DBSP August 13th, 2002, 03:46 PM

I'm not shure wether you've got the right wool. If it is very fine steelwool it's the wrong thing. The wool you are to use is the
thicker wool that more lookes like springs. I you wait untill tomorrow I'll uppload a pic of my packing.

That would be greatly appreciated. The steel wool that I have is fairly fine. Is the wool you have loosely packed with no binder?
I had been boiling the wool I have for a long time and some sort of brown glue(i think) kept coming off it.
DBSP August 14th, 2002, 07:22 AM

<a href="http://w1.478.telia.com/~u47804009/E&W/packing.JPG" target="_blank">http://w1.478.telia.com/~u47804009/E&W/
packing.JPG</a>
<a href="http://w1.478.telia.com/~u47804009/E&W/packing_fastened_on_Al_rod.JPG" target="_blank">http://
w1.478.telia.com/~u47804009/E&W/packing_fastened_on_Al_rod.JPG</a>
The packing is fastened on a thin Al rod in order to make it easy to insert it into the culumn. Thus it is as easy to remove it
which makes the cleaning easy.
You shuldn't pack the cuolumn to much because if you do the still will choke and the pressure can become to high which could
be a security problem.
imported_reodor_felgen August 14th, 2002, 12:02 PM
There is an updated version of the still-construction .pdf located at:
<a href="http://www.moonshine-still.com/page2.htm" target="_blank">http://www.moonshine-still.com/page2.htm </a>
(Click the download PDF at the very bottom of the page)
If you are looking for the right packing, maybe this would help a bit?
<a href="http://www.raschig-rings.com/default.html" target="_blank">http://www.raschig-rings.com/default.html</a>
[Edit: The first link should work now.]
[ August 14, 2002, 05:16 PM: Message edited by: reodor_felgen ]
Eliteforum August 14th, 2002, 01:46 PM

The first link gives me a page not found, you sure you've got the right link?

I went to the hardware store today(Lowe's) looking for some steel wool like that and didn't find anything that even remotely
resembled it. That stuff looks more like chain link fence than steel wool. Does anybody have any idea where I can get that
sort of steel wool or some that would be suitable for this purpose?
0EZ0 August 14th, 2002, 11:28 PM

You may be able to find such a thing in a Supermarket. I know that over here, something resembling that can be bought as a
heavy-duty kitchen scourer.
firebreether August 15th, 2002, 12:12 AM

I have a question about the Height Equivalent to a Theoretical Plate of each packing. I know that stainless steel scrubbers
have around .1 m HETP. Does that mean that you could just use a plate system that has a 10 cm clearance between plates
and have just as effective use of the height of the column. At small diameters of the column it would be more trouble than its
worth, but at a diameter of around maybe 10 cm, I think it would be easier to use plates, has anyone tried using plates for a
fractioning column? Maybe use sections of the column that screw together to just add on each section if you need to.
edit- the kind of plates i would use would be the perforated plate system where the gas pushes up through holes in each plate
and the liquid flows down through a tube to each level.
[ August 14, 2002, 11:35 PM: Message edited by: firebreether ]
NoltaiR August 15th, 2002, 02:38 AM

Hey boys..
Nutrients are only needed when the liquor mix you have made (in some cases known as the 'must') does not provide enough
nutrients of its own for the yeast to survive/reproduce properly. In many cases just letting the pulp of the fruit (in fruit wines
only..obviously) ferment with the rest of the mix will give off enough of the needed nitrates and phosphates that fermentation
will go on well even after the pulp has been strained. But in any other situation a nutrient (found in any homebrewing shop
and on occasion at your local wal-mart) is required otherwise the yeast will reproduce using their own bodies as nutrients;
therefore only a few generations of yeast are formed and a VERY low alcohol content is found. But if nutrient is not available,
substituting some of the sugar required by brown sugar along with a small chunk of tomatoe paste (this is a little trick of the
trade) should do just satisfactorly--but not as well as if you had actual nutrient.
Another problem facing home wine-makers is providing correct outside conditions so that the yeast may reproduce as
expected. The temperature--if possible--needs to be held between 65 and 70 degrees F. If you let your wine-to-be mix stand
in a too cold enviroment, your yeast will either reproduce much too slow, or go dormant until the temperature rises again. If
your outside temp is too high, your yeast will begin to die off prematurely and you risk losing large amounts of alcohol due to
it turning into vapors and escaping with the CO2 given off.
The sweetness of wine:

As yeast reproduce and live out their microscopic lives in the mix, they feed on sugar, and as a by-product give off alcohol. It
was first estimated that out of 100 parts of sugar that is fermented, about 52% is released as CO2 and 48% remains as ethyl
alcohol. Later it was to be found that this equation only accounts for about 90% of the sugar used because of other byproducts
that are formed (such as acids and higher alcohols). Although yeast ferments sugar into alcohol, it can only withstand a certain
concentration of alcohol before the alcohol kills off the yeast (otherwise you would be able to make rediculously high
concentrations of alcohol without use of a still). If the sugar is used up before the maximum concentration is reached (about
18% alcohol if using wine yeast, and about 14% alcohol for those of us using bakers' yeast) then the yeast will starve to death
and you will have a very dry wine. If the yeast reaches the maximum alcohol content before all the sugar reserves are used,
then the alcohol will kill the yeast and the remaining sugar will remain giving you a medium-sweet to sweet taste.
Well thats all for now, bye.

Alright, I am back again with more 'in-case-you-wanted-to-know' information about homemade wine and distilled alcohol from
the various books that I have had my head stuck in for the past week or so.
First off to speak of legalities:

The head of any family (must include AT LEAST two adults) may produce up to 200 gallons of wine per year that is not to be
sold legally. Usually the government likes if you still get a permit (its free) from the ATF on which you would document all of
the wine you made throughout the year incase any government officials had reason to suspect that you were doing something
illegally. But even if you were not to pick up the permit and you obviously made no more than 20 or so gallons during the year
(its quite easy for an inquiring ATF agent to determine whether a person is a beginner that only likes to make a little 'just to
try out' or if the person is an expert wine maker that likes to make a few gallons every afternoon that he gets off of work and
gets bored).
A single adult may produce up to 100 gallons with a similar permit, once again as long as it is not to be sold.
If you plan on making large amounts of wine (200+ gallons a year) or if you are planning on selling it, than a special permit
must be purchased depending on exactly how far you are planning to go with it and you must prove that you have satisfactory
'utensils' and tools along with sanitary processes of making the wine. These special permits can run up to about $500 or more
if you were the type of enthusiest really planning on making a business out of it in which you would have to pay a ATF agent/
worker to personally inspect and certify your operations. Also all homemade wine manufactured under a selling permit must
have taxes paid on it BY THE MANUFACTURER. Meaning even if you don't sell it, your stuck paying the tax.
Moving along, a little about wine and beer in history. As you probably all know, wine making goes back into the biblical times.
And yet yeast wasn't a required ingredient in wine recipes until about the early 1900's. So why is it that the sugar in the fruit
mix break down into alcohol as it does in modern days? The answer is simply that there is wild yeast spores in the air
everywhere around you. By the nutrient rich grape/water/sugar mix being left partially exposed to outside contaminants
(including wild yeast), the fermentation would commence as usual after a few days. The problem is that they could only use
very few types of fruits, because only a few (for example grapes, elderberries, and blackberries) have the right amount of
phosphates/nitrates as well as acids in them to make them suseptible to the wild yeast.
In fact many of the older people (people born around the 20's and 30's) that grew up using their parents method of
fermenting, the age-old process of leaving the sugar/water/fruit mix to take care of itself, actually were a bit resentful to the
idea of adding cultivated yeasts. It was obvious that adding yeast on your own would speed up the process dramatically (the
'old way' usually took about 3-4 days to begin fermenting and it was a very slow start; simply adding a packet of bakers yeast
to the same original mix will usually have it fermenting rapidly within 5-6 hours). But they were so used to the taste that the
old wines had (even if that taste would probably make modern wine-drinkers puke) that they just couldn't get used to the new
wine.
Also a very big problem with the 'old-style' process is that many bacterias also grew alongside the wild yeast in the barrel of
sugar/water/fruit mix; the most infamous of these bacterias is that which converted the remaining fruit mix into acetic acid
(vinegar). Once that happened, the investment in everything used in the wine was a waste.
So to 'convert' some of the old-timers to liking the new-style wine, they combined the age-old techniques of making beer with
making wine. Meaning instead of adding yeast, they would add a cupful of mash (sprouting corn). And this triggered the
ferment much quicker than without anything at all and it also allowed for the wine barrel to be closed off the entire time so
that there was much less chance of having the wine turn sour (turn to vinegar). So this style of wine was still different than the
old style, but it had that hint of beer to it which was actually quite satisfying to many at the time.
And one last thing before I leave about distilling alcohol:

Incase you didn't know (and this is the most basic principal of distilling alcohol), ethyl alcohol boils at 173F and water boils at
212F. Just heat your wine/beer mixture (usually between 12-20% alcohol) to slightly higher than 173F and you will have vapors
that are up to 95 percent alcohol. The vapors are cooled in a condenser and the remaining liquid drips out in a separate dish.
Obviously don't worry about your original wine/beer being made of any special fruit or mash mixture, because during
distillation all flavorings are stripped. To flavor the final liquid (the distilled alcohol), you would need to dilute it down to about
40%-45% alcohol and make a liquor out of it (there are many recipes on the net) by simply mixing it with sugar and the fruit
of choice (NO YEAST IS ADDED, AT THIS CONCENTRATION THE YEAST WOULD DIE ON CONTACT WITH THE ALCOHOL ANYWAYS)
and allowing it to sit in a tightly corked bottle for a week or so and the pulp is strained. Then age to your desired taste.
Alright, enough for tonight, goodnight.

And one more thing in case I haven't mentioned it previously, moonshining is still illegal so don't get caught with one using it
for any purpose other than to purify water or to make alcohol for experimental fuel purposes! <img border="0" title=""
alt="[Wink]" src="wink.gif" />
andreas August 17th, 2002, 11:34 AM

I could be wrong but here I go.
Water boils at 100 centigrade
Ethyl alcohol boils at 79 centigrade
A mixture of both boils at 73 centigrade becouse i forms a azeotrope just like nitric a 70%
so with each destillation you gain a few percentages of alcohol in the water.
To get it up to 95,6% you would need severall destillation steps. Or and this is much quicker you make a reflux still wich does
all those separate steps in one go( if constructed correctly). <img src="http://www.geocities.com/homedistilling/images/
diagram_1.gif" alt=" - " />
As you can see from this diagram you can't go from 10% to 95%
firebreether August 17th, 2002, 11:43 PM

Here is a picture I drew of two kinds of plate stills.
<a href="http://www.angelfire.com/fl5/grrr6/images/still.jpg" target="_blank">http://www.angelfire.com/fl5/grrr6/images/

still.jpg</a> <- copy/paste into new browser
Each has their advantages. With a perforated Plate Still, PPS from now on in this post, it is simple, very effective with alot of
gas mingling with the liquid on each plate due to the fact that small bubbles are formed. However, if designed with too much
area drilled out for holes, or a constant pressure is not kept in the boiler, the plates may dump and send all the liquid through
the holes instead of being held on the plates and carried down by the downcomers. While more complex, with a Bubble Cap
Plate Still design, now BCPS, it solves the problem of dumping, however the bubbles formed are smaller so it is possible, and
likely, that this would reduce the effectiveness of each plate.
I personally would go with a PPS and just drill out very small holes and keep the hole area down at first to test the
effectiveness. This seems to me to be as cheap or more so as having to buy rachig rings, or other "industrial" or more regular
packings than SS scrubbers, which are only really effective for small diameter columns. But since nearly everyone here is going
to only need a small diameter column this is best for most.
In the picture you see how I would space the plates. You probably only need one rod to connect each plate, but I drew three
for each. One might do the job but I'd say use two if not for supporting the plates but to prevent them from turning relative to
each other. If you could find a threaded rod that would go the whole length of the column to support every plate that would be
the best choice just run it straight up the middle.
NoltaiR September 3rd, 2002, 02:43 PM

It has been a little over a month since I made my first batch of wines which included 1 gallon of black grape, 1 gallon of white
grape, 2 gallons of cherry, 1 gallon of pineapple, 1 gallon of a black grape and cherry mix, and 1 gallon of strawberry. Well
due to the poor racking techniques that I used because of lack of experience, I lost a lot of wine along the way. I have only
drank a quart of the black grape, but the rest have only had very small amounts taken from them for use as taste tests.
Currently the amount left from that batch is, 2.2 gallons of cherry and black grape mixed, .6 gallons of white grape, .6 gallons
of strawberry, and .6 gallons of pineapple. Definetly not a good turn out but it was all for the sake of learning anyways. Just
last week was the final racking and taste testing; they were all still a bit dry so a added some more sugar, so by now the wines
should be ready to drink whenever I get a free night to call over some friends and party. The wines are perfectly clear now that
all the sediment has fallen out of them and the alcohol levels are very high (for wine anyways). Previously I had posted that
bakers' yeast can only make 14% alcohol.. this was taken from an old wine book. The bakers' yeast that I have is an 'active
dry turbo yeast' which has made--according to my hydrometer--and average of 30%-35% alcohol.
Anyways since then I have improved my techniques and my newest batch started last week with 2 gallons of what started out
to be a light vanilla rum as well as 1 gallon of a peach/pear mix. The reason I call it 'light vanilla rum' is because real rum is
fermented using blackstrap molasses rather than sugar. I just used a mix of household pancake syrup and brown sugar.
Anyways I have already racked all 3 gallons once and had very little loss. Also because yeast requires a nutrient of some sort
(some wine makers use a formula type nutrient) and my choise was just the age-old technique of using a 'rot'. Which is just
the addition of cut peices of fruit to the wine after it has had its first racking and straining. They cannot be just any fruit
though, it has to be a type that, as the name of the procedure implies, rots easily. Therefore most types of canned fruit would
be unacceptable for this.
In the vanilla rum I used a half pound of coconut shavings for aditional flavoring and pieces of banana for my rot. So far this
wine/rum has been the first fermenting mix that I have made that actually had a delightful smell during the ferment. Also
once the rot has been in place for a while and a slow to steady ferment is occuring, the addition of more pure table sugar will
spead up the ferment drastically. In fact, if done right, up to 80% of the new sugar added will make the transition from sugar
to alcohol in a matter of 10 seconds or so.. this can be viewed as the ferment foams incredibly as all the CO2 is suddenly
released. The rot will be removed in a day or two and the rum will be racked for the second time. I will add a little more sugar
for flavoring and then the mix will be allowed to sit unshaken as it ages for about 3-4 weeks more.
Basically the same for the gallon of pear/peach wine. The original mix of the fruit was pureed in a food processor and used in
the wine. This pulp was removed during the first racking and a few large slices of ripe to overripe pear (with the peeling still
intact) was used as the rot.
The final reports of these wines (first and second batch) will be posted in a week or so.
And just as a personal question that just relates to alcohols in general, is it possible to synthesize methyl alchol (methanol)
EASILY?
[ September 03, 2002, 01:48 PM: Message edited by: NoltaiR ]
Boob Raider October 2nd, 2002, 06:03 PM

Here is an IDEA it might be un-economical in large quantaties but should work for small ones. Lets say I ferment potatoes and
cheap rice for a while decant the clear liquid, stick it in the freezer and concentrate the Alcohol % and later on move up to dry
ice to freeze the H2O out and assuming the concentration can be taken up to ~75% (someone please tell me how to calculate
this) anyways ... after that add maybe a couple of drops of dil H2SO4 and electrolyse out the remaining H2O and it should
leave ~100% C2H5OH. So what do you guys make of this ?
Marvin October 2nd, 2002, 07:46 PM

Ok, firstly making 30% alcohol/vol by fermentation alone is flatly impossible. My hydrometer wont even go neer the numbers
youd need to end up with 30% alcohol however! I think whatever method you are using is calculating the alcohol concentration
in %proof. 30% proof is about 15% vol. Most modern information defines 100% vol as 200% proof simplifying the maths
somewhat. 100% proof spirit was defined as the minimum amount of alcohol in water that would fail to extinguish gunpowder
and was slighlty more than 49.28% of alcohol by mass, or 57.1% by vol. Its fairly easy to see where the modern interpretation
came from, the value 49.28% is quoted frequently in literature without specifying mass or volume, and people assume volume
by default. Ordinary brewers or bakers yeast will go up to around 15%vol, what happens at slightly below this, 1 or 2%, the
yeast dies in its own excrement (The alcohol) and the enzymes that do the work stick around long enough to push it up
slightly higher. There is a special yeast thats apeared recently that will do between 18 and 20%/vol from sugar, but it is very
temperature sensitive.
Making alcohol from potatoes or rice. Dont bother, more trouble than its worth unless you are planning an industrial scale
method. You have to make a mash with water, apply enzmes to break the starch down, ferment, which produces an alcohol
level similar to beer, and get the stuff out all of which is done with a solution the consistancy of wallpaper paste. If you can
make neer 20% with sugar its just not worth the hassle. Domestic freezer just isnt cold enough to get anywhere with
reasonable amounts of alcohol. Adding dry ice will not freeze out pure water, youd have to do repeated melting/freezing to
avoid losing large amounts of ethanol. I had somewhere a good freezing point table for ethanol/water mixtures up to 25%
ethanol, but I need to find it If you can avoid oxidation of the ethanol at the anode, for example having a multi part cell,
electrolysis will work, very very slowly. Its total current passed that matters and that is likley to be very very small even with
fairly high voltages (for electrolysis). Its not worth trying I suspect, but try NaOH rather than acid, with nickle electrodes if you
want to give it a go. Just dont ever try drinking the product.
Making a simple pot still is easy, just buy a pressure cooker and about 60cm of 1cm dia copper tubing. Make a simple liebig
condensor out of the copper tubing with some wider plastic tubing and attach it to the pressure cooker. If you have to braze
use lead free solder, then you can prepare drinkable alcohol if you know how to make sure your drinks contain no methanol,
small amounts of which form during normal fermentation. Temperature measurement can be dispensed with, you will be able
to tell when you have most of the alcohol out of the solution, discard tops and tails. Repeat the operation a few times to get
neer 95% ethanol. Drying that with anhydrous magnesium sulphate will get you about 99.5% ethanol for chemical preps.
Methanol free ethanol is useful for a few things and far preferable if all you can get is mineralised methylated spirits, which
contain crude pyridine to make it smell and presumably taste utterly foul. I wont work with the stuff, it turns my stomache.
To answer a query much furthur up the thread, 1 theoretical plate is not equivalent to 1 bubble plate becuase the liquid above
is only slightly enriched, not containing the same composition as the condensate of the vapour going through it. All values of
theoretical plate for reflux stills depend on the amount of liquid you take from the top. The slower you remove distillate, the
higher the value and the purer the product. The better you insulate the column the less power you need to apply to keep the
reflux going. 1 drop per min is not unknown in organic preperative methods with a value of 200 theoretical plates, presumably
for around a 1 meter column.
Tyler_Durden October 2nd, 2002, 09:15 PM

Just a small addition to Marvin's post.... I believe it is not said to be "100% proof", you would just call it "100 proof", if you are
doing it customarily. And yes, the proof is equal to twice the percentage in volume. So 200 proof alcohol is, in fact, 100%
alcohol. Alcohol with a proof of 80, then, is 40% alcohol. But, as far as I know, it's not referred to as "90% proof" and so on.
...just a tiny little detail.
NoltaiR October 2nd, 2002, 11:31 PM

Ha! I forgot about this post. You guys are right about the percentages, I meant to say 30 proof which is in fact 15% alc. by
volume. And the highest percentages that can be achieved by fermentation alone is about 18-20% alcohol and this is only with
specialized yeasts that are more standing of slightly higher alcohol concentrations. My wines (depending on the fruit used)
have ranged from between 10-14% alcohol and to some of them I just added a *little* Crown Royal whiskey to give it more of
a kick.
But anyways yes I am still in the wine business. I tried constructing a very basic still a while back with some glass piping and
couplings but it took forever just to get a little condensation because it all just kept coming out as vapor :(
So I just stuck to fermenting and then adding a little whiskey to make it around 20-22% alcohol.
I have about 8 gallons left.. the last couple batches that I made was about a month ago which were two gallons of vanilla and
coconut wine and a gallon of peach and pear wine. I never used campden tablets as suggested (I could never find any place
that would sell them except for liquor stores and they required me to be 21) but my wines have never gone sour. I am getting
quite good at this hobby; best of all my parents don't take it away from me. When the wine is ready to be served I find the
best thing to do for flavor is to add a bit of fruit extract (I have been using vanilla, coconut, lemon, orange, and jamaican rum
extracts which can really a quite elegant flavor even if the wine hasn't aged very long).
Also my wines have all cleared. The first wines that I made are still setting and they have aged for a little more than 2 months
now and next time I get a chance to invite some friends over we will open a few bottles.
In the end, I think I might just want to find a career in bartending.. :D
Mendeleev April 2nd, 2004, 04:09 AM

I have fermented mead before and took a small sip of that, nothing hapenned. I plan on distilling it soon. Also, because I
can buy pure methanol, Denatured Ethanol at 95% for $10/gallon, and 91% isopropyl, I was more interested in butyl alcohol. I
read it can be fermented from starch, so I was thinkng about dissolving those packaging noodles in water and fermenting
them, I believe they are pure starch. Does anybody think this is feasible?
Tuatara April 5th, 2004, 07:37 PM

I'd doubt fermenting directly to butyl alcohol is possible. Most starch ferments include malted grain, which provides amylase
IIRC to convert the starch into glucose, which the yeast can use.
Noltair, I've been doing homemade wine for a number of years now - some success, some dismal failures, and one broken
demijohn that put 4.5 litres of plum wine into the carpet :(
Some things I've found:

1: Sterilise everything , including yourself (I go up to my elbows with the bisulphite.)
2: If to don't have grapes, then a good mix of fruits is needed to get the flavour balance.
3: Banana gravy is a fabulous addition - it adds body, and assists clearing (boil a ripe banana in a cup or so of water, strain,
and add liquid to the must).
4: Methode champagnoir is huge fun, and works really well with wine made from pears and apples. Maturation of at least a
year in the bottle is essential.
5: Don't go short on the fruit, or the result will be thin and tasteless.
Currently in production: 4.5l of boysenberry port - 1year old now and showing huge potential, just needs a little sweetening
with honey.
vulture April 6th, 2004, 06:58 AM

1: Sterilise everything , including yourself (I go up to my elbows with the bisulphite.)
Keep in mind that high SO2 content in wine is responsible for the "Chateaux Migraine" syndrome of bad quality wines.
tmp April 6th, 2004, 05:13 PM

I've made applejack without distillation by fermenting with distiller's yeast that
can go up to 22% alcohol by volume without imparting any flavors or aromas
so typical of wine and champagne yeasts. After the yeast settles out, I siphon
off the clear liquid and freeze it. Pour off the still liquid part while leaving the
ice behind. This takes 2 or 3 times to get a significant portion of water out of
the mix. When it will freeze no more I'm done. My hydrometer at 59 F tells
me that I have about 85 proof. Commerical producers actually used this
method for many years but now they just distill it to produce an apple brandy.
The yeast nutrient mentioned in previous posts is diammonium phosphate.

You only need 1/4 teaspoon at most for every gallon of fermentable mix.
It helps to bubble air through the mix before adding the yeast. Some yeasts
like oxygen in the mix for the initial growth stage before full fermentation
begins. The best dry yeast I've ever used is Alltech Superstart. The Lalvin
EC-1118, K1-V1116, and UvaFerm dry yeasts made by Lallemand of Canada
are also good choices. For liquid(and more expensive) yeast the champion
in this category is Eau de Vie(Water Of Life), made by Wyeast(#3347), which
can produce over 20% alcohol by volume. Don't use baker's yeast unless you
like a bread taste in your finished product.
If you don't mind the cost, a good still is made by Destilabs of Sweden.
It's made of stainless steel, uses broken up pieces of glass tubing in the reflux
column and produces 96% alcohol by volume if the temperature is kept at
78 C(Thermometer comes with the still). This one doesn't depend upon an
internal heating element so it can be run on a stove top. Look for them on
eBay.
As a side note, in the U.S. one of the early tax revolts occurred in 1794 -
The Whiskey Rebellion. George Washington called out the militia to backup
the tax collectors who were coming under fire by distillers in Western
Pennsylvania.

Keep in mind that the freeze process for increasing alcohol content does not remove the methanol! There's a bit of Irish
folklore which says the first glassful off the still must be offered to the fairies - thats the one with the bulk of the methanol in
it (poor fairies, no wonder there's so few of them about).
Vulture: when I said sterilise everything, I was referring more to any equipment used. You are quite right in that over-zealous
use of SO2 in the wine itself can lead to nasty product. I usually rinse equipment with bisulphite, followed by boiled water, and
I've had very few problems with bacterial spoilage.
The other yeast nutrient I always use is a little vitamin B1, about 5mg to 5l of must.
Wahur April 15th, 2004, 01:09 PM

Heh. Making homemade wine is easy. Just mix a lot of juice with sugar, about one kg sugar for 10l of juice, let it stand for a
while until it starts bubbling and ends it(don't let any oxygene get nearm you'l end up with a unpleasant surprise), then
filtrate, add more sugar and let it stand again until all the sugar is fermentated. My dad makes it every year from apples, god
it tastes good. He had about 80l of wine. And my granpa has the destillation machine for getting the ethanole out, he gets
nearly 94% pure alcohol.
Efraim_barkbit April 15th, 2004, 05:47 PM

I'd be weary of drinking home distilled alcohol, because take off the wrong fraction and you've got methanol... How do you
ensure you avoid this DBSP?
I talked to my chemistry teacher about that a couple of years ago, and she said that it wasnt possible to get methanol when
fermenting regular sugar.
it is produced when fermenting cellulose if I am not mistaken
When people die from methanol poisoning after drinking moonshine, it is because people has "cut" the booze with methanol
before selling.
Thats a reason not to buy moonshine from total strangers.
BUT I guess that it is only swedes that have this kind of problem, with our 200SEK (25US$) tax/liter of 40% alcohol :(
EDIT: I thougt the thing about thowing away the first dl is due to it containing a lot of fusel oil (you know, the stuff that makes
the booze taste like shit if not filtrated) because they have slightly lover boiling point or something
BTW, what the fucks happened to DBSP? :confused:

In my experience there is more than just ethanol produced. Certainly there was alcohol coming off my still before the BP of
ethanol. I dump that bit just to be safe - it was only 50ml or so out of 4.5l. It is also possible to get traces of the higher
alcohols too. Doubtless these are produced because one is not normally fermenting pure sugar, but a mix of cane sugar and
fruit sugar and all kinds of odd compounds from the fruit. This may also be one of the reasons why wine tastes disgusting for
at least the first 6 months - these alcohols slowly form esters with the acid in the wine (acetic, citric, malic, ascorbic and tartaric
acids will be present in varying amounts).
At any rate, for distilled alcohol I dump the first fraction, keep the rest up to about 98C, and filter the distillate twice with
activated carbon.
nbk2000 April 15th, 2004, 07:43 PM

DBSP has gone the way of the dodo, through voluntary extinction, so don't be expecting any replies from him anytime soon. ;)

Efraim,
Some methanol is inevitable when fermenting sugar. I suspect your chemistry teacher is probably not aware you can make
glycerol in large amounts by simple fementation of sugar either. This rather cunning trick was used to suppliment
nitroglycerine production in the past.
Aside from deliberatly adding methanol, the biggest problem is that in most countries people (including moonshiners) dont
generally ferment sugar to make alcohol for distilling, because sugar is expensive. They use foods with high starch, like grain,
potatoes or rice, and rely on enzymes to break the starch down to simple sugars for the yeast to ferment. If the breakdown
isnt complete fermentation of the starch produces methanol.
tmp April 19th, 2004, 05:34 AM

Just got a call from my sister yesterday. She wants some of my applejack
for my nephew's college graduation party. I told her I'll have to make a new
batch. I'm going to use the same technique I posted previously with some
modifications in hope that I can increase the proof(last batch was 85 proof).
I'm not sure this can be done without distillation. I'll post on this again when
I'm finished. Wish me luck ! :D :D :D
The_Rsert August 26th, 2004, 12:20 PM

Take 1kg sugar, 10g normal(!!!) barm/yeast and 4-5l Water and let it in an warm place (20-25C) for about 2-3 weeks.
Destill it.
You will get about 94% ethanol.
When you like to get anhydrous ethanol (98%+) mix it with a lot of calcium chloride and destill it again.
Efraim_barkbit September 14th, 2004, 02:19 PM

What do you all think about the "plastic still"?
www.amazingstill.com
sounds like a plan, dirt cheap too...

pays itself after about 3liters if you live in sweden hehe...
Marvin September 14th, 2004, 04:32 PM

Not a bad idea if all you want is drinkable spirits. Its the survivalist still turned inside out essentially. 1 litre in 24 hours
though, thats not exactly quick, but then it doesnt need supervision so maybe these things even out.
If people want to distill a lot of ethanol, or want high proof alcohol in one step I still think the best way is to mutilate a
pressure cooker adding a water condensor, very short length of copper pipe, say 30-40cm and add a cooling jacket would do.
The_Rsert September 24th, 2004, 04:36 PM

A few monts ago i had made alcohol from 1kg Sugar, 10g Yeast an 5l Water.
After about 2 Weeks in a aitight and oxygenfree container I destilled it.
Yield: About 500ml of pure Ethanol, 90%+.
croc January 15th, 2005, 10:23 PM

Sorry to bring up last years topic but have been looking left right and centre for information on how to test ethanol for
methanol.
I have read somewhere on http://www.homedistiller.org/ that the methanol content is found by observing the vapour
temperature but there is no method on how or where to get started.
I m sure there are also other ways to test bu t I just don t kno w how. Can anyb ody help me out?
tmp January 16th, 2005, 01:12 AM

Methanol, acetone, and other nasties come off a reflux column at less than
70C. The smell of the acetone is quite noticeable. The temperature in the
reflux column will rise up to about 78C. That's when the ethanol starts to
boil off. When the temperature exceeds 80C your getting the fusils(YECH!).
It takes some patience and practice to get just the ethanol fraction.
lucas January 21st, 2005, 03:08 AM

Using baker's yeast produces an inferior product to using brewer's yeast and yeast nutrients. I home brew quite a lot and also
home distill. Try to make a wash of 15-17%. Dont use more sugar than that as unfermented sugar will cause problems when
distilling. Also, is using yeast other than brewing yeast, the final alcohol strngth achievable may be less than 17% which
brewer's yeast can produce. Try to make 12-15% in that case. Citric acid is usefull as a nutriuent if you dont have anything
specificaly for the porpose. Allow the wash to settle for at leat a week after fermentation stops to allow the yeast and residues
to settle to the bottom. The wash should be almost as clear as water, or ideally as clear when distilled.
The first 1-2% of distillate collected is discarded. IE if distilling 4 litres of 17%, discard the first 10ml or so of the 750ml you
collect. The temperature of the collected vapour should be 78-80 when you start keeping the distillate. It depends on how
much reflux your still generates. Stop distilling at or before 90dec C. If you have a normal, non reflux still you will get 40-50%
from a 17% wash. A reflux still 70%, if you have a really good still, 80 %. Double distillation is neccesary for highter than that.
Pack your still with as much stainless steel wool as possible to increase the reflux.
The product should be diluted to 50% or so and then cleaned by use of granular activated carbon. preferably by passing
through a column of the material, slowly. Otherwise the alcohol can be cleaned by letting the activated carbon sit in the alcohol
for 1 week or more. The carbon cant be reused. The carbon should be washed with lots of water before use to remove mineral
salts and the finest carbon dust.
95% can also be turned into anhydrous alcohol by codistilling with a small amount of benzene. The first fraction is benzene/
water/ethanol, the second is benzene/ethanol and the third is ethanol. The product is undrinkable due to traces of benzene.
croc January 23rd, 2005, 11:09 PM

I don t think that I would go to the trouble of building a still and wasting money espe cially on cadmium free silve r solder, I m
taking into interest the different ways of purifying the alcohol instead of distilling.
http://www.homedistiller.org
Up the top go to, equipment/making a still/Stills that Aren't Stills.
As I have already made an alcoholic mix with normal yeast I think I will discard it and buy some winemakers yeast to mix with
store brought sugar.
This mix will first be separated from containing solids by distilling all liquids from solids. I have already joined 2 glass jars with
a copper pipe and silicon glue which will be heated on a hotplate.
Next I will purify it to 30-40% so it can be treated carbon, probably by freezing or slow evaporation.
When treating is finished I will leave it sit at a temperature s lightly above methanol s b oiling point (probably a bout 65c) until
2-5% has evaporated this will remove any excess methanol.
Lastly I will concentrate it as strong as I can get it.
Before I start my procedure is there anything I should know or mistakes I have made in my write up?
And would silicon or some plastics corrode into my mix or would they contain harmful substances which would make my product
non drinkable quality?
I will let u know how it goes.
xyz January 24th, 2005, 05:33 AM

If you leave it to sit at 65C until 2-5% has evaporated, you'll be losing a reasonable amount of ethanol along with what little
methanol there may be in there.
If you use pure white sugar for your wash then theoretically you shouldn't get methanol. Methanol comes from the breakdown
of pectin by the yeast, and is the result of washes made from fruit, vegetables, or grains.
In practice, you'll still get traces of methanol even in a sugar based wash, but the amounts will be seriously tiny. Commercially
produced vodka will contain much more methanol than alcohol made from a sugar based wash even if no steps are taken to
remove any of the methanol from the wash.
I once made 2.5L of approx 35% alcohol from 9L of 13% wash (which had been made using only water, white sugar, brewer's
yeast, and yeast nutrient, and fermented slowly at 20C). I concentrated it using the freezing method in a deepfreeze set at
the coldest possible setting. It had hardly any taste at all, leading me to beleive that it contained hardly any methanol or
fusels (ethanol itself is tasteless).
croc February 8th, 2005, 01:27 AM

I have the equipment I have information all I need now is the nutrients.
with fruit pulp or grapes not much yeast has to be added or nutrients because of the content in them already but when using a
sugar base alcohol nutrients have to be added.
What are the essential yeast nutrients which the yeast needs to survive under and what did you use to get your alcohol?
Have found the following nutrients that can be used.

Magnesium sulfate, marmite, fermaid k, folic acid, diammonium phosphate, citric acid (for pH.), niacin, calcium pantothenate,
thiamine hydrochloride and lallvin.
But have only found the following chemicals in brewing stores and other places. diammonium phosphate, citric acid,
magnesium sulfate(at supermarket) and some potassium salt which name I forgot.
FrankRizzo February 14th, 2005, 10:20 PM

Anyone have a copy of the brewing program, ProMash?
EDIT: Nevermind :) Cracks are available for the free eval version.
FrankRizzo February 23rd, 2005, 11:47 PM

Well, I guess I still DO need a copy of ProMash, or a link to a working crack for version 1.8a. The cracks that I found do not
work (file size mismatch or something).
Sorry about the double-post, I guess you can't edit your posts after a certain period of time.
Child-of-Bodom February 24th, 2005, 02:06 PM

Did anyone try immobilisation of yeast cells to produce alcohol?
It is very simple, and effective: make a suspention of yeast cells in a 2-3% sodium alginate solution, drip them into 0.2M
CaCl2, (a Ca-alginate complex forms, and you will get beads of 3-5mm diameter).
Filter the beads out, load them into a column and let water+sugar go through the column. (from under or above, depending
on you equipment).
With a simple pump and some simple glassware this would be a very nice system, you produce every hour of the day, and
your cells are not intoxicated by the alcohol as there is not a very high concentration.
You can get up to 8% alcohol with this method, and if you really like engineering you can probably build a continious (sp?)
destillation unit next to it....
Cells should remain active for a very long time, as they get alle the nutrition they want.
To keep the system sterile is also not too hard, just boil you water + sugar for an hour (to be sure), and there will be no
contamination as almost everything gets washed away. Na-alginate can be hold at 100C for 30 to get sterile. (autoclaving will
destroy it... I found out after 2 weeks trying... :( )
The only drawback will be probably the availebility of Na-alginate, but it is completely harmless, so it must be available via a
pharmacy or something.
Here is some more info: http://www.fao.org/docrep/w7241e/w7241e0a.htm
FUTI February 24th, 2005, 04:55 PM

Didn't try this but seen it work once when I visited a friend. Good fermentation rate!
Elucifer March 1st, 2005, 02:43 PM

canada rocks
rubbing alcohol compound at SDM = 97.5% ethanol, dry it with OTC dehydrated epsom salts
hydroponic store has conc. nitric acid at $40/3 litre
battery wholesaler has conc. sulfuric acid at $20 /3 liter
hydroponic store has ammonium nitrate in huge bags!!!! +/- 25 kilo
plastic wholesaler DCM in 4 litre can
hydroponic store has 40 % hydrogen peroxide
diesel truck store has 4 liter 98+% methanol
diesel truck store has 12 volt controlled ether injector which neatly empties can of ether into bottle (cooled) ($78) ( all big
diesel engines use ether injectors. propellant gases off, others separate easily using simple crockpot, 4 liter bottle, simple
column.
you folks try way to hard to get that which is easily had
all universities with chemistry departments have a place where glassware gets made or fixed, see the loney guy in the glass
lab for your needs
Jacks Complete March 7th, 2005, 08:47 PM

Alginate can be found at some model shops, as it is used for casting and moulding.
I made a batch of Schnaps with one of the super yeast kits once. Bloody horrid until you were drunk, then it was great. Trick
became obvious - either drink with mixers or drink something shop-bought first, then move on to the homebrew!
Really harsh homebrews can often be saved by a dash of lemonade. Works incredibly well with dodgy scrumpy (apple cider)
and has lead to more than one night of druken debauchery. :)


Stormhelm March 21st, 2005, 10:15 AM


I have made one of those, and I'm rather pleased with it.
Doesn't need supervision, doesn't look like your average still, especially when dismantled (which means no attention from the
cops...), and it makes decent alcohol.
Also, it lacks the dangers of a "normal" still (electricity, flammable liquids, heat, pressure...)
I usually run the alcohol through it twice. I get 35-40% in the first run, and about 60% in the second, which is more than
enough when it comes to recreational purposes :D . I haven't tried a third run, but if it works as a simple pot still, it should get
stronger. In fact, it's running right now... ;) Needless to say, I pour it through a column of activated carbon (40 x 1200 mm) to
polish it.
The production rate may be a bit slow if one seeks to mass-produce, but it's superb when one only needs a little booze for the
weekend.
Apart from spirits, I've also made my share of beer and various wines.

polish it.
weekend.


polish it.
weekend.
xyz July 6th, 2005, 01:15 AM

Sorry to dig up an old thread and all, but I have a new piece of kit to show off :D
A few australian members who I chat with on MSN have seen this, and persuaded me to post it here.
Basically it's a 50L gas heated reflux still that produces around 6L of 90% alcohol in 2 hours.
The reflux column (covered in purple insulation in the photos) is 75mm diameter and about 1.2m high, filled with 40-50
copper scouring pads as packing. The sheer size of the column and height of the packing is an attempt to make up for the
fact that the still has a reflux ratio of "sweet fuck all", relying entirely upon heat loss from the still head and the lyne arm (the
tube between the column and the condenser) to generate reflux liquid. This means that our purity is limited to around 90%
(compared to the 95.7% that could be obtained with more reflux) but that our still doesn't take very long to run at all. The
gauge at the top is a thermometer to monitor the temperature in the still. As you can see from the photos, the roof of the
shed was not high enough to accomodate the column, and had to be extended slightly.
The boiler is a 50L stainless beer keg that screws onto the column, my friend and I have 7 of these, and do our fermenting in
them before attaching them to the column to extract the alcohol, then attaching another, and so on... The gas burner is
extremely powerful, allowing us to heat the keg up to the right temperature within about 15 minutes, before turning down the
gas right down to do the actual distilling.
Condenser is a huge air cooled monstrosity taken from a water cooler, and placed in front of the biggest fan we could find. It's
mounted out on the roof of the shed. A small copper tube goes from the bottom of the condenser, back through another hole
drilled in the roof, and into a bottle, allowing the distillate to be collected.
The distillate is still flammable even when mixed 50/50 with water :cool: , hence why I felt the need to photoshop a nice label
for it :) .
xyz July 6th, 2005, 01:15 AM

Sorry to dig up an old thread and all, but I have a new piece of kit to show off :D
A few australian members who I chat with on MSN have seen this, and persuaded me to post it here.
Basically it's a 50L gas heated reflux still that produces around 6L of 90% alcohol in 2 hours.
The reflux column (covered in purple insulation in the photos) is 75mm diameter and about 1.2m high, filled with 40-50
copper scouring pads as packing. The sheer size of the column and height of the packing is an attempt to make up for the
fact that the still has a reflux ratio of "sweet fuck all", relying entirely upon heat loss from the still head and the lyne arm (the
tube between the column and the condenser) to generate reflux liquid. This means that our purity is limited to around 90%
(compared to the 95.7% that could be obtained with more reflux) but that our still doesn't take very long to run at all. The
gauge at the top is a thermometer to monitor the temperature in the still. As you can see from the photos, the roof of the
shed was not high enough to accomodate the column, and had to be extended slightly.
The boiler is a 50L stainless beer keg that screws onto the column, my friend and I have 7 of these, and do our fermenting in
them before attaching them to the column to extract the alcohol, then attaching another, and so on... The gas burner is
extremely powerful, allowing us to heat the keg up to the right temperature within about 15 minutes, before turning down the
gas right down to do the actual distilling.
Condenser is a huge air cooled monstrosity taken from a water cooler, and placed in front of the biggest fan we could find. It's
mounted out on the roof of the shed. A small copper tube goes from the bottom of the condenser, back through another hole
drilled in the roof, and into a bottle, allowing the distillate to be collected.
The distillate is still flammable even when mixed 50/50 with water :cool: , hence why I felt the need to photoshop a nice label
for it :) .
CommonScientist July 14th, 2005, 04:22 PM

What do you guys use to ferment your wort? I was thinking about making 200 liters of mash, it would take a 55 gallon plastic
drum, and the airlock, ever important, would consist of a 5 gallon bucket filled with water, and peice of hose running from the
top of the barrel to inside the barrel. Gasses can escape, but nothing can go in. Distillation of that amount of mash would yeild
22L of 95% alcohol on a reflux still. According to homedistiller.org, I would need 100kg of sugar. Add 138L of water, that
makes 200L of mash at 29.4% alcohol.
Now, I dont know about you foreign guys, but im pretty sure that 100kg of suger is a lot of money, in US$$ that is. Since I
have an apple tree on my property, I think I will use apples, or use some corn meal from a local farm.
Now all I have to do is get the materials for the still.... I can get a 55 gallon SS drum, more $$ though.
Keep in mind, Im using this for fuel purposes

What do you guys use to ferment your wort? I was thinking about making 200 liters of mash, it would take a 55 gallon plastic
drum, and the airlock, ever important, would consist of a 5 gallon bucket filled with water, and peice of hose running from the
top of the barrel to inside the barrel. Gasses can escape, but nothing can go in. Distillation of that amount of mash would yeild
22L of 95% alcohol on a reflux still. According to homedistiller.org, I would need 100kg of sugar. Add 138L of water, that
makes 200L of mash at 29.4% alcohol.
Now, I dont know about you foreign guys, but im pretty sure that 100kg of suger is a lot of money, in US$$ that is. Since I
have an apple tree on my property, I think I will use apples, or use some corn meal from a local farm.
Now all I have to do is get the materials for the still.... I can get a 55 gallon SS drum, more $$ though.
Keep in mind, Im using this for fuel purposes
xyz July 14th, 2005, 10:37 PM

No way in hell you'll get 29.4% alcohol just by fermenting a wash. Even the strongest commercial turbo yeasts can't take that
kind of punishment.
You want to keep your sugar concentration below 0.25g/mL for baker's yeast or below 0.35g/mL for turbo yeasts.
This is for two reasons, the first being that if there's too much sugar in the wash then the difference in osmotic potential will
kill most of the yeast as soon as you add it (the sugar draws too much water out of the yeast cells).
The second is that alcohol becomes toxic to yeast at high concentrations (after all, yeast being in alcohol is equivalent to a
human being in sewage). Turbo yeasts will tolerate higher concentrations of alcohol without being killed off, but still not as
high as 29.4%.
The highest alcohol % I've ever heard of being produced by fermentation by yeast is around 22% using a highly specialised
turbo yeast, accurate temperature control, and adding the sugar in "steps" to reduce osmotic shock to the yeast.
Personally, I just stick to sugar concentrations of 0.25g/mL or below, where baker's yeast works fine. This is because I can get
15Kg (yes, Kg...) of baker's yeast for $45AUD, compared to turbos which cost $9AUD for 20 grams... :rolleyes:
Anyway, back to your question...
DON'T waste apples on fuel alcohol (if it's really for fuel that is... ;) ). It will be far cheaper to use sugar than have to worry
about juicing the apples and boiling down the juice to 1/2 volume to reach a good concentration of sugar in it.
Far better is to have a pot still and make some decent apple brandy / calvados from those apples.
Corn meal sounds like a good way to go, but then you need to add malted grains to the wash in order to get some enzymes
in there to break the corn starches down into fermentable sugars.
Back to sugar, for 200L of wash, you'd want a maximum of about 50Kg of sugar in there if you're using baker's yeast (the only
way to really go for a wash that size, turbos will generate so much heat that they kill themselves unless you can cool the wash
somehow).
Now I don't know about you, but here it costs $40AUD for 50Kg of sugar from a bulk food supplier, which isn't bad at all when
you consider that 50Kg of sugar means over 30L of 90% alcohol.
xyz July 14th, 2005, 10:37 PM

No way in hell you'll get 29.4% alcohol just by fermenting a wash. Even the strongest commercial turbo yeasts can't take that
kind of punishment.
You want to keep your sugar concentration below 0.25g/mL for baker's yeast or below 0.35g/mL for turbo yeasts.
This is for two reasons, the first being that if there's too much sugar in the wash then the difference in osmotic potential will
kill most of the yeast as soon as you add it (the sugar draws too much water out of the yeast cells).
The second is that alcohol becomes toxic to yeast at high concentrations (after all, yeast being in alcohol is equivalent to a
human being in sewage). Turbo yeasts will tolerate higher concentrations of alcohol without being killed off, but still not as
high as 29.4%.
The highest alcohol % I've ever heard of being produced by fermentation by yeast is around 22% using a highly specialised
turbo yeast, accurate temperature control, and adding the sugar in "steps" to reduce osmotic shock to the yeast.
Personally, I just stick to sugar concentrations of 0.25g/mL or below, where baker's yeast works fine. This is because I can get
15Kg (yes, Kg...) of baker's yeast for $45AUD, compared to turbos which cost $9AUD for 20 grams... :rolleyes:
Anyway, back to your question...
DON'T waste apples on fuel alcohol (if it's really for fuel that is... ;) ). It will be far cheaper to use sugar than have to worry
about juicing the apples and boiling down the juice to 1/2 volume to reach a good concentration of sugar in it.
Far better is to have a pot still and make some decent apple brandy / calvados from those apples.
Corn meal sounds like a good way to go, but then you need to add malted grains to the wash in order to get some enzymes
in there to break the corn starches down into fermentable sugars.
Back to sugar, for 200L of wash, you'd want a maximum of about 50Kg of sugar in there if you're using baker's yeast (the only
way to really go for a wash that size, turbos will generate so much heat that they kill themselves unless you can cool the wash
somehow).
Now I don't know about you, but here it costs $40AUD for 50Kg of sugar from a bulk food supplier, which isn't bad at all when
you consider that 50Kg of sugar means over 30L of 90% alcohol.
Jacks Complete July 15th, 2005, 05:26 AM

CommonScientist, just get yourself down the wholesalers, and you will find sugar is actually silly cheap in bulk. I once bought
something daft like 12 Kilos because it was as cheap as one and a half bags from the supermarket!
I agree with not wasting the apples - make cider! And you will have a lot more trouble with the apple skins clogging things up.
Having said that, apple skins tend to have yeasts on them, which is how cider used to be made. Just crush and go! But that
would tend to ruin a turbo yeast system.
XYZ, could you not simply breed the yeasts and make yourself more money? Just stop the reaction at 10% alcohol by dilution
with a weak sugar solution, until it gets back up to 10%, and you will soon have lots of turbo yeast. Then stop the reaction
(not sure how - freeze? freeze dry? dry?) and you would have a load to sell on.

CommonScientist, just get yourself down the wholesalers, and you will find sugar is actually silly cheap in bulk. I once bought
something daft like 12 Kilos because it was as cheap as one and a half bags from the supermarket!
I agree with not wasting the apples - make cider! And you will have a lot more trouble with the apple skins clogging things up.
Having said that, apple skins tend to have yeasts on them, which is how cider used to be made. Just crush and go! But that
would tend to ruin a turbo yeast system.
XYZ, could you not simply breed the yeasts and make yourself more money? Just stop the reaction at 10% alcohol by dilution
with a weak sugar solution, until it gets back up to 10%, and you will soon have lots of turbo yeast. Then stop the reaction
(not sure how - freeze? freeze dry? dry?) and you would have a load to sell on.

XYZ, 50kg of sugar in a 200L wash would yeild roughly 15% alcohol. Thats great for me.
I have abandoned the reflux still design, and have opted for the pot still. I will have a thumper between it and the condenser,
which I figure will be a coil of 1" copper tubing in a 6" coil 86" long. My input water temp is 15* C and exit is 30*C, and I am
thinking of using an old car radiator and fan for cooling the water down to 15*C = 59*F, if I am lucky, I can get it colder. I was
also thinking of a triple jacketed coil, would have the main water jacketed coil inside, and another jacket about an 2" larger in
diameter than the other jack, so I have an inch space on either side. Inside, I will have fins on the main coil jacket that will
conduct heat out into the windstream of a fan mounted on top, input for cooling water and vapor line come through.
Check out the attachment I have added here, its a crappy paint sketch, but it gives you an idea.

XYZ, 50kg of sugar in a 200L wash would yeild roughly 15% alcohol. Thats great for me.
I have abandoned the reflux still design, and have opted for the pot still. I will have a thumper between it and the condenser,
which I figure will be a coil of 1" copper tubing in a 6" coil 86" long. My input water temp is 15* C and exit is 30*C, and I am
thinking of using an old car radiator and fan for cooling the water down to 15*C = 59*F, if I am lucky, I can get it colder. I was
also thinking of a triple jacketed coil, would have the main water jacketed coil inside, and another jacket about an 2" larger in
diameter than the other jack, so I have an inch space on either side. Inside, I will have fins on the main coil jacket that will
conduct heat out into the windstream of a fan mounted on top, input for cooling water and vapor line come through.
Check out the attachment I have added here, its a crappy paint sketch, but it gives you an idea.
xyz July 16th, 2005, 06:30 AM

Jack, first off, any yeast on apple skins should have no effect on turbo yeasts. The turbos work so quickly that the naturally
occuring yeasts will die of alcohol poisoning before they can affect anything by much.
As for breeding a turbo yeast, I've considered that, 2 problems though...
1. Turbos are not known for their genetic stability, and 10 generations down the line your yeast may be nothing like what it
was before, and may do nasty things to the wash (produce excessive amounts of unpleasant byproducts, e.t.c.)
2. "Turbo Yeast" doesn't just contain yeast. It also has a ridiculously complicated nutrient mixture in there as well (in order to
make sure that people need to use all of it I assume, because the companies just wouldn't stand for letting people use less
than the whole sachet...).
My nutrient mix for a 50L sugar wash is 1 iron tablet, 1 multivitamin tablet, and 200g of CHEMICAL lawn fertiliser (NOT
anything organic). Yeah, it may sound crazy putting fertiliser in there if the alcohol is for drinking, but remember that it's
distilled first and all the fertiliser is removed, just as the salt is removed from distilled seawater.
Anyway, this nutrient mixture, along with 500g of baker's yeast, seems to perform quite well up to the 15% mark, taking
around 5 days to ferment at 25C.
I can't view your attachments yet, but whatever you do with a car radiator, DO NOT let the car radiator come into contact with
the distillate in ANY way. Never use a car radiator as a condenser. This is because they're lead soldered. There were many
cases of serious lead poisoning back during the prohibition in America due to people using car radiators as the condensers in
their moonshine stills.
As for 50Kg of sugar in 50L of wash, I only hope that was a typo and you meant to say 200L of wash...
xyz July 16th, 2005, 06:30 AM

Jack, first off, any yeast on apple skins should have no effect on turbo yeasts. The turbos work so quickly that the naturally
occuring yeasts will die of alcohol poisoning before they can affect anything by much.
As for breeding a turbo yeast, I've considered that, 2 problems though...
1. Turbos are not known for their genetic stability, and 10 generations down the line your yeast may be nothing like what it
was before, and may do nasty things to the wash (produce excessive amounts of unpleasant byproducts, e.t.c.)
2. "Turbo Yeast" doesn't just contain yeast. It also has a ridiculously complicated nutrient mixture in there as well (in order to
make sure that people need to use all of it I assume, because the companies just wouldn't stand for letting people use less
than the whole sachet...).
My nutrient mix for a 50L sugar wash is 1 iron tablet, 1 multivitamin tablet, and 200g of CHEMICAL lawn fertiliser (NOT
anything organic). Yeah, it may sound crazy putting fertiliser in there if the alcohol is for drinking, but remember that it's
distilled first and all the fertiliser is removed, just as the salt is removed from distilled seawater.
Anyway, this nutrient mixture, along with 500g of baker's yeast, seems to perform quite well up to the 15% mark, taking
around 5 days to ferment at 25C.
I can't view your attachments yet, but whatever you do with a car radiator, DO NOT let the car radiator come into contact with
the distillate in ANY way. Never use a car radiator as a condenser. This is because they're lead soldered. There were many
cases of serious lead poisoning back during the prohibition in America due to people using car radiators as the condensers in
their moonshine stills.
As for 50Kg of sugar in 50L of wash, I only hope that was a typo and you meant to say 200L of wash...

Just as a thought, I heard yesterday that sugar is three times more expensive in the EU than outside, due to trade restrictions
and quotas!
Something I just thought of, which could be quite a fun trial. Take your water/sugar mix, and put it in a sectional tank with a
very fine (molecular sieve) filter in it, that will let the alcohol molecule pass through by osmosis. Add yeast to one side of the
tank.
Remove alcohol/water/sugar only side every time it gets up to a high enough concentration, and replace with sugar/water. This
will keep the alcohol concetration down low, so that the yeast doesn't die. Distill off the alcohol, then return the sugar water left
behind to the mix.
I don't know if this would work - the water/alcohol/sugar mix might caramelise, or something, and the whole thing might not
work.
However, if it does, then the whole thing could be turned into a continuous production line! Using vacuum distillation would
probably be better than heat, though.
Please realise I'm no expert in this stuff - I did a home brew kit once in my life - but those who know better might be able to
comment on or use this for something.

Just as a thought, I heard yesterday that sugar is three times more expensive in the EU than outside, due to trade restrictions
and quotas!
Something I just thought of, which could be quite a fun trial. Take your water/sugar mix, and put it in a sectional tank with a
very fine (molecular sieve) filter in it, that will let the alcohol molecule pass through by osmosis. Add yeast to one side of the
tank.
Remove alcohol/water/sugar only side every time it gets up to a high enough concentration, and replace with sugar/water. This
will keep the alcohol concetration down low, so that the yeast doesn't die. Distill off the alcohol, then return the sugar water left
behind to the mix.
I don't know if this would work - the water/alcohol/sugar mix might caramelise, or something, and the whole thing might not
work.
However, if it does, then the whole thing could be turned into a continuous production line! Using vacuum distillation would
probably be better than heat, though.
Please realise I'm no expert in this stuff - I did a home brew kit once in my life - but those who know better might be able to
comment on or use this for something.

Where would I get a molecular sieve? It sounds as it would work...just dont know how or where to get one..
Anyone here ever use a water heater to make a still, Im thinking 50-80 gallons, but I need to find some elements/coils to put
in it. It takes 12kW to heat the 200L of wash to boil from room temp in 77 minutes, and roughly 70 minutes for 20kW to heat
the 302L(80 gallons) of wash to boiling. Where Im going to get that kind of power, im not sure, I might just use a wood fire,
put some heavy steel plate on the bottom of where the burner would hit it normally on the bottom, so it doesnt burn out or
rust out as much. Post any comments or advice, any knowledge is power.

Where would I get a molecular sieve? It sounds as it would work...just dont know how or where to get one..
Anyone here ever use a water heater to make a still, Im thinking 50-80 gallons, but I need to find some elements/coils to put
in it. It takes 12kW to heat the 200L of wash to boil from room temp in 77 minutes, and roughly 70 minutes for 20kW to heat
the 302L(80 gallons) of wash to boiling. Where Im going to get that kind of power, im not sure, I might just use a wood fire,
put some heavy steel plate on the bottom of where the burner would hit it normally on the bottom, so it doesnt burn out or
rust out as much. Post any comments or advice, any knowledge is power.
Jacks Complete July 16th, 2005, 07:36 PM

I was thinking some kind of permeable barrier, something like an ultrafine filter paper. I can't remember much about osmotic
forces, I'll have to search.
Right, it would be reverse osmosis. You could perhaps use a Gortex filter, or one of the filters used for water purification.
Apparently, sucrose is stopped by them, but water is not. I don't know whether ethanol would be or not.
I think this idea is a bit of a bust, since it would cost a lot more than just doing it normally.

I was thinking some kind of permeable barrier, something like an ultrafine filter paper. I can't remember much about osmotic
forces, I'll have to search.
Right, it would be reverse osmosis. You could perhaps use a Gortex filter, or one of the filters used for water purification.
Apparently, sucrose is stopped by them, but water is not. I don't know whether ethanol would be or not.
I think this idea is a bit of a bust, since it would cost a lot more than just doing it normally.
FUTI July 17th, 2005, 03:51 PM

to Jack's Complete: Yes sugar will decompose partially during destillation...that's why they check for furfural level inside the
strong alcoholic beverage...to stop you doing that recycling sugar step. Nice idea though only if it wouldn't make more trash to
emerge in the batch (some ketones and higher alcoholes for example) and in time due to accumulation of the same kill the
yeast that makes the stuff.
Did you mean pervaporation in the last post Jack, or something like reverse osmosis?
FUTI July 17th, 2005, 03:51 PM

to Jack's Complete: Yes sugar will decompose partially during destillation...that's why they check for furfural level inside the
strong alcoholic beverage...to stop you doing that recycling sugar step. Nice idea though only if it wouldn't make more trash to
emerge in the batch (some ketones and higher alcoholes for example) and in time due to accumulation of the same kill the
yeast that makes the stuff.
Did you mean pervaporation in the last post Jack, or something like reverse osmosis?

FUTI,
it would be reverse osmosis. I don't think the "trash" would emerge, since you would only be removing the alcohol, glucose
and water, plus anything else that went through the barrier. The anything else is what you would need to check up on!
Mash particles, ketones, etc. should never get out of the one side, and should also be kept to a low level because the alcohol
concentration should never get very high, and the sugar concentration should never drop too low. You could also drop a little
more yeast in every so often, too, to keep the yeasts as a genetically stable population.
This would allow a stream production, rather than a batch production, in theory.
FUTI,
it would be reverse osmosis. I don't think the "trash" would emerge, since you would only be removing the alcohol, glucose
and water, plus anything else that went through the barrier. The anything else is what you would need to check up on!
Mash particles, ketones, etc. should never get out of the one side, and should also be kept to a low level because the alcohol
concentration should never get very high, and the sugar concentration should never drop too low. You could also drop a little
more yeast in every so often, too, to keep the yeasts as a genetically stable population.
This would allow a stream production, rather than a batch production, in theory.
CommonScientist July 20th, 2005, 01:45 AM

I just calculated that if I can get 20% in my wash by using turbo yeasts, and distill 80 gallons(302L), I can get roughly 60L of
95% alcohol (15.8 gallons) out of it. Thats enough alcohol to make 150 gallons of 10% gasohol, or 100 gallons of 15%
gasohol. 15 gallons on the otherhand, can be dilluted with NM to make a superfuel, which would be great on a Jr. Dragster, or
a drag bike, or maybe a super go-kart. :) :D ;)
CommonScientist July 20th, 2005, 01:45 AM

I just calculated that if I can get 20% in my wash by using turbo yeasts, and distill 80 gallons(302L), I can get roughly 60L of
95% alcohol (15.8 gallons) out of it. Thats enough alcohol to make 150 gallons of 10% gasohol, or 100 gallons of 15%
gasohol. 15 gallons on the otherhand, can be dilluted with NM to make a superfuel, which would be great on a Jr. Dragster, or
a drag bike, or maybe a super go-kart. :) :D ;)
FrankRizzo July 28th, 2005, 01:47 AM

Common,
If you're thinking about trying alternative fuels, don't. The energy necessary to distill alcohol and refine it to a grade suitable
for burning in an engine will far exceed the energy that you will get out of the resulting material; just spend the money on
gasoline.
OTOH, if you're making drinkable spirits, more power to ya :-)
FrankRizzo July 28th, 2005, 01:47 AM

Common,
If you're thinking about trying alternative fuels, don't. The energy necessary to distill alcohol and refine it to a grade suitable
for burning in an engine will far exceed the energy that you will get out of the resulting material; just spend the money on
gasoline.
OTOH, if you're making drinkable spirits, more power to ya :-)
NoltaiR November 15th, 2005, 03:42 PM

This is my newest work. Have been experimenting with various kits online (both liquid and solid mixes). I am thinking of just
starting to grow my own stuff. Anybody tried this?
xyz November 19th, 2005, 05:22 AM

Yeah, I've tried absinthe from some commercial liquid kits and am currently stalled partially through the process of doing it
the real deal way with wormwood (I have A. absinthium and A. pontica plants).
The alcohol used was home distilled and diluted back to 70% from 90%, search the forum for "xyz reflux column alcohol" or
something along those lines if you want to see my setup. EDIT: It's on page 3 of this thread, I'm silly...
The liquid kits made a rather nice drink with definite wormwood and anise tastes, but I can't say I noticed anything in the way
of activity from that stuff.
The home made stuff on the other hand (wormwood, fennel seed, aniseed, angelica root, and a few other minor ingredients I
can't remember offhand, the first three beign the main ones) produced a drink that was ridiculously dark green and
horrendously bitter after maceration (no, I don't drink it like this, I just tasted it :) , bad...).
Due to the small volume (1 litre) that I macerated I don't want to put it through the still as I know that it will probably boil dry
before I get any appreciable amount out of the condenser. My still is meant to handle 50 litres, not 1, so I'm scared to mess
around with small volumes. Yes, I know I could just go really slow, but it would still be far from exact or certain.
So, basically I won't have the results of my homemade stuff until I either get around to macerating some more, or build a
small potstill for projects such as this (something I'm planning on doing eventually, because although a gigantic fuckoff reflux
still wins for purity and output, it just doesn't involve the same degree of art as a potstill).
Back when a friend and I first started distilling I was of the opinion that it's all science and that stories of the art involved or of
individual stills having their own "personalities" were a load of rubbish. Now I simply beleive that the science involved is far too
complicated for a scientific approach to be taken, so thinking of it as an art makes things easier. Yes, stills definitely do
behave like they have individual personalities, and you have to know how yours behaves before you can get really good
results. Changing even a small, seemingly insignificant detail (such as whether a part is copper or stainless steel (in areas
where heat transfer doesn't matter), seems like it would have no effect and this one puzzled scotch distillers for quite some
time, but they now know copper helps to catalyse the decomposition of some impurities) will noticeably change your results.
One last word, avoid plastics at all costs. I once used some food grade plastic tube as a collection tube from the condenser.
The alcohol in contact with it wasn't hot or anything, just barely above room temperature, but to cut a long story short the
distillate had a horrible plastic taste and an inspection of the tube showed it had been noticeably reacted with on the inside.
NoltaiR November 20th, 2005, 12:01 AM

My first batch that I have ever made was a 'dry kit' that I ordered online. It came with little baggies of wormwood, star anise,
licorice root, etc. The only requirement was that I have a litre of high proof alcohol. It didn't specify which and I just happened
to have new bottle of Bacardi 151 available.
I prepared the stuff as instructed.. used dark-colored glass containers for storage during the process of making it.
When I was done, I had this absolutely astringent (bitter seems like an understatement) liquid. And due to the naturally
golden color of Bacardi 151, I ended up with a litre of brown alcohol that smelled terrible.
I tried taking it in shots but I would gag and just couldn't hold it down. Then I made jello shots with it. This definitely covered
the taste.. I just several jello packets so that the resulting gelatine was hard enough that it could be swallowed without the
wormwood taste making me puke.
I had a bit of a drunken feeling but it wasn't anything like how I normally feel when intoxicated.. but then again I am not sure
if that was because of the thujone or just the vile mix being in my stomach.
Anyways I have long since progressed since then. I now use liquid kits available online... they are a bit harder to come by and
produce far less thujone (20-30mg as opposed to the 60-100mg from solid kits) but they make a very consumable drink.
--You still need to use the sugar to cover the taste though... plus thats the ritual anyways.--
I also have gotten smarter and use Everclear now.
Well like I said I want to make this stuff from scrath.. i.e. grow my own plants.. but then I will be back to square-one using a
solid mix. I have heard that the commercial plants that make absinthe distill the final product even after the thujone has been
induced. This will be my next endeavor.
THe_rEaL_dEaL January 27th, 2006, 12:30 PM

Ive read lots of differing opinions about the use of alcohol as a pure car fuel and as a gasoline mix (gasohol).
For gasohols the EtOH must be very pure (water impurities in the ethanol mix makes mixing with non polar parts of gasoline
hard and they tend to separate out. This high purity level uses large amounts of heat to achieve.
Water/Alcohol injection for cooling and as part fuel/octane increasing source only requires alcohol of only approx 50% (100
proof) which would decrease the amount of energy required in the distillation dramatically.
Pure alcohol as a fuel can be 90% to 95% and work fine while also having a much higher octane (approx. 110-115 octane)
In Brazil molasses and sugar from sugarcane is fermented into alcohol. The leaf and stalk waste (baggasse) is burnt to
produce steam for dist of the alcohol for fuel and to power the factory. Some factories have enough energy left over that they
sell it to the power grid.
Here are some good links:
Use of ethanol as a fuel in Brazil and its production from sugarcane

http://en.wikipedia.org/wiki/Ethanol_fuel_in_Brazil
Detailed info and theory on distillation apparatus.

http://lorien.ncl.ac.uk/ming/distil/distilop.htm#
"The Manual for the Home and Farm Production of Alcohol Fuel"
Info and specs on feed stocks, fermentation, dist. and use as a fuel.
http://journeytoforever.org/biofuel_library/ethanol_manual/manual_ToC.html
croc January 29th, 2006, 02:39 AM

Last night I herd from my friends that distilling alcohol (possibly grapper) lets off a huge stench. They were told from
somebody who has tried. It stunk out their whole block for d ays. I don t kno w how m uch overexaggerating was do ne there
but it made me think. Even if it only stunk out your next door neighbours houses for a few hours people could get suspicious
and call the police.
Has anybody else has trouble with the stench which I herd of or does this only happen when distilling spirits like grapper?
xyz February 1st, 2006, 03:25 AM

First off, it's grappa, not grapper...
Yeah, grappa stinks when distilled, which is why the local italians always pay attention to which way the wind is blowing when
they fire up their stills.
As for distilling a neutral spirit wash (sugar and nutrients), there is hardly any smell whatsoever, although some mighty wierd
smells can get produced (pineapple, to name one...) due to the formation of trace amounts of esters by the yeast. You'll only
notice it if you smell the still outlet or afterwards when cleaning it though, the smells from a sugar wash are not strong at all.
Dog House June 28th, 2006, 01:09 PM

It is necessary in just about every country to have a license to distill spirits. Emphasis on the distill part, you can ferment all
you want legally, although drinking just that will most likely kill you. In the US at least the license is rather cheap and they
have to give it to you.
Interesting idea. I have a few questions:

All of which can be answered by searching the internet your own damn self. :)

and Improvised Chemistry > potassium nitrite synthesis
Log in
View Full Version : potassium nitrite synthesis

for the past few weeks i've been working on DDNP as a primary. everything can be made or aquired easily apart from a nitrite
salt. i have posted this new topic for people to just throw ideas nomatter how extraordinary or insane (may provoke thought)
they sound for the preparation of HNO2 or a salt of it such as KNO2. i am particularly interested in preparing it from KNO3 as
this is readily available. i have tried using Al and KNO3 which seems to work but the yields are really poor. also is there a
method to prepare NO and NO2 from one reaction?
any help will be appreciated.

While nitrites have never interested me, I do recall that nitrates can be decomposed into nitrites by heating. I doubt it may be
that simple, but then again it may not be too far off. You may have to mix the nitrates with something to liberate the oxygen.
mongo blongo July 27th, 2002, 10:42 PM

Yes heating with elemental lead to remove the oxygen. It will give PbO and a metallic nitrite (if you used a metallic nitrate).
kingspaz July 28th, 2002, 08:12 AM

i am aware of both of those processes as i recall nbk a while ago saying if you left KNO3 molten long enough it would
gradually decompose. also the lead process, why lead? is it due to the low melting point? other than that i cannot see any
reason why lead would be used since there are many much more reactive metals which could be used more effectively. also is
there a way to generate NO and NO2 simultaneously as this may prove easier than synthesising a nitrite.
mongo blongo July 28th, 2002, 11:01 AM

Lead is a good choice because the melting point is low and the reaction is easy to control. There are some more reactive
metals but using something like Al or Mg with say KNO3 is a bad idea. Also Pb is very easy to find and quite cheap.

mongo, have you had any success with the process? if so can you please describe the procedure you used, ratios of KNO3 and
Pb aswell as heating time....i think heating time is the crucial thing.
[ July 28, 2002, 05:13 PM: Message edited by: kingspaz ]
xoo1246 July 28th, 2002, 06:00 PM

Aren't you thinking of sodium nitrite?(the more noble the metal the more metal oxide you get)
Then you separate the nitrite from PbO by dissolving it in distilled water I assume.
Edit: From The Hive
Helvetica">On a laboratory scale, the melt-phase reduction of alkali nitrates (preferably NaNO3 is used) with metallic lead is
suitable for the production of nitrites:
NaNO3 + Pb ==> NaNO2 + PbO
One melts 1 mol (85 g) sodium nitrate in an iron crucible of approx. 15 cm diameter and 1 mole (207 g) of metallic lead (cut
into small pieces) is added slowly with good agitation. After all the lead is added, the mixture is agitated for a further 30-45
minutes until all the lead is oxidized. Careful agitation is important for the achievement of a good yield. After cooling the
reaction mixture, the solid cake left is cut up into smaller pieces and placed in a larger iron container. The formed sodium
nitrite is extracted with 200ml of warm water, followed by two 75ml portions of water, and the insolubles is filtered off (Caution:
Lead oxide is very poisonous!). To remove remaining lead from the aqueous solution, carbon dioxide is bubbled through for
one minute (not longer!) and the insolubles again filtered off. After neutralization with dilute nitric acid, the solution is
concentrated under vacuum. The first crop of crystals which precipitates consist largely of sodium nitrate. Now the solution is
evaporated to dryness, and the still molten residue (consisting of sodium nitrite contaminated with some sodium nitrate) is
washed briefly with ethanol. Care must be taken not to heat the sodium nitrite much higher than its melting point (271C) as
the compound decomposes at 320C, with evolution of nitrogen oxides. <hr /></blockquote>
[ July 28, 2002, 05:19 PM: Message edited by: xoo1246 ]
Polverone July 29th, 2002, 12:50 AM

I tried a number of times to prepare potassium and sodium nitrite from metallic lead and the nitrates before I gave up and
just ordered the NaNO2. The nitrites of both K and Na (IIRC) decompose at nearly the same temperature as the nitrates
decompose to form the nitrite. So it was very tough for me, since I wasn't able to keep the temperature very controlled. One
could (I suppose) keep the temperature at a reasonable level by repeatedly withdrawing the heat source until the liquid begins
to solidify, then replace it, so that the material is always held near its melting point. But I didn't have enough patience for
that, especially since I found a place that would sell me NaNO2 for $3.00 a pound. I'd just e-mail you the name of the dealer
but you're in the UK so it'd do you no good :(
When I made my attempts with lead I heated the material strongly and stirred with a spoon. It looked like the lead was
oxidizing nicely but when I filtered my reactants I saw that most of the lead had remained unchanged. The material I obtained
gave only the faintest haze of red gas when I added HCl to it, and pure NaNO2 gives you copious red-brown clouds upon
addition of HCl. I made some attempts with lead and some without, and the ones without it actually seemed to work better,
but I can't guarantee that since the heating conditions were so uncontrolled.
Gleaned from the Hive:
US patent 792,515
2NaNO3 + 2NaOH + C = 2NaNO2 + Na2CO3 + H2O
2NaNO3 + Ca(OH)2 + C = 2NaNO2 + CaCO3 + H2O
(CaCO3 is insoluble in H2O)
US patent 670,021
NaNO3 + CaO + SO2 = NaNO2 + CaSO4
KNO3 + K2SO3 = KNO2 + K2SO4
If you get frustrated with the lead-reduction procedure those patent methods might be worth trying.

hey thanks guys!
i'll look at those patents and if neither of the processes are workable i'll have an attempt at the lead process as xoo has
posted.
thanks again!
edit: i tried one synth from the patent following this equation:
2KNO3 + Ca(OH)2 + C ---> 2KNO2 + CaCO3 + H2O
i used graphite as a carbon source as the patent recomends it. also it is pure carbon which charcoal is not. the reaction seems
to have worked as upon addition of the carbon a scentless gas was produced. i think this was water vapour. water vapour
continued to be evolved for around 2 minutes. i then allowed it to cool and dissolved what i assume to be KNO2 out with a little
water then passed through a filter. i then boiled the water off. i tested it by adding it to a little picramic acid in weak H2SO4.
the picramic acid didn't dissolve which was gay so i added the KNO2 anyways. i got a couple of little flecks or orange brown
precipitate and a funny smell (decomposed HNO2?). for dissolving the picramic acid would concentrated H2SO4 be a good idea
then add this to water containing KNO2?
thanks for the help.
[ July 29, 2002, 04:26 PM: Message edited by: kingspaz ]
Polverone July 30th, 2002, 02:18 AM

You assume you got KNO2? Well I would test it first, myself. Dump a bit of the solid into HCl. No red fumes, no KNO2. I'd be
interested if this method worked out well for you, since I like to keep nuggets of knowledge around for the day when I might
not be able to buy certain things.

yes, i forgot to add into the edit on my last post 'i know i shouldn't assume things'. the problem is i can't get HCl and i have
run out of H2SO4 for the time being. i will however make up a large batch using this process and i will test it when i have some
H2SO4. thanks for the help!
andreas July 30th, 2002, 10:53 AM

As a means of temp. controll use a bath of molten lead as the heat sorce. It would keep the lead molten but wouldn't
overheat the reaction.
Polverone July 30th, 2002, 04:11 PM

Do you have any acids? Citric, acetic, oxalic, phosphoric? Any of these should be plenty strong enough. I would dilute the
H2SO4 if you use it for testing, since concentrated H2SO4 will produce fumes to some extent even with nitrates.

hey i do have some citric lying round actually. i can't remember why i bought it. thanks polverone i'll use that to test. the art
place doesn't get the graphite sticks in for 2 weeks though :(....assholes...
i do have 3 though so thats about 30g of graphite which is enough for a decent amount of KNO2. thanks for the help. i may
not get this done for a few days though because of the rain.
megalomania July 31st, 2002, 01:24 AM

Could you tell us what patent number that is?
Polverone July 31st, 2002, 01:57 AM

Yes I could. In fact, I already did <img border="0" title="" alt="[Wink]" src="wink.gif" /> . Look above the equations in my
earlier post.
kingspaz August 4th, 2002, 10:50 AM

right, the great rain that has persisted the last 6 days, day and night has stopped! so today i'm going to make some KNO2 via
the last method i tried. using graphite as a carbon source. also before i tested the KNO2 i made with the Al method:
2Al + 3KNO3 ---> Al2O3 + 3KNO2
i added about 10-15g of the crude product to a concentrated citric acid solution. the stuff fizzed a fair bit and the solution
turned orange and began to fume vigourously. the fumes had an orange colour and did not leave the flask but stayed at the
bottom with the liquid.
about half the crude KNO2 i added did not react or dissolve so i assume that would be KNO3 impurities. but as i have leanrt i
shouldn't assume <img border="0" title="" alt="[Wink]" src="wink.gif" />
i'd just like to know whether an orangy colour is acceptable in this chemical test as i've never had experience with this.
nbk2000 August 4th, 2002, 03:33 PM

The orange gas sure sounds like NOx to me.

right,
i've just purified the KNO2 from the slag left over from the carbon method. i have then tested it using a strong citric acid
solution as i did above. the results where disapointing as when i added the 'KNO2' nothing happend. it just sank to the bottom
and began to dissolve which tells me its most likely KNO3!
back to the my old Al method i think...
Microtek November 6th, 2002, 01:43 PM

I would like to recommend a procedure for nitrite production that I have just discovered ( it's not my idea, I just read a book ).
The method is derived from Griess's original procedure for DDNP synthesis and can be used directly if desired.
Griess prepared DDNP by bubbling nitrous gas through an alcohol solution of picramic acid at low temp. The "nitrous gas" is an
equimolar mixture of NO and NO2 and acts almost exactly as nitrous anhydride N2O3. This gas was generated by reducing
HNO3 of density 1.30-1.35 g/mL with starch. Now I have been generating NOx by dissolving Cu in HNO3 which is rather
impractical, so I tried out this new method and this is how it went:
20 mL of 50-55 % HNO3 was poured on 2-3 teaspoonfuls of starch in a flask. Nothing happened at first but after shaking
gently and heating until the mix turned brownish, bubbles started forming and heat was removed as gas evolution
accelerated. From this point, huge volumes of brown gas was evolved over the course of about 5-10 minutes. The evolution
was very steady.
( additional info in a while )
kingspaz November 6th, 2002, 07:06 PM

thats an interesting idea. i suspect the equilibrium is similar to this:
NO2 <=> N2O4
so:
NO + NO2 <=> N2O3
do you have any information as to exactly how the starch reduced the HNO3? if this was bubbles through KOH then you should
get KNO2 solution (KNO2 purified by evapouration) so HNO2 can be made as needed as KNO2 is storable.
Marvin November 6th, 2002, 08:53 PM

I'm not happy with the current methods of estimating nitrite. I think reacting it with an ammonium compound, with some
catalytic TM ions around to make sure it goes to completion and measureing the amount of nitrogen gas produced would work
well.
Reacting nitric acid with copper or starch is supposidly a good method for small amounts, there is no definate single reaction
going on, and the ratio of NO2 to NO in the product depends on the concentration of the acid as well as the reducer, the more
dilute the acid, the more NO. For very dilute nitric acid you eventually get hydrogen with active metals. Get the ratio right and
its quite possible to produce nitrite in which there is no chemically detectable amount of nitrate formed. As it reacts and the
nitric acid dilutes the ratio changes to excess NO, which is wasteful but doesnt contaminate the product.
Id think nitrous acid should be acidic enough to displace carbonate, which is a lot cheaper than potassium hydroxide, if you
need K salts. If you cool an equimolar amount of NO and NO2 enough you get solid N2O3 crystals. Its questionable whether
this formation is crucial to formation of nitrite in solution though.

I made use of this easy way of producing NO/NO2 by bubbling the gas through a solution of 4.80 g NaOH in demineralized
water for about 2-3 minutes. I then evaporated the water until the crystals were completely dry ( by heating and passing dry
air over the soln ) and weighed the material. A total of 8.1 g was produced. I did a qualitative test for nitrite by adding 50 %
sulfuric acid to a soln of the material and got nice foaming with a brown gas.

Its nice it works, but what you got might be contaminated with a lot of unreacted NaOH. Theres a few niggling questions I
havnt been able to find answers to. Will a solution of nitrite in water absorb oxygen from the air.... and would a mixture of
nitrate and hydroxide absorb NO with the production of nitrite......
If the latter is true, then we could make maximum use of nitric acid if we choose to use that method, and if the former is true
then multiple recrystalisations might not actually be increasing the purity of the nitrite.
I think the 'best' method of determining quantity of nitrite might simply involve titration in mild acid with permangonate.
Titrations are spectaculaly dull, but do give very reliable results.
Microtek November 9th, 2002, 08:20 AM

I'm not sure what would happen if pure NO was bubbled through NaOH soln, but it is quite easy to determine if NO2 is present
in the gas stream simply by looking at the colour. Air could then be added to the stream if too little NO2 was present.
Or two gas generators could be set up, one with a high concentration of acid, the other with a low concentration. The gas
streams would be merged, and bubbled through the NaOH soln. As the concentrations dropped the low conc generator could be
shut down while the high conc one progressed to the NO/NO2 production concentration. Once it was diluted further, it could be
used as the low conc generator etc. etc.
PS. How would you use this titration? What indication would there be that stochiometric amounts had been added?
[ November 09, 2002, 07:23 AM: Message edited by: Microtek ]

If a solution of nitrate and hydroxide would produce nitrite from NO, this would be a big improvement. Firstly the yeild of nitrite
from nitrous gasses would be doubled, and secondly its much easier to use dilute nitric acid, which only produces NO without
adding air.
I'll refersh the idea of titration for those who dont know. You have an indicator in solution that tells you if the chemical you are
testing for is still present, then you add a carefully made concentration of a chemical that destroys it, a bit at a time until its
all gone. From the equation of the destruction, and the amount of destroyer used, you can work out the amount of chemical
your interested in knowing the amount of.
This is a bastardisation of a very wide ranging method, but it will serve. In the case of nitrite with permanganate, we produce
nitrate, and depending on the ph, probably either manganese dioxide, manganous oxide or manganese chloride. Since the
permanganate is deep purple itself, we dont need an indicator, we just add it, preferably from a buiret, but a gradiated
cyclinder will do, until we get a faint perminant purple colour in the solution.
Normally, we'd do a double titration to work out the total amount of undecomposed permanganate used from a reagent that
doesnt decompose, but this isnt required. What we do need is a method of weighing quite accuratly the permanganate to form
the known concentration solution. Any sort of balence will do. I suspect the product in mild acid would be Mn (II).
Permanganate stains can be removed with conc citric acid solution. I apologise if this is an overly simplified answer Microtek,
but others might find it useful.
I suspect nothing would happen if NO was bubbled through hydroxide on its own, hyponitrates can be made, but require rather
more subtle methods. My idea that it would reduce nitrate is based on NO2 + NO producing only tiny amounts of nitrate if
balenced correctly, if the production of nitrate was irriversable, I would expect a fairly sizable amount of nitrate formed.
At the moment I'm lookiing at decomposition of TM metal nitrates to NO and NO2 and the metal oxide. The quantities are
often right for pure nitrite production, owing to the valence of oxygen relative to nitrate. They decompose at temperatures
reachable with pyrex containers. The nitrates themselves are often impossible to prepare free of water, but if a mixture of
sodium nitrate and the metal chloride is used the anhydrous TM nitrate is formed and decomposed in situ to leave the metal
oxide and sodium chloride. Any chlorine/HCl formed would contaminate the product, but this should not be large, and easily
removable if needed. This could work, this could definatly work.

Just for the record that is an over simplification, but I don't take offense quite so easily so no apology needed.
I wasn't asking what a titration is but how you would indicate the transition from nitrite to nitrate. I wasn't thinking that MnO4-
would be reduced to colorless Mn(II)2+, silly me.
Anyway, I tried this and it works brilliantly though you need to acidify the soln very carefully, otherwise the reduction will be
along these lines:
2[MnO4]- + 3NO2- + H2O --> 2MnO2 + 3NO3- + 2OH-
Where it should have been
2[MnO4]- + 5NO2- + 6H+ --> 2Mn(II)2+ + 5NO3- +3H2O
So of course you can use both reactions, but one or the other and if the first one is used pH must not be too high or the
reduction will proceed too slowly.
BTW, what do you mean by TM? Transition metal? If that is the case then I'm pretty sure it will work. At least I think I read
somewhere that Cu(NO3)2 decomposes to give NO2 + NO + CuO. And when you prepare the coppernitrate you get a lot of NOx
as well.
frogfot August 23rd, 2003, 04:54 PM

Tested the KNO3/Pb method. Had 10 g KNO3 and 20 g lead in a beaker, heated with gas burner for 30 min and stirred with
glass rod. Whole thing melted and turned to yellow-brown (a sign of PbO). Not all lead was consumed. When i left beaker to
cool, it cracked when salt solidified (duh!), thats why theyre using iron cup.. It was hard to separate all Pb and PbO so I didn't
weight them..
Anyway, nitrite was extracted with hot water. On test with HCl sample turned yellow and bubbled slightly, NOx smell was present
:) The clear solution was left for some hours and it became turbid, most probably PbCO3 forming in contact with airs CO2..
I dont understand following:

carbon dioxide is bubbled through for one minute (not longer!)
What is the reason not to bubble it longer? The dissociation constants show that HNO2 (4E-4) is much stronger than H2CO3
(4,31E-7), so evolution of HNO2 couldn't be the reason..
Btw, another less user friendly alternative to CO2 would be H2S, this would give much purer product, though this wouldn't be
nescessary for most purposes of nitrite...
Trinitrotoluene August 23rd, 2003, 05:47 PM

A while ago I tested the KNO3/Pb method. I used 41grams of Pb metal from fishing weights, and 20 grams of KNO3 from
stump remover. It was placed into a copper crucible and heated under a hotplate. I did manage to get the lead of melt and it
stayed at a molten state for 5 minutes, but the hotplate wasn't hot enough. My goal was to obtain PbO. The nitrate/nitrite was
washed away with water, I only received a fairly thin layer of PbO covering the Pb.
DBSP August 23rd, 2003, 06:03 PM

During my attempt to synthesise CTMTNA I tried making sodium nitrite by reducing it with lead. And I got a fair ammount of
PbO, I might still have the PbO left in the filter paper, check that later. I heated the NaNO3 and lead together in a melting pot
used for casting lead over a propane burner. And I was able to maintain a fairly high temp because of the gas burner. As soon
as the NaNO3 had melted(when melted alone) it started releasing its oxygen(noticed small bubbles at the hottest places).
mongo blongo August 23rd, 2003, 10:10 PM

I have tried NaNO3/Pb many times. I would definitely advise heating the nitrite extract with Pb twice or more (to react any
remaining NaNO3). I can tell you this because the amount of PbO collected was less than half than expected after simple
stehiometric calculations.( Not using nitrite weights because of the uncertainties of the product). This was after only the first
reaction by the way.
I tested my nitrite presence with Iron II Sulphate and distilled acetic acid (gives brown solid suspension which is dissipated with
heating).
I do admit that I haven't actually used my nitrite in any synthesis except Cyclotrimethylenetrinitrosamine in which the result
was very convincing. I never tried it with DDNP though.
frogfot August 29th, 2003, 09:05 AM

70 g Pb/51 g KNO3 gave 43 g unreacted KNO3 after 40 min of heating.. and occasional stirring. I think that continious stirring
is very important to drive reaction faster. Next experiment will be on bigger scale with a motor stirrer..
Mongo, whats your usual yield of nitrite?
Btw, what if one heats KNO3 with some widely available catalyst? For example, would iron(III) or manganese(IV) decompose
nitrite too?
mongo blongo August 29th, 2003, 10:41 AM

Can't remember any yields sorry dude. It was some time ago. How did you know how much KNO3 reacted? It looks exactly the
same as nitrite.
frogfot August 29th, 2003, 03:51 PM

Well, I evaporated extracted liquid to 50 ml and precipitated KNO3 at 0*C (it cann't be nitrite because of its solubility..).
Remaining 10 ml was evaporated to dryness, got about 3 g solid, from which <1,3 g is KNO3 (calced from its solubility).
tiac03 November 26th, 2003, 02:25 AM

the only place i read about getting nitrite is from the book "CIA explosive-preparations" since i havn't tried any of the
methods in it i can't tell you if it actually works. (or if anything they say is safe to do) i downloaded it off of kazaa. (pdf file
someone scanned the manual and put it into pdf format)
(since the manual is about improvised explosives they use easy to find containers.)
an exerpt:
Mix 12g of lead and 4G of potassium nitrate (or sodium nitrate). place in an iron pipe (with an endcap) and heat with a blow
torch or hot coals for an hour or more.
remove container from heat, allow to cool and then chip out the yellow solid (with screw driver).
put in a mason jar add 1/2 cups (120 ml) of methyl alcohol to it. (orange brown solid, cream color in alcohol)
heat it in a pan of hot water untill it reacts (solution turns darker upon heating)
filter mixture through paper towel. solid left on paper towel is lead monoxide. wash it twice with 1/2 cup hot water. then let dry
before using in explosives (such as lead picrate).
the liquid you filtered the lead monoxide out of (in a jar) is then put into a hot water bath untill all alcohol has evaporated. the
remaining powder is nitrite.snowy liquid; some white powder appears but not much.
well that is a paraphrased version of what is written in the manual. i can't tell you if it will work or not.
and i guess they use lead (to answer your question) because you can then use the lead monoxide to make lead picrate (used
as a primary explosive in detonators)
metal dragon March 4th, 2004, 02:10 AM

While mindlessly flicking through a chemistry book I found something interesting. It was preparation of potassium nitrite. It
was simple example as well potassium nitrate was put into a small boiling tube (test tube) and a Bunsen burner was used to
heat this sample, O2 was given off, this was proven by the ignition of a glowing splint. The mixture that remained was in fact
KNO2 . This procedure wa s take n from a series of books ca lled chemlab .

Now, why didn't everyone else think of that five years ago?
Oh, wait, we did.
I have a little experiment to do with sodium metabisulphite, results posted when I have them...
kddflx April 18th, 2004, 12:45 AM

here's an idea for reducing HNO3 to HNO2 using Hydrogeniodine from 'Van Nostrandd's Scientific Encyclopedia Fifth Edition':
under the heading Iodine, it reads: "Hydrogen Iodine, HI, is the least stable of the hydrogen-halides, and correlatively, the
best reducing agent, readily reducing vanadic acid, nitrous oxide to ammonium, nitrous acid to nitric oxide, and HNO3 to
nitrous acid."
nbk2000 April 19th, 2004, 01:18 PM

HI, better known as hydriodic acid, is also a schedule 1 meth precursor, making simple possession of it a felony under various
drug control acts. Either use it for making crank or, better yet, leave it the fuck alone and find better ways of making HNO2.
frogfot September 24th, 2004, 04:59 AM

I've recently tested Pb/KNO3 synth with 99,95% lead and got some really strange results.. after about 12 min heating 207g
Pb/101g KNO3 and stirring constantly the mix started to heat up on its own until a red glow! So I removed the gas burner and
mix continiued glow for about a minute.. During reaction there separated some solids (hight mp, probably potassium oxides).
Those who tested this synth many times, is this normal? Is it some kind of runaway..?
On extraction I've got 55 g KNO2 (very basic on dissolution, probably contains alot of KOH because of potassium oxides..) and
215 g yellow powder of PbO. Why doesn't any source mention this runaway??.. :(
Bugger September 24th, 2004, 06:00 AM

HI, better known as hydriodic acid, is also a schedule 1 meth precursor, making simple possession of it a felony under various
drug control acts. Either use it for making crank or, better yet, leave it the fuck alone and find better ways of making HNO2.
I presume you are in the States. Has the U.S.A. gone that Fascist, outlawing even dear old HI? I cannot think of any other
country where even use, let alone possession, of HI is illegal. And besides, it can be easily made as a byproduct of iodination
of hydrocarbons, or direct reaction with gaseous H2 (made by action of an acid or alkali on a suitable metal), using iodine
bought OTC as a disinfectant. If you live close to the Canadian or the Mexican border, how about setting up a laboratory in
either of those countries, if you want to keep and use HI?
chochu3 September 27th, 2004, 06:19 AM

Heating a nitrate salt will take off an oxygen but after cooling most of it will suck up back the oxygen giving you the nitrate. I
read somewhere in one my books (to lazy to reference) that nitric acid can be reduced to nitrite by reduction with hydrogen
iodide. I myself haven't tried this but might be worth time.
K9 September 27th, 2004, 08:26 AM

Heating a nitrate salt will take off an oxygen but after cooling most of it will suck up back the oxygen giving you the nitrate. I
read somewhere in one my books (to lazy to reference) that nitric acid can be reduced to nitrite by reduction with hydrogen
iodide. I myself haven't tried this but might be worth time.
That's the purpose of heating with something like lead. The formation of PbO should take care of the problem.
Jome skanish September 27th, 2004, 10:50 AM

How about use one of these for preparation of KNO2:
Cr2O3+4KOH+3KNO3--->2K2CrO4+3KNO2+2H2O
or
2MnO2+2KOH+3KNO3--->2KMnO4+3KNO2+H2O
EDIT: These are reactions performed at high temperature, at least one of reactant has to be molten, which for KOH means a
temperature of at least 360 degrees centrigrade. Just felt I had to mention this so no one would mistake them for being "wet"
or someting...
The first one definately work. Its on frogfots page! The second I think I saw proposed here somewhere, but I dont know if
anyone ever successfully performed it.
It seems quite easy to separate the KNO2 from remaining KNO3or KMnO4, KNO2 is a very soluble salt at low temperatures
(73,6g/100ml H2O @ 0 degrees centrigrade), and that goes for only two of the possible contaminants. (solubility: KNO3 13,3g,
KMnO4 2,83g, they should be easy to separate, but KOH and K2CrO4 is highly soluble, ~60 and 58,2g /100g H2O @ 0
degrees centrigrade.
My idea: First, separate out the low-solubility salts by fractional cristallisation (these are KNO3, KMnO4 or just KNO3 depending
on which reaction you chose)
That should leave you with a solution of KNO2, KOH and K2CrO4 or KNO2 and KOH. Adding copper sulfate to the first solution
(from the Cr2O3 reaction) should precipate out Cu(OH)2 and CuCrO4, leaving in solution K2SO4 and KNO2. Adding to the
second solution (the MnO2 one) should precipate out Cu(OH)2 + a little CuMnO4, Cu(MnO4)2 and so on (manganates and
permanganates of copper).
Now, from both experiments we are left with only K2SO4 and KNO2 in solution. K2SO4, as opposed to KNO2, has a very low
solubility @ 0 degress centrigrade....
One would probably have to repeat some of the steps to get clean nitrite, but it should work, shouldn't it?
Bugger September 27th, 2004, 06:30 PM

The problem with the second of those reactions, in which MnO2 is allegedly oxidized to KMnO4 on heating with molten KOH
and KNO3 (which is partially reduced to KNO2), is that KMnO4 decomposes at less than 240C, below the melting-point of KOH
which is 380C (and KNO3 melts at 333C). And, MnO2 decomposes to Mn2O3 at less than 230C. So this reaction is a defnite
non-starter. Where did you get this spurious reaction from?
Chromate is much more resistant to heat, though, and nitrate just might be capable to oxidizing Cr2O3 to chromate(VI) while
undergoing partial reduction to nitrite, under these conditions.
Jome skanish September 27th, 2004, 06:59 PM

I dont know if this particular reaction is possible, but the more commonly quoted synthesis for KMnO4, (with MnO2, KOH and
KClO3, like here: http://www.roguesci.org/theforum/showthread.php?t=934&highlight=potassium+permanganate ) also seems
to be performed at similar temperatures. Whats interesting is that even though the temperature causes decomposing of the
KMnO4, the processes that promotes its formation is faster, at least until some kind of equlibrium is reached
However, if one were producing nitrite by the Pb+XNO3 method, simply adding water and filtering out PbO would stil leave
XNO3 and XOH as impurities. They could be removed by the exact purification-method described above!
meselfs September 28th, 2004, 12:41 AM

I've always mixed a small amount of sugar with KNO3, without melting or even powdering them. The amount of sugar must be
more then what is used for cheap rocket fuel...
Then ignite. It won't exactly burn, it'll smoke alot, boil, and produce sparks and heat.
If it fails to sustain itself, use more sugar. If it ends up with alot of black crud, use less sugar.
It's crude, but it works, it's always done the job for me.

The above post I should of metioned the reaction did proceed with lead and formed its oxidize and was stirred and let to
bubble for an hour, but the remaining KNO2 did turn back into KNO3. Maybe the reason for this is because the contents was
mostly in contact with air as a small wide rxn vessel was used.
nbk2000 September 28th, 2004, 02:11 PM

So burning sugar and nitrate forms nitrite? Are you sure it's not carbonate?

meselfs, I didn't get what this have to do with nitrite synth..
About how to separate K2CrO4 and KNO2, theoretically there are a simple way.. mp of the first one is 968*C and mp of second
is 387*C (thats difference by 2,5 times). So, if only there was an easy way to filter those apart while KNO2 is still liquid..
This shure would be an easier nitrite synth than Pb/nitrate synth (and one would also increase yields of dichromate :) )
meselfs September 29th, 2004, 01:43 PM

So burning sugar and nitrate forms nitrite? Are you sure it's not carbonate?
Definitely it contains carbonate, but it's mostly nitrite.
Jome skanish September 29th, 2004, 05:32 PM

Frogfot: Melting it!?
How about adding Fe/CuSO4, filter out the precipate (mostly Cu/FeCrO4, but also some Cu/FeCO3 and Cu/Fe(OH):s.) then
cool the solution to precipate the sulfate, which has low solubility at low temps.
frogfot September 30th, 2004, 02:00 PM

Sounds nice, but I wanned to recover the chromate also to make dichromate.. although maby Cu/FeCrO4 have some good
uses too.
It's kinda easy to melt nitrite while keeping chromate solid, even with a gasburner..
Jome skanish October 1st, 2004, 11:29 AM

Oh, you have tried it! Is it an effective method, does it separate good?
If it is possible to add acetic acid before removing the nitrite (I dont know how acidic soln. has to be to release HNO2?), then it
would be much easier to precipate out the formed potassium dicromate, and then use CuSO4 and after that fractional
crystallisation to remove KOH,K2CO3 and KNO3 from the nitrite soln. The dicromate, in turn could simply be recrystallised at
low temps (everything else is more soluble)
Now you have both quite pure K2Cr2O7 and KNO2 :D
frogfot October 1st, 2004, 07:35 PM

I havn't tried to separate them.. yet. When melted it becomes like a goo of chromate crystalls soaked into nitrite.. so
somekind of suction filtration is required.
Yp, one could recover nitrite after dichromate recovery, but solution releases some NO2, and even more if heated (gotta heat
to concentrate it). Thats a bit nasty (and there will be some acetate left).
Neutralising the acid would give more work.. though maby it's worth a try when more time comes (school have just started..).
Jome skanish October 2nd, 2004, 09:02 PM

I found some chart on solubilities in alcohol and water, it seems like NaNO2 is insoluble in etanol, but Na2CrO4 is slightly
soluble (0,34g / 100 ml). If etanol is added to a water solution of the two, perhaps NaNO2 precipates like KNO3 and NaNO3
does when one is making black powder! But first one would have to remove to remove all remaining NaO/KOH, since its
soluble in alcohol. Potassium cromate doesn't seem to be soluble etanol, so If potassium cromate is needed you'd have to
precipate it out of Na-soln. with KCl or something. I cant find anything on KNO2, but I doubt it is soluble i etanol.
What can we make of this?

Na2CrO4 and NaNO2 is made by fusing together NaOH, NaNO3 and Cr2O3.
They are filtered from remaining Cr2O3.
Possible contaminants are NaOH, NaNO3 and Na2CO3. Some Ca(NO3)2 is added and all carbonates and hydroxides are
precipated. These are filtered of.
By adding etanol everything but Na2CrO4 precipates, the solution is filtered once again. The filtrate is mostly NaNO2 and some
NaNO3. NaNO3 can be removed too, but in most nitrite uses nitrates does not make any difference. I dont know how they can
be separared if it's needed, their solubilites seems pretty "close".
The liquid that went though when the others separated out contains Na2CrO4. The etanol should probably be removed, but
that's a piece of cake, just heating. Adding K-ions (by KCl or KNO3) one can crystallise out K2CrO4 at low temps, perhaps
more than one time if product purity is important.
Only flaw with this procedure I can see is the difficulty to separate out the nitrate. As soon as I find cheap Cr2O3 in sweden I
will attempt it!
EDIT: Perhaps stupid CaCrO4 precipates when adding Ca-nitrate. I dont know its solubility but it "sounds" like a low-solubility
salt, anyone with a table?
frogfot October 3rd, 2004, 07:38 AM

0,34g/100ml is quite low solubility.. for 34 g one would need 10 litre alcohol..
Heres some info on solubility of CaCrO4*2H2O in 100 ml water:

22,4 g@0*C, 16,3 g@20*C, 18,2 g@45*C
I have a bottle with about 500 ml of acidic nitrite containing liquid from last preparation of chromate (about month old), it's
black and theres a visible amount of NOx inside the bottle. I would try to extract the nitrite if only there was no NOx..
Jome skanish October 3rd, 2004, 09:23 AM

Perhaps IPA or acetone could be tested instead if it is more soluble in one them?
Now im just guessing. I guess I should try to actually do something instead...
Ca(OH)2 probably wont form in solutions with only a little NaOH, its precipation requires very high pH's. I tried to precipate it
out of Ca(NO3)2 soln with ammonia, but it seems like ammonia is not alkaline enough. NaOH worked only if concentrated, so
I guess adding Ca(NO3)2 to remove hydroxides and carbonates wont work :(
Dont you have a fan or something? (!) Or perhaps you mean you nitrite is decompsed?
nbk2000 October 4th, 2004, 02:06 PM

What about seperating the nitrite from the carbonate after sugar/KNO3 combustion/reduction?
The simplier, the better, as this would remove the need for a furnace for reducing large amounts (pounds), by simply adding
the mix as a constant feed into a crucible where it's kept burning by the heat of that which has already burnt, jsut fast enough
to keep the flame going, but not fast enough to generate a huge smoke plume.
meselfs October 4th, 2004, 03:26 PM

Well, I can't say exactly how much carbonate forms, but I think it's mostly nitrite.
The idea is that you make your proportions so that you have slightly less sugar (or whatever fuel) to reduce the nitrate to
nitrite, mix them well, and ignite.
The carbonate is less anionic then nitrite, thus nitrite is favored.
Any carbonate that does form can usually be ignored, I think. I've never had trouble with it. The only trouble is knowing how
much nitrite you have so you can mix your reactants properly... but I always use excess nitrite. It's hard to get in a pure form
in general no matter what you use. It even takes oxygen from air (slowly) to turn into nitrate.
bobo October 5th, 2004, 11:51 AM

According to Shimizu, nitrite is often found in the ash of incomplete burning of nitrates. For instance, the author states that the
mixture of sodium nitrate and shellac 10:2 produces liquid residue and strontium nitrate and shellac 10:2 leaves a solid ash.
Both residues are mainly nitrite.
For potassium nitrate, the author states that potassium nitrate with an ordinary organic fuel (rosin and shellac are named as
examples) burns mainly to nitrite, and it takes carbon and sulfur to get all the oxygen out effectively.
The numbers produced by Shimizu are 0.396 g oxygen from 1 g of KNO3 maximum versus about 0.158g for inferior fuels.
0.396g/g would indicate that K2O is quantitatively formed from the oxidant. 0.158 corresponds stoichiometrically with nearly
complete reduction to nitrite.
The_Rsert October 5th, 2004, 03:28 PM

Has anyone information of oxalic acid (?g in 100ml water at 0C, etc.)?
Because, maybe you will get some oxalic acid, if you react KNO3 and sugar.
C12H22O11 + 9 O2 ----> 6 HOOC-COOH + 5 H2O
But I'm not sure of this.

Well, with hexa, sugar/nitrate, and HCl, you've got HDN, so if the nitrite is somewhat ghetto purity, so what, as long as it works
when you need it to, and can make it anytime. :)
bobo October 7th, 2004, 11:19 AM

why would you use nitrite in HDN synthesis, if nitrates will do? Not that I would ever consider HDN unless as a precursor, but
that is due to the cost of making hexamine here.
The_Rsert October 14th, 2004, 10:09 AM

Has anyone information of making HNO2?
Marvin October 14th, 2004, 12:13 PM

Rsert, How ignorent of chemistry do you need to be not to know you add HCl to a solution of sodium nitrite in an ice bath?
This is very simple chemistry for diazotisation.
If you are wondering how to make nitrites from HNO2, the only real way is to lead the right mixture of NO and NO2 onto a
base in solution. The mixture can be made correctly by diluting nitric acid to a specific point and then reacting it with starch.
Heating sodium nitrate with a manganese (II) salt to produce NO and NO2 might also be a useful method but these are
generally less easy and require higher temperatures.
The_Rsert October 16th, 2004, 07:44 AM

Yes, thats clear, but I need another way without nitrite/HCL?
Maybe reducing 20% HNO3 or somwhat like that i mean.
Without reducing nitrates before of course.
Sorry about my bad english.

Ok, I see.
I thought I had exact instructions for the starch process but these seems to be not true. The method recommended in Mellor
is to react nitric acid with starch and feed the gasses into a freshly made slurry of sodium carbonate out of contact with air. The
concentration of the acid and temperature needs to be regulated to leave a very small excess of NO which will pass through
undissolved. Excess NO2 than required to form nitrite will produce nitrate as well as nitrite, a small excess of NO will form only
very very tiny amounts of nitrate. The bubbling needs to be continued until the solution is acid, and then boiled out of contact
with air until neutral. It can then be safely exposed to air to evaporate/concentrate in order to crystalise the nitrite. A guide to
roughly how concentrated or hot the acid needs to be it doesnt say, you'll have to use the undissolved NO coming through as a
guide if you want to try this.
This and the fused nitrate methods seem to be the only reasonable options so far.
Edit, just to clarify for anyone not following,
Reduction of very dilute nitric acid produces NO, reduction of concentrated nitric acid produces NO2, so at some stage of
dilution you get 1:1 NO:NO2 you need to make nitrous acid. Temperature will also affect it.
The_Rsert October 17th, 2004, 04:50 PM

Thanks for the little info, Marvin.
But that's very inefficient.
I will fuse some sulfurless BP in a beaker, than I will mix it with cold water, than I will filter it and than I will recrystallize the
filtrate.
And than I will see how pure the KNO2 is...
Rosco Bodine October 18th, 2004, 03:02 AM

There is another patent regarding the use of sulfur as
the reducing agent for making nitrites from nitrates ,
the temperature of the melt being low enough so that
the sulfur mixes and reacts with the melt , and does not
simply deflagrate on contacting the melt .
US572819
The reactions described for two nitrites are :
3 NaNO3 + 2 NaOH + S -----> 3 NaNO2 + Na2SO4 + H2O
3 KNO3 + 2 KOH + S -----> 3 KNO2 + K2SO4 + H2O
If it is not necessary to produce the Na or K nitrite alone as

a single pure compound , I speculate that it may be easier to
produce a mixed nitrites , from a combined mixture of the
Na and K nitrates and their hydroxides in some proportions
which may lower the melting point of the mixture still further ,
if this is found desirable to facilitate a controlled reduction .
According to another patent describing a eutectic mix of nitrates

for use in a fusible variation of black gunpowder , a mixture of
55 parts KNO3 and 45 parts NaNO3 is a eutectic .
GB715828
Magnesium nitrate or perhaps calcium nitrate , and their oxides

or hydroxides added to the system could also lower the melting
point of such mixtures . Perhaps the reaction requires a temperature
high enough for the melt that the sulfur will also be molten , but
I am uncertain about this factor . It may be that the reaction
is temperature dependant at a different rate for the different
salts and would have to be run at an optimum temperature so that
the different reactions run in reasonable harmony . Or the experimental
use of a eutectic melt may be no advantage . This is simply an
additional idea offered for whatever value it may have .
bobo October 19th, 2004, 07:45 PM

do you get nitrite/nitrate mixed with polysulfides maybe? I think, this method is based upon sulfide formation and hence the
impurity to be expected is sulfide. That may or may not be problematic, but the waste surely stinks to high heavens and even
in a fumehood it may rise to unacceptable. It sure got some wrong attention when more than one dead bird was found on the
roof near the same location.
Rosco Bodine October 19th, 2004, 11:39 PM

There would likely be some sodium polysulfide formed in situ as
an intermediate , transition compound , then oxidized to a normal sulfate .
Also it may be that some sulfur dioxide or even sulfur trioxide may be
produced in small amounts , and escape the mixture as fumes , however
the reactions as stated above would predominate at a conservative
temperature . As for the dead birds , chemistry is not a pastime
for the foolish or careless , and has left many dead ducks for proof as well :eek:
Marvin October 21st, 2004, 02:00 AM

Molten solutions of nitrates and sulphides can detonate, cf Yellow powder, so this doesnt sound like the safest method. If
sulphur dioxide is acceptable, or even sulphites there is a method that uses it in aq. solution. The sulphate is precipitated as
calcium sulphate but its not clear if this drives the reaction forward.
Overall,
NaNO3 + CaO + SO2 => CaSO4 + NaNO2
Its not 100% clear this is in solution, but it seems to be. So far nothing beats the simplicity and reliability of fusing nitrates
with a 15% excess of granulated lead, everything Ive read recommends that process.
"As for the dead birds , chemistry is not a pastime for the foolish or careless "
Or birds it would seem.
Rosco Bodine October 21st, 2004, 03:24 AM

The danger of explosion in such a mixture would be present
if all of sulfur was mixed together at once with the
oxidizer mixture and an uncontrolled exothermic reaction
proceeded faster and faster , as a "runaway" reaction .
But such a danger would not be present for sulfur added

gradually in small portions . Watching the temperature ,
and controlling it by the rate of addition of the sulfur ,
the reduction should proceed smoothly . It seems possible
that whether or not the sulfur takes fire on contacting the
melt could even be useful as a visual indicator of the temperature .
The sulfur previously added should have already been
converted to sulfate , so the reaction mixture itself is
not flamable and would not be set afire even from the
ignition of sulfur on contact with the surface of the melt
were it allowed to become too hot .
I have never tried this particular method , but using a

mixture of the nitrates and hydoxides which could provide
a low temperature melt should result in a smooth reduction
with little danger of explosion .
K9 March 21st, 2005, 08:25 PM

I was just taking a look at my KNO2 and I was wondering if it's supposed to look like it does. Now from reading its msds, I see
"Appearance: White or slightly yellow granules." So far so good. And it has a solubility of 300g in 100g of water, so that would
explain the hygroscopicity (I think I spelled that one right). When I take some in my hand it sort of melts when squeezed
between my fingers. I'm just wondering if it has too much water in it.
I got it from a friend who gave a me a bunch of his old chemicals and it's a pretty old lab bottle. I would hate to think I'm
weighing out 10 grams when in reality it's a lot less and has a large water content.
This is what it looks like:

http://img.photobucket.com/albums/v78/wolfhound/KNO21.jpg
Is it good the way it is? Or should I let it sit in a container with some silica gel packets to desiccate? Any help would be
appreciated. Thank you in advance.
K9 March 21st, 2005, 08:25 PM


K9 March 21st, 2005, 08:25 PM


mongo blongo March 22nd, 2005, 12:32 PM

Well the obvious thing to do is heat it and see if it gives off water vapour/looses weight. I'm sure you didn't need me to tell
you that. :rolleyes:



a n d I m provised C hemistry > C opper liner
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View Full Version : Copper liner
xoo1246 A ugus t 5t h, 2002, 06: 12 PM

I'm working on a SC that uses a thin copper liner. I will be propelling the the liner by som e ANNM(the highe st Vod I can
acco mplish this far).
The AN has been drie d, still I'm a bit worried about Cu(NO3)2 form ing when the liner is in contact with the AN. I filled the
c o n t a i n e r o n c e t o g e t a n a p r o x i m a t e n u m ber on how m any gram s it could hold, em ptied it and left it, som e AN was left and
after a a day blue dots were visible. The copper cone had been cleaned and thus there wa sn't m uch oxide on the surface. I
h a v e c l e a n e d i t a g a i n with iron wool to rem ove the marks. Now I have to assem ble it again.
The question is, can the problem be solved by heating the liner under a flam e for a while to create a protective coating of
copper oxide ? I don't want to coat it with glue and I don't want m y device to auto-ignite. (EDIT: I will try it overnight on a piece
of copper plate, but I want to have your opinion on the m ather too)
W hile I'm at it, what kind of stand-off is acceptable whe n it com es to an inperfect cone such as this one(certainly not 6xd), and
should the the cone sides be overlapped?
Here are pictures of the device for anyone interested:
<a href="http://w1.478.telia.com /~u47802930/SCPrototype01.jpg" target="_blank">http://w1.478.telia.com/~u47802930/

SCPrototype01.jpg</a>
SCPrototype03.jpg</a> (won't use legs)
SCPrototype06.jpg</a> (taken minutes ago, it looks uggly now due to all the rough handeling)
<sm a l l > [ A u g u s t 0 5 , 2 0 0 2 , 0 5 : 1 8 P M : M e s s a g e e d i t e d b y : x o o 1 2 4 6 ] < / s m a l l >
kingspaz A ugus t 5t h, 2002, 06: 27 PM

its n ot coppe r nitrate you should be worried about but tetram ine copper nitrate (TAC N).
<a href="http://www.roguesci.org/ubb/ultimatebb.php?ubb=get_topic;f=1;t=000417" target="_blank">http://www.roguesci.org/
ubb/ultim ate bb.php?ubb=get_topic;f=1;t=000417</a>
it sh ould only form th e hydrated form when the AN is in place be cause of residual m oisture inside the AN. b ut i wouldn't bet on
it! you could coat the inside of the cone with solder. solder is composed of lead and tin wh ich don't form com p l e x e s . m a k i n g
the copper oxide coating will increase the reaction as it is the oxide layer that reacts with the AN. nom atter how well you polish
the cone it will ALLWAYS have an oxide layer because its allways in contact with oxygen in the air.
edit: m y point with the hydrated form was that its insensitive as a prim ary as i've tested it for possibilities and it couldn't be
detonated. with a cap it would probably be detonable though.
but don't rely on the hydrated TACN form ing. all you need is a pocket of dryness and you'll have dehydrate d TACN which is (i
guess) about as sensitive as TACC which is a prim ary explosive.
<sm a l l > [ A u g u s t 0 5 , 2 0 0 2 , 0 5 : 3 1 P M : M e s s a g e e d i t e d b y : k i n g s p a z ] < / s m a l l >
Polverone A ugus t 5t h, 2002, 07: 25 PM

W hat about heating the liner and coating it with wax? That should protect the m etal from any interaction with the NH4NO3. You
can also find spray-on plastic coatings in craft stores that would probably do the same job.
xoo1246 A ugus t 5t h, 2002, 08: 07 PM

T h a n k s , e v e r y d a y y o u l e a r n s o m ething new. I had though about coating it with wax/spray plastic/glue, but I wanted to know if
C u O was ok first. O n c e a g a i n , t h a n k s .
Anthony A ugus t 5t h, 2002, 08: 25 PM

I think a standoff of 2x cone height is said to work for im provised stuff.
W hat's the angle of your liner by the way?
I wouldn't overlap the edges of the cone as the variance in liner thickness would probably give a non-uniform jet.
xoo1246 A ugus t 6t h, 2002, 02: 27 PM

I have fixed it now, used the edge of a plastic bag resistant to NM that fit very go o d ( h e a t e d i t i n s o m e water for an even better
f i t ) . T h e a n g l e i s a r o u n d 6 0 d e g r e e s . ( d i a m eter 4.6 cm , height 4 cm ). The plastic spray I had at hom e didn't work, neither d id
a glue said to be resistant to RC fuel(obviously they didn't think about NM in fuels). Didn't try vax, since I have an ok solution
now. I will try 2xd as stand-off.
Edit: I did overlap around 1m m , will see how it works, probably tom orrow.
bonnsgeo A ugus t 6t h, 2002, 02: 36 PM

h e m ..xoo .. i know its not the topic but i sent u an em ail about blu tac ...could u read it ? :rolleyes:
thx
bye
Yi A ugus t 6t h, 2002, 08: 26 PM

Looks nice :) W hats the thickness of the coppe r and how m uch ANNM are you using? I might repeat your te st with Picric acid if i
m anage to g et enough.
For anyone planning on wax coating copper liners, once the wax is on there it will com e of very easily <im g border="0" title=""
alt="[Frown]" src="fro wn.gif" />

a n d I m provised C hemistry > Nitrogen fullerenes
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View Full Version : Nitrogen fullerenes
BleedingLips August 6th, 2002, 08:05 AM

February 2, 1999
New Nitrogen Ion Carries Warning: Handle With C a r e
B y M A L C O L M W . BROW NE
For a century, chem ists doubted that such a substance could exist, but
scientists at an Air Force laboratory have create d a freakish form of
n i t r o g e n b e l i e v e d t o b e o n e o f t h e m o s t v i o l e n t l y e x p l o s i v e s u b s t a n c e s e ver
m ade.
To the acclaim of many other scientists, a team of chem ists hea ded by Dr.
Karl O. Christe and Dr. W illiam W. W ilson at the Air Force Research
Laboratory at Edwards Air Force Base, Calif., reported their achievem ent
at a recent m eeting of the Am erican Chem ical Society.
The new com pound is a positively charged ion, or molecular frag m e n t ,

consisting of five nitrogen atom s chem ically bonded to each other in a V
p a t t e r n . I t i s s o s e n s i t i v e a n d e x p l o s i v e , t h e m a g a z i n e C hemical &
Engineering News reported, that a few tiny grains of the substance
accidentally detonated, destro ying part of the apparatus being u s e d t o
analyze it.
The newly synthesized allotrope, or form, of nitrogen (N5 ) is only the

third such form of the element ever discovered.
Nitrogen in its most com m o n , g a s e o u s f o r m , consisting of two atoms of

t h e e l e m e n t c h e m ically bound to each other (N2 ), makes up four fifths of
the earth's atm o s p h e re and is quite stable and chemically unreactive. Th is
form of nitrogen was identified in 1772.
The next allotrope of nitrogen to be discovered was the azide ion (N3 ),
containing th r e e b o u n d n i t r o g e n a t o m s, which was synthesized in 1890.
Azides combined with m e t a l s a s s a l t s a r e u n s t a b l e a n d e x p l o s i v e ; l e a d
a z i d e , f o r e x a m p l e , h a s b e e n u s e d c o m mercially to detonate high
e x p l o s i v e s , a n d s o d i u m a z i d e i s t h e e x p l o s i v e u s e d t o i n f l a t e a u t o m obile air
bags.
T o c h e m ically bind increasing num bers of nitrogen atom s to one another

r e q u i r e s e n o r m o u s e n e r g y , a n d c h e m ical theorists had predicted that
nitrogen allotropes with more than three nitrogen atom s would b e s o
unstable they could n ot exist.
Dr. Christe's team , however, has confo u n d e d t h e e x p e r t s .
Over four m onths, his group succeeded in synthesizing a salt in which the
positive ion consists of five nitrogen atoms and the neg ative ion consists of
an arsenic atom with six fluorine atoms. The group obtained pro of of the
substance's chemical com position using laser spectroscopy, but after the
analysis was com pleted, several grains of the white crystalline powder
exploded, demolishing the sam ple chamber.
T h e m a t e r i a l i s s o d a n g e r o u s t o h a n d l e t h a t o n l y a h a n d f u l o f l a boratories
would be able to perform Dr. Christe's synthesis, chem ists said.
Dr. Steven H. Strauss of Colorado State University at Fort Collins, who is

familiar with Dr. Christe's work , said in an interview that even the m ost
e x p e r i e n c e d c h e m ists regard the synthesis of an allotrope with five nitrogen
atoms as astonishing .
"Just having shown that this substance can exist even tem porarily is a
giga ntic achievem ent," he said. "Theorists who may have considered this
type of com pound impossible will have to do some recalculating."
Dr. Christe is known for another tour de force in chem istry: the first
successful separation, in 1986, of pure fluorine from a fluorine com p o u n d
using chemical reactions alone. Fluorin e , a p o i s o n o u s p a l e y e l l o w g a s , i s
normally prepared by passing a current of electricity through molten
fluoride salts. Fluorine is the most violently reactive of all elements, and it
c a n b e s e p a r a t e d f r o m its com pounds only with the help of large am ounts
of energy. Most chem ists had believed that chemical separation of
e l e m ental fluorine wa s probably im p o s s i b l e .
Dr. Christe works at the propulsion division of the Air Force laboratory at
Edwards Air Force Base, and his research, som e of it secret, is financed
by the Air Force, the Defense Advanced Research Projects Agency and
the National Science Foundation.
He said in an interview that the new nitrogen allotrope was likely to find
u s e s , b u t h e d e c l i n e d to say what they would be. However, the m aterial is
such a powerful oxidizing agent that it explosively rips water molecules
apart.
Dr. Christe said that the latest goal of his group was to synthesize an
all-nitrogen salt consisting of a positive ion of five nitrogen atom s b o u n d to
a negative ion of five nitrogen atoms. Such a com p o u n d , c o n t a i n i n g 1 0
m utually link ed nitrogen atom s, would be extremely difficult if not
im possible to synthesize, but it would probably pack stupendous chem ical
energy that m ight be released with great explosive force.
Interesting links:
<a href="http://www.llnl.gov/str/June01/Manaa.htm l" target="_blank">http://www.llnl.gov/str/June01/Manaa.htm l</a>
<a href="http://www-cms.llnl.gov/buckyballs/research_proj.html" target="_blank">http://www-cms.llnl.gov/b uckyballs/
rese arch_proj.htm l</a>

wonder how he managed the elemental fluorine by chemical means...

???
T h e c o m m ercial m ethod is sim ple electrolysis of fluoride salts, e ither in water or in a polar aprotic solvent (though I doubt
c o m m on DMSO or DMF could be used due to low solubility) to release elemental fluorine.
T h e a l k a l a i i s r e m oved from the reaction via absorption into a m ercury cathode form ing an amalgam which is contin uously
p u m ped to p revent solidification. It is perodically discha rged and replaced, and the m ercury distille d u n d e r n o b l e g a s to reco ver
t h e a l k a l a i m etal free of oxydation. This type of process also the first industrial process used for m a n u f a c t u r i n g a l k a l a i m e t a l s ,
before the Downs Process was invented.
But alas, researchers have it easy today. No longer lim ited like their alchem ist ancestors who had to synthe size all their own
reagents for experimentation, researchers today just BUY whatever they need from chem ical mega giants like S-A or Fisher.
There's a certain pride in mak ing EVER YTHING yourself, even if it does take longer.
I think thye just bought a fluo rine canister personally, lol. The cooled it with liquid N2.
The concept of Total Synthesis is almo st lost to our vocabulary today. Ho w sad.
Prim oPyro
kingspaz A ugus t 6t h, 2002, 06: 07 PM

from the above article 'Dr. Christe is known for another tour de force in chem istry: the first successful separation, in 1986, of
pure fluorine from a fluorine com p o u n d u s i n g c h e m ical reactions alone'
thats why i was confused! flourine cannot (to my sim ple knowlegde) be reduced by anything other than electricity.
total synthesis is m y speciality by the way :D .....'neccessity is the m othe r of all invention'.....or som thing like that <im g
border="0" title="" alt="[W ink ]" src="wink.gif" />

Ah well, it's always po s s i b l e t h e n t h a t h e e x p l o i t e d a c o m plexing m echan ism, like Friedel Crafts principals for exam ple, where
strong Lewis Acids com plex with halogens to form extrem ely electron hungry species. I am sort of unfamiliar with this region of
chemistry, but I don't think that it would be im possible to liberate fluorine chemically from an organic comp o u n d a t l e a s t , u s i n g
a EW D-lewis acid com plex to form a more electronegative entity, which could replace the fluorine through a usual su bstitution
m echanism pathway, and then the com plex could be destroyed afterwards.
All speculation though. I have no articles on this.
Glad to hear you like Total Synthesis. I do as well.
Heh, it's not "purely" chem ical, but alpha particle bom bardment would lib erate bipositive fluorine ions that could be led away
into a cathode. :p
N o ? C h e a t i n g y o u s a y ? W e l l o k , I g u e s s y o u k i n d a g o t m e there....but it IS cool, you have to adm it. :D
Prim oPyro
<sm all>[ August 06, 2002, 10:34 PM: Message edited by: Prim oPyro ]

Jesus Christ! Fucking Duh!
T h e s a m e a n a l o g o u s r e d u c i n g s y s t e m for ALL halides/halates --> halogens.
Halide + Halate --> halogen.
This would have to be a special situation for this to work on fluorides. You would need to exploit solubility. (W hen do you NO T
have to??)
A norm a l e x a m ple of this (and hits hom e hard for m eth cooks) is the preparation of iodine from iodide salts. Granted this can
of course be done with acid and either hypohalite or hydrogen peroxide, BU T the yields with this method are always much much
better, nearly quantitative actually.
NaIO3 + 5Na I +6HCl --> 6NaCl + 3I2 + 3H2O
Now this cannot directly be used for fluorides because we need a m ore electronegative halide than fluorine and that sim ply
does not exist. But if you were to exploit solubility, you could force such a reaction using sodium fluoride, sodium fluorate, a n d
another acid. The acid choice and solvent are k ey.
W h a t n e e d b e d o n e i s c h o o s e a s o l v e n t a n d a c i d t h a t a ) b o t h s o d i u m f l u o r i d e a n d sodium fluorate are soluble in, and b)the

s o d i u m salt of the acid is not soluble in that particlular solvent.
T h e s o d i u m salts precipitate out of solution forcing the reaction to proceed to com pletion. Hell, if you could cheat and start with
the dry acids themselves, HF and HFO3, you co u l d u s e P 2 O 5 t o d e h y d r a t e t h e m t o F 2 + H 3 P O 4 (not balanced).
I love figuring these possibilities out.
Prim oPyro
Pu239 Stuchtiger August 7th, 2002, 01:45 AM

T h e [ F O 3-] ion doesn't exist. O nly [O F-] exists, and that is very unstable.
How about this?
3 H O F + 3HF + P2O5 ----> 2H3PO4 + 3F2
T h a t j u s t s e e m s t o o s i m ple to be real! :D
<sm all>[ August 07, 2002, 12:48 AM: Message edited by: Pu239 Stuchtiger ]</sm all>

I see you are correct. I have to adm it I'm slightly emba rrassed, I did not ever realize this. It never occurred to me to consider
that.
Hypofluorites can also substitute for fluorates then, if used with strong dehydratin g conditions like P2O 5.
Halates are just m ore com mon. Heh, "Not with fluorine they ain't!"
Prim oPyro
<sm all>[ August 07, 2002, 12:55 AM: Message edited by: Prim oPyro ]
Marvin S e p t e m b e r 2 8th, 2002, 10:57 PM

Flourine from only com p o u n d s , h m m . Maybe if you started from XeF4.....

a n d I m provised C hemistry > 5-Am inotetrazole (5-ATZ) synth.
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View Full Version : 5-Aminotetrazole (5-ATZ) synth.

I was expecting a sample of this stuff, but I'm not sure if that's going to arrive or not so I've started making it.
It is a cyclic compound, =C(NH2)-NH-N=N-N= (join the ends up), having a very high nitrogen content of 82%. It can form salts
with acids such as HNO 3, HClO 4, and can form com plexes with copper, nickel etc. It is being used / developed for gas
generators in airbags and monopropellants.
I intend to m a k e a m m onium dinitram ide with sulpham ic acid, fo llowing the synth posted by Alchem ist, and try to get a
dinitram ide salt of 5-ATZ. But first, the 5-ATZ m u s t b e m a d e !
T h e p a t e n t s I a m u s i n g f o r r e f e r e n c e a r e # ' s 5 , 4 2 4 , 4 4 9 a n d 5 , 5 9 4 , 1 4 6 , e x c e p t t h a t I a m m a k i n g a m inoguanidine by reducing

nitroguanidine with Zn/acid. The aminoguanidine is reacted with HNO2, and the product is then cyclised to form 5-ATZ.
I a m just about to m a k e t h e a m inoguanidine, using 30g Zn, 14g nitroguanidine and 60mL 70% HNO3 (probably diluted to c.
1 0 0 m L with H2O). I'll let you know how it goes...

W ell, it has been confirmed that the sam ple IS coming! 2kg, for free! :D
But, I shall continue trying to m ake it anyway.
I u s e d 3 0 g o f Zn (5um ), 14g of Nitroguanidine (NG) and 60mL of HNO3.
The NG is long crystals which have a habit of clum ping together. To ensure that it was m ixed well with the Zn (screened to
r e m o v e l u m ps), I mixed it up before I added any water. This caused slig ht accident #1. Residual H2SO4 in the NG disagreed
with the Zn, and the m ixture started sm oking... I dumped it into c. 100m L of cold water, this seem ed to he lp. A slig ht fizzing
for c. 3 seconds, then quiet.
I cooled it to c. 5*C, and started adding HNO 3. At this point I realised that HNO3 probably wasn't the best choice since it
releases NO 2 when reacting with metals, and I'm trying to reduce the NG, but I ca rried on regardless.
All the HNO3 was added at such a rate as to ke e p t h e t e m p below 30*C. The m ixture initially turned yellow due to
nitrosoguanidine (fun stuff, burns like HMTD but without flam e, releasing a cloud of smoke), then the yellow colour was
reduced as the nitrosoG was reduced to aminoG. It's now slightly yellow.
Next step: purify the am inogu anidine...

I think I'll try adding NH3 (g), this should com plex with the zinc and mak e i t m o r e s o l u b l e , I h o p e . . .
A n y i d e a s o n purification?
Alchemist A ugus t 7t h, 2002, 12: 14 PM

Hello all,
Mr. Cool, did you m ake the Nitroguanidine also ? I f s o d i d y o u u s e o n e o f t h e m ethods from the
pat's you posted to get Guanidine Nitrate. Again if so, d id you go straight to Guanidine No3 or to
a So4 or HCL first the n t o t h e N o 3 ? T h a n k s !
Mr Cool A ugus t 7t h, 2002, 12: 54 PM

No, I got it from a chem com pany. Sorry!
If you want to buy som e, try <a href="http://www.omikron-online.de/cyberchem ." target="_blank">www.om i k r o n - o n l i n e . d e /
cyberchem .</a> I haven't used them, but they sell all over the world, their GN is quite cheap, and appear to sell to individuals.
Rhadon August 19th, 2002, 08:06 PM

I doubt that O mikron will ship the GN, because it is m arked with **. That indicates a substance which they don't like to give to
private persons. In order to get it, you will either have to order to a com pany or fill a special form that tells them about your
"abilities to work with dangerous chemicals". See <a href="http://www.om ikron-online.de/cyberchem /" target="_blank">this</
a> site for further information (Germ a n l a n g u a g e ) .
Has anyone ever tried to order ** chem icals from Om ikron?
vulture August 21st, 2002, 04:07 PM

Mr. Cool, i'm a bit confused. I found a compound in my chemistry encyclopedia described as tetrazene, with the form ula
C 2 H 6 N 1 0 a n d i t s e e m s a bit similar to what you describe, however searching chem finder for it results in a com pound with
form ula N4H4.
Unfortunatly I cannot find an image of tetrazene.

Tetrazole Analogues
Preface: If this topic should go into a new thread, go ahead and delete this post, and em ail me about it, and I will report it in
it's own thread. Or just leave it here. :p
H a s t h e s y n t h e s i s o f 5 - m e t h y l t e t r a z o l e b e e n d o c u m e n t e d h e r e ? I t s h o u l d b e v e r y e a s y f r o m t h e s i m ple reaction of acetonitrile

with sodium azide. This looks slightly less powerful than 5-ATZ but should still pack quite the punch as long as it do e s n ' t h a v e
a n a b n o r m ally low density.
Also, is the 5-am ino position the only nitrogen that form s a m m onium salts? If so , then th e 5 - m e t h y l a n a l o gue shouldn't form
any salts. Bu t looking at a compound with another such im ino group, the NH function, perhaps this too form s iminium species,
thus resulting in salt form a t i o n ?
I think I'm hoping for too m uch when I propose using sodium cyanide and sodium azide to, upon quenching with water, form
5-H tetrazole. Anothe r interesting possibility is to incorporate a trim er of this tetrazole into a nitrog en core, by either reacting
3M cyanogen bromide with 1M am monia, or reacting 1M NCl3 with 3M NaCN (speculation warning on that last reaction.)
This compound, N(CN)3 would likely be very poisonous on it's own, but if used in conjunction with sim ple so dium a z i d e , y o u
end up with a nitrogen core with three tetrazole functions dangling off it (or two if three provides too m uch steric hindrance for
reaction) bonded at the 5-position. Extrem e p o wer density.
Bang!
<img src="http://www.aerojetfinechem icals.com /azide.gif" alt=" - " />
Prim oPyro
Microtek S e p t e m b e r 1 st, 2002, 12:53 PM

I just stum bled on another high nitrogen explosive which m ay in terest you; hydra zine azide N5H5, nitrogen content 93.3 %.
I h a v e f o u n d the following pro perties:
Density 1.30 g/cc ( not so good )
Heat of formation 3043 J/g
Melting point about 75 C
Quoted as "completely insensitive to o rdinary mechanical stim ulus"
D e c o m position tem p a b o u t 1 0 0 C
Usin g sim ple approxim a t i o n s , I h a v e f o u n d a V O D o f 7 2 0 0 m / s a n d d e t o n a t i o n p r e s s u r e o f 1 8 4 K b a r , b u t o n t h e o t h e r h a n d

the Berthelot approxim ation g i v e s a g a s v o l u m e * e n e r g y r e l e a s e product of 170 % relative to TNT.
Synthesis is relatively sim p l e . O n e m e t h o d w a s t o r e a c t a m m onium azide with hydrazine hydrate and let the produced NH4OH
and water evaporate.
Mr Cool S e p t e m b e r 1 st, 2002, 02:25 PM

T h a t r e m i n d s m e, I was going to try m a k i n g a m m onium a z i d e s o m e time, but never got round to it though (like so m any
things :()
93.3%, lol, that's pretty high! I was wondering, how are those VoD's, det pressure s etc calculated? I did a search, but only
found things like "calculated VoD for explosive X is high er than that of RDX...", nothing that told m e how to calculate it...
My sample did arrive, but I'll carry on with the synth anyway (I totally forgot about it!). I was able to sepera te the
a m inoguanidine, I filtered unreacted zinc out of the solution (he ated to 60*C, to dissolve everything soluble), and then
reduced its volume to c. 50m L, then I acidified it strongly with 70% HNO 3. Aminoguanidine nitrate ppted, I weighed it a few
m inutes ago and got just over 5g. Tha t's as far as I got, I left it to dry and forgot about it!
So far I haven't done m uch with the 5-ATZ I recieved, the nitrate salt is rather fun (burns FIERCELY), I haven't tried the
dinitram ide yet. I was all set to m ake ADN, I even had the dry ice, then got distracted and all the dry ice sublimed before I
r e m e m bered :(. I tried a very quick, half-arsed attem pt at m aking 5-nitram inotetrazole, using 5-ATZN and H2SO4, but didn't
get anything. I'm really not surprised though, I took literally no care when doing the experim ent (a pinch of 5-ATZN, a m L or
two of room t e m p H 2 S O 4, I ju st mixed it together, waited until I got bored, and dumped it into a few m L of water).
nbk2000 S e p t e m b e r 1 st, 2002, 03:11 PM

Just curious as to how you got the sam p l e . D i d y o u u s e t h e s a m p l e s c a m where you're "Research Com pany X"? <im g
border="0" title="" alt="[W ink ]" src="wink.gif" />
Microtek S e p t e m b e r 1 st, 2002, 03:21 PM

If you do a search on the subject ( calculating detonation pressure or som e such ) within alt.engr.explosives, I think you'll get
s o m ething - that's where I found it ( though I've found it elsewh ere since ).
You'll need to test the calculations against a few known explosives because the poster was not certain of, o r did not bother
with, the correct units cal/g or J/m ol for the heat of detonation for instance.
Mr Cool S e p t e m b e r 2 nd, 2002, 07:22 AM

It was very easy to get the sam p l e , I e - m a i l e d t h e c o m p a n y f r o m a m y n a m e @ h o t m ail.com accoun t, asking them if they would
s e n d m e a 2 k g s a m p le so that we could test it before we placed an order, to see if it was suitable for our needs (always "we",
"our" etc). Then add the usual "Thank you very m uch for your help", "we look forward to d oing business with you", "with best
regards, Mr. My Nam e (representative X of imaginary co mpany X)" etc.
I've used this basic e-m ail to succesfully get mannitol, sem icarbazide*HCl and 5-ATZ, and I would've got a lot of other chem s
with it, but they often asked m e to pay shipping for a 1.5kg parcel from China etc., which is norma lly aroun d $ 8 0 a n d t h a t
defeats the object of getting free sam p l e s . A l s o I ' v e f o u n d I n d i a n c o m p a n i e s t o b e m o r e h e l p f u l t h a n C h i n e s e o n e s f o r s o m e
reason.
Mr Cool S e p t e m b e r 1 0th, 2002, 04:35 PM

Just synthed what I believe to be 1,4-ditetrazolyltriazine!
I was reading about tetrazene in CO PAE, and discovered that som ething called 1,4-ditetrazolyltriazine could be m a d e b y
reacting 5-ATZ with NaNO2 and excess CH3CO OH. I use d citric acid, since I had no acetic acid stronger than vinegar, and citric
is th e least useful of the carboxylic acids that I have.
I added the 5-ATZ and citric acid to 150m L of water, and stirred until the citric had dissolved. 5-ATZ isn't very soluble, but this
didn 't seem to m atter. It all reacted in the end.
As the NaNO2 was slo wly adde d, the solution tu rned to yellow, orange, red, and then a very fine (looks am orphous, but could
just be cryptocrystalline) sandy-coloured ppte started to form , and eventually settled. I left it overnight (I started yesterday) to
fully ppte, now there are also som e slightly more reddish particles in the ppte, I think these are larger crystals of the same
stuff. I'll try recrystalising it all soon to see wha t happens. Oh, and the only tim e I used cooling wa s when I added a bit too
m uch NaNO2, and it started to fizz too much.
Anyway, the dried ppte is nicely flam e sensitive , s m a l l a m o u n t s m a k e " P U FF!", "C RACKLE!" kinda noises when put into a flame.
I'll try to recrystalise it and let you kno w what happens in case anyone's interested.
Ricky August 26th, 2006, 04:05 PM
I`ve searched a while and found 5-mercaptotetrazole-1-acetic acid is a explosive stuff. It dosen`t exist detailed informations
about a mercaptan of a tetrazole or something like this but i belive it will give som e i n t e r e s t e d s u g g e s t i o n s . D o e s a n y o n e h a v e
idea s to the synthesis way to 1-chlorotetrazole-5-tiol ?
megalomania August 26th, 2006, 04:54 PM

Is 1-chlorotetrazole-5-tiol the correct n a m e f o r t h i s c o m p o u n d ? D o y o u h a p p e n t o h a v e a C A S n u m ber, or a reference that
m entions this substance?
Bradt August 31st, 2006, 02:41 PM

I can`t found som ewhat to 1-chlorotetrazole-5-tiol but i found som e i n t e r e s t e d c o m p o u n d s t o t e t r a z o l e s .
5 - a m i n o - 1 H - t e t r a z o l e m onohydrate, Cas-Nr. 15454-54-3

N-(1 H-tetrazol-5-yl)-guanidine, CAS-Nr. 66591-60-4
bis-(1H-tetra zol-5-yl)-am ine, C AS-Nr. 127661-01-2
1 - a m i n o - 4 , 5 - d i h y d r o - 1 H - t e t r a z o l e - 5 - o n e , C AS Num ber: 84143-61-3
I believe this will have interest,

5 - a m i n o - 1 H - t e t r a z o l e m onohydrate and bis-(1H-tetrazol-5-yl)-am ine in +99% HNO3 and N2O 5 ->
1-nitro-5-am inotetrazole and bis-(1-nitro-tetrazol-5-yl)-amine.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Recycling Calcium
Sulfate, is it Possible?
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View Full Version : Recycling Calcium Sulfate, is it Possible?
megalomania August 11th, 2002, 10:30 AM

A big concern in any lab is economical use of chemicals. Perhaps more so with myself I try to conserve as much chemical waste as possible. While review a number of chemical
reactions that I perform, and hope to perform in greater quantities in the future, I observed that I will produce a rather large quantity of calcium sulfate waste. This is primarily
due to the usefulness of sulfuric acid in many chemical reactions providing abundant sulfates.
Upon reviewing methods of converting calcium sulfate back into either sulfuric acid or obtaining the sulfur in some way I was distressed to note that it is largely insoluble and
inert. Unless I want to add some to my garden, or plaster my walls there isnt much I know to do with it.
Perhaps electrolysis to lime water and sulfuric acid could be possible, but would this be economical in any way? The solubility of calcium sulfate is, according to my calculations,
about 2.5 g per gallon of water. This assumes I even have the specific hydrate that can achieve even this high solubility (compared to the other calcium sulfate solubilities). I
wonder if a 55 gallon drum filled with 50 gallons of water and excess calcium sulfate could maintain a saturated solution of a whopping 125 g of the stuff. Would this be far to
wasteful of electricity and time?
I wonder if molten electrolysis is out of the question. I found a melting point of 1450 degrees C and a boiling point of 1193 degrees C. Yes, I know the boiling point is lower
than the melting point, strange. I did find that it could be decomposed at elevated temperatures, but not what that temperature may be. The solubility can be increased in nitric
or hydrochloric acid which is a plus I suppose. On the other hand it is practically insoluble in sulfuric acid, which would be bad in aqueous electrolysis.
I have heard it can be a problem at landfills when calcium sulfate is subjected to a moist, anaerobic, low pH environment producing hydrogen sulfide gas. A biological approach
maybe? I gather it can be burned to sulfur dioxide gas, so perhaps it can be directly reconverted into sulfuric acid, or at least an easier to deal with sulfate.
If anyone has any suggestions or novel ideas to help me as I begin this research project it will be appreciated.
nbk2000 August 11th, 2002, 10:44 AM

Could it be used as a neutralizer for acid spills? The stuff is pretty useless except on an industrial scale, so why bother with trying to recylce it?
Wait, isn't Calcium Sulphate also known as "Plaster of Paris"? If so, then that'd be useful as molding material for casting things that go boom.
rikkitikkitavi August 11th, 2002, 01:26 PM

CaSO4 is a LARGE byproduct of the fertilizer industry , where phosphate fertilizers are produced- sofar no one have found a economically way of turning into more useful
chemicals. Ergo it is used as plaster. In sweden a large fertilizer factory build a
island in the ocean with it and on that island now 20 windmills stand.
Probably as usefull as it gets.
The high melting point points out that is is very stable. Electrolysis of molten CaSO4 with graphite would probably lead to
formation of CaS and CO(CO2) since CaSO4 can be reduced to the sulfide with carbone at 1200+ K .
At even more extreme temperatures it decomposes into CaO and SO2 like all sulfates.
This could be the reason why the boiling point was stated to be lower than the melting point, since it is physically impossible for a substance to boil before it melts at the same
pressure.It simply starts to decompose at the lower temperature and the decomposition of course accelerates at higher temperatures.
CaS can be used to genereate H2S of course .

Sulfides are strong bases (S-- + H2O = OH- + HS-)
Electrolysis in a aqeous solution would only yield

H2 and O2, and due to the low solubility conductivity is very low, hence demanding high voltage to get the current flowing.
I would just dump it. It is fortunately not harmful. It is a powerful drying agent however and can be used as one. In the CRC handbook there is a table of drying agents affinity
for water, and I think that only P2O5 and H2SO4 had higher absorbtivity.
/rickard
[ August 11, 2002, 12:43 PM: Message edited by: rikkitikkitavi ]
vulture August 12th, 2002, 08:48 AM

Well, perchloric acid is a stronger acid than H2SO4 and approx. has the same volatility so conversion to Ca(ClO4)2 could be possible. I have however no idea how soluble that
would be.
But I think using perchloric acid for this would be even more a waste of precious chemicals.
Pu239 Stuchtiger August 14th, 2002, 05:47 PM

It could be used as an exceptionally shitty dessicant.
It could be used to build a giant new lab separate from your house.
CaSO4 will dissolve in HCl solution for this reason:
CaSO4 + HCl ----> CaClHSO4
CaSO4 dissolves in many acids due to very similar reactions.
A-BOMB August 14th, 2002, 07:04 PM

Or you could make some of that thermite that NBK was talking about a while ago. Or you could do some powdered fuel FAE studies, or you could just drive down rt 65
spraying it out to make a quasi-smoke screen causeing 15 car pile-up up and down rt 65.
vulture August 16th, 2002, 05:53 PM

CaSO4 won't dissolve in many acids simply because H2SO4 is a strong acid with a high boiling point.
Only acids which are stronger and have the same volatility or acids which have the same strenght but a much higher boiling point can do that. HCl is stronger but very volatile
and is not easily obtainable in full strenght which would be required.

I have made a modicum of progress on this front recently. Apparently you can react ammonium carbonate with calcium sulfate to swap the ol ions and get ammonium sulfate
and calcium carbonate. A quick check of the chemistry leaves something to be desired though, I would suspect a bisulfate in there somewhere. Now I just have to figure out
how to make and utilize ammonium carbonate. Since the Merck was kind enough to inform me ammonium carbonate doesnt really exist, its actually a mix of ammonium
bicarbonate and ammonium carbamate.
I have reason to believe from what I read that you can mix gypsum and ammonium (bi)carb together, dry, and heat strongly (red heat) to get this conversion. Otherwise the
two are mixed in solution, a not altogether desirable proposition considering the low solubility of gypsum.
If successful the ammonium sulfate could be readily decomposed by heating or electrolytic methods. The ammonia could be recovered and processed back into a bicarbonate
with CO2 (I still have to work on this part). That just leaves a bunch of calcium carbonate, which I could certainly use (I would probably turn it back into lime to neutralize the
sulfuric acid that makes all the gypsum in the first place). This seems like a neat and tidy recycling project.
Of course my references are dated, I may be totally off base, and who knows if I have misinterpreted an ancient chemical name I present this idea for peer review now while
I figure out how to make ammonium carbonate for experiments in the future.
rikkitikkitavi August 25th, 2002, 03:44 PM

I believe I have read somewhere that it was a method in industrial scale where CaSO4 , NH3 and CO2 was reacted into CaO, [or Ca(OH)2],(NH4)2SO4 and CO2.
First
NH3 + CO2 + H2O => (NH4)2CO3
like megalomania wrote, it is not really NH4CO3 but it acts like it in solution:)
(NH4)2CO3 + CaSO4 => CaCO3(s) + (NH4)2SO4

the much lower solubility of CaCO3 than CaSO4 leads to the reaction progressing.
They simply had a slurry of CaSO4 in a pressurized wessel and lead CO2+NH3 into it (pressure increased the rate of gases reacting)
and letting it stand for a while.
Afterwards the CaCO3 was filterd off, the soltion evaporated and (NH4)2SO4 recovered. CaCO3 was converted into CaO by heating.
The energy for this came from coal , thus producing CO2 ,or recovering the CO2 from the CaCO3 decompostion.
/rickard

Ive been thinking about this for some time. I think unless you plan to build a small chemical plant possibly needing high pressure ammonia and carbon dioxide it wont be much
use. You could try it in small amounts using a sodastream type carbonator and aq ammonia. Solvay (Which produces Sodium carbonate and Calcium chloride from calcium
carbonate and NaCl) only needs 880 amonia and CO2 bubbled in at neer atmospheric pressure to make the reaction work (These are intermediates). I suspect a sodastream,
or similar home carbonator could be modified to produce quite high pressures of carbon dioxide if required.
Ultimatly recycling requires wasting one resource or other but if we can reduce it to a cycle requiring only electricity I think we can say we have succeeded. CaSO4 is reduced
by carbon at high temp to give CaS, which unfortunatly has an ungodly melting point. If you had HCl you could produce H2S and CaCl2 both of which are useful. Turning CaCl2
into HCl and oxide or bleaching powerder, or using the chlorine in another way is promising, but H2S is, lets face it, rather poisonous, and liberated from HCl and CaS might be
difficult to put to constuctive use.
CaCl2 cant be electrolysed directly, the sparingly soluable hydroxide clogs up the electrodes forcing the voltage up until its impractical. You can mix with sodium carbonate, and
electrolyse the salt, and roast the calcium carbonate to CaO. If you can get mercury, which has long term toxicity problems to worry about, you can make something like a
whiting cell, or a castner chlorine cell to decompose NaCl completely into sodium hydroxide and chlorine. The cell can be aranged similar to the castner chlorine cell such that
the mercury is always covered by liquid and a rocking motion distributes the amalgam between the compartments, though I would advise against an exact copy of this cell
which might alow mercury ions into the hydroxide product. With a purely passive reaction between the amalgam and water the product should be virtually free of mercury and
assuming this cell is outside and doesnt have to be dissasembled on a regular basis mercury toxicity should be not a problem. Chlorine, sodium hydroxide and hydrogen have
vast numbers of uses. You can easily make concentrated bleach, HCl directly and from those 5 chemicals the possabilities are vast. Salt is very very cheap. I'm ignoring how
unpleasent/potentially fatal chlorine gas is but if you cant build equipment to use this safely, even if its only making bleach and venting the remainder, then you shouldnt be
doing chemistry at all. Work outside and dont botch the job, build it to last or dont built it at all. If you need to dissasemble the cell, drain the water without losing any mercury,
get as much of the mercury as possible into an air tight bottle (much easier said than done), and douse everywhere the mercury has touched with sulphur dust. Sweep up and
discard apropriatly. This paragraph is much less a how to, and much more an idea in motion, needs to be expanded. Suggestions needed.
How about this idea for CaSO4 though. Reduce to CaS, add FeCl3, which is available everywhere for etching PCBs, obtain CaCl2 and iron sulphide Fe2S3 as a ppt. This turns
into Ferrous sulphide and Iron disulphide (Iron pyrites) on heating at 60C, it can be dried and burned to produce the oxides and SO2 which can be used to make sulphuric acid.
Iron oxides can be reduced by C in a very high temp furnace to make iron, this is certainly possible in a garden furnace specifically designed for iron and can be made out of
clay. Recycling the CaSO4 requires vast amounts of power and carbon, and a lot of semi industrial process, but it can be done.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > potassium permanganate synthesis
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woo-jong August 28th, 2002, 09:22 PM

This information is from my book 'Inorganic synthesis experiments'(This book doesn't exist in USA. it's a Korean book)
this says how to synthesis potassium permanganate from manganese dioxide.
What we need : KOH 10g

KClO3 5g
MnO2 10g
a crucible , heating source, iron wire
Procedure :
1) Mix crushed 10g of KOH and 5g of KClO3 in a crucible.
2) While stirring with iron wire, heat to 400 degrees Celsius to make it melt. Stop heating when all of the mixture melts.
3) Slowly add 10g of powdered MnO2 to melted mixture. procedure 2,3 needs stirring with iron wire. If you don't stir enough, it will be difficult to perform next procedure
4) Harden the melted mixture and powder it. Dissolve this in 200ml of boiling water.
5) To neutralize excess base, we should bubble CO2 gas through the solution of procedure 4
6) Let the precipitate(MnO2) settle down into the bottom of beaker. and filter it with glass filter(not filter paper)
7) Finally , let the solution evaporate. There will be purple crystals. this is potassium permanganate. Wash it with a small amount of cold water and store it.

I have recently conducted a review of the synthesis of this substance for my work on OTC benzene. While that procedure closely fits with what I have, I should add one step. To obtain a superior homogenous
mixture of potassium chlorate, potassium hydroxide, and manganese dioxide dissolve these in a minimum amount of water. Upon heating to remove the water they will be well mixed. The manganese dioxide does
not dissolve of course, just the potassium compounds
It is not entirely necessary to use the CO2 as you will get KMnO4. However, it will improve yields. Most assuredly there will be some potassium manganate (K2MnO4) that the CO2 will convert into
permanganate. 3K2MnO4 + 2CO2 --> 2KMnO4 + MnO2 + 2K2CO3. The manganese dioxide can be recovered after this.
I want to take this to the next step. There are a few pressing issues that should be addressed in making this a worthwhile synthesis. Basically they all revolve around where to get the starting materials and how to
recycle the waste products.
For the recycling it will be necessary to get back all of the potassium chloride and carbonate that is left behind. It is also desirous to purify the potassium permanganate by removing these materials. If you just let
the final solution evaporate, you will get a mixture of potassium permanganate, potassium chloride, potassium carbonate, and most likely some potassium hydroxide and potassium chlorate. That seems like a
mess to me. Fortunately potassium permanganate is the least soluble of these. It can be recrystallized as it were by reducing the volume of water and chilling it in an ice bath to precipitate the crystals. This may
take some time to do effectively, or may take a few batches.
I would say keep all the potassium compounds because you may want them to make KOH. This leads me in to where to get KOH as well as the chlorate. I do believe there are various methods of making
potassium chlorate out there? If there are I am not familiar with them at this time. I do know that getting potassium compounds are not all that simple. As far as I know the only commercial OTC source of
potassium ions is driveway ice melter, and this is a mix with sodium, potassium, calcium, and magnesium chlorides.
Ahh but in the Poor Mans James Bond there is that wonderful bit about making potassium ferrocyanide. The first step is to extract potassium carbonate from wood ashes. Bingo, plenty of potassium compounds
there. Now I dont recall if that stuff can be purified, but I do know it can be done. I once obtained a nice crop of crystals (it helps to have a fireplace that is frequently used). From here it should be a simple matter
of flower pot electrolysis to obtain KOH. After doing this you can substitute the waste potassium compounds in the same electrolysis. IIRC you also make potassium chlorate by electrolysis? This should take care
of both the hydroxide and chlorate.
Now then, what about manganese dioxide? I have heard you can get this from batteries. Specifically dry cell non rechargeable types, especially the big lantern kind. I have begun collecting batteries a few months
ago in anticipation of cracking them open. What I do not know is what to do when I open them. I gather you want the central black core of the battery, the powdery black stuff. I could have sworn I once saw a
website that had a diagrammatical representation of the battery with info on plundering the MnO2 core. I have not yet obtained a big lantern battery (I am waiting for one to die), but I imagine they would give the
greatest yield on time invested. Meaning it is just as easy to cut one of those open as it is to cut open a AAA battery, but with a lantern battery you get much more.
I think the MnO2 is in a paste with a base. Chucking it into water may dissolve everything but MnO2. I am sure someone here has more experience with this than I.
Alternatively one could buy KMnO4 for their water purifier or their pond. Potassium permanganate is now listed on the DEAs watch list and as such its availability is diminishing. I have prepared some writings on
legit uses of permanganate so as to have some plausible excuses as to why to buy it from a water store (like a Culligen man, any place that sells water purifiers, softeners and such). Its use in water softeners is
dwindling because only older ones use it. It can be purchased online for adding to ponds (algae control I believe, I have some excuses for that as well).
I still find it necessary to know how to make potassium permanganate from manganese dioxide because after you use potassium permanganate you end up with lots of manganese dioxide. Cheap bastard that I am
I find it shameful to go through all the trouble of getting either potassium permanganate or manganese dioxide and then just throwing it away.
I have some experimenting to do it seems. I am documenting this information for my OTC benzene project, which uses potassium permanganate to oxidize toluene. It is a requirement that everything be OTC and
so I have studied up on where to get potassium permanganate, and how to recycle it. Any and all criticisms and comments on my theoretical steps outlined here will be much appreciated.
Pu239 Stuchtiger August 29th, 2002, 03:57 AM

Potassium cations are plenty easy to come by. Potassium hydroxide lye, for example. Potassium nitrate! Potassium chloride is sold as a salt substitute.
The chlorate anion can be prepared by heating a solution of hypochlorite anions.
3[OCl-] ---> [ClO3-] + 2[Cl-]
It can also be prepared by bubbling chlorine dioxide through water - results in a stoichemitrically equal amount of chlorite and chlorate anions.
Hot solutions of chlorides can be electrolyzed, resulting in the formation of chlorates. Alternating current is desirable.
I have no trouble finding potassium permanganate. I buy it at the local hardware store; 2.27kg for $25.
[ August 29, 2002, 03:07 AM: Message edited by: Pu239 Stuchtiger ]
Polverone August 29th, 2002, 04:01 AM

<blockquote>quote:<hr />As far as I know the only commercial OTC source of potassium ions
is driveway ice melter, and this is a mix with sodium, potassium, calcium, and magnesium chlorides.<hr /></blockquote>Nope. Look for muriate of
potash - potassium chloride - at agricultural supply outlets and many home and garden centers, and also for sodium-free water softening. Many premium alkali drain openers contain potassium hydroxide and
potassium hypochlorite. Cream of tartar - potassium bitartrate - is available (at a high price) in the spice section of grocery stores and is easily converted to potassium carbonate by heating in air. Potassium
nitrate has a number of OTC sources. KOH may be obtained in pure form as a supply for soapmaking.
You can react K2CO3 with Ca(OH)2 to obtain KOH if you don't want to use the slow, tedious electrochemical method and you have a source of calcium hydroxide.
You can obtain MnO2 from batteries, but only the old-style non-alkaline type, which are harder to find nowadays. Far better is to buy your MnO2 by the pound from a ceramics supplier.
<blockquote>quote:<hr />Alternatively one could buy KMnO4 for their water purifier or their
pond. Potassium permanganate is now listed on the DEA's watch list and as such its availability is diminishing.<hr /></blockquote>KMnO4 has been on
the DEA's watch list for quite some time, but since it is used for cocaine production in South America they don't seem to care about small (less than dozens of kilograms) domestic purchases. Acetone is
"watched" too, yet you can buy it any hardware store. KMnO4 isn't too hard to find, you just have to hit the right store. It's not suspicious to purchase from a dedicated dealer, either.
KClO3 can indeed be prepared electrolytically, or by bubbling chlorine through hot KOH solution.

Carbon-zink batterys are the cheapest nonrechargeables, they contain mix of carbon powder with MnO2 soaked in NH4Cl solution. Havn't heard about ammounts :(
I have extracted the NH4Cl, but don't really see how to separate MnO2 from carbon.
Cricket August 29th, 2002, 09:02 AM

I had never heard of glass filter paper before, so I nosed around and found a place to buy it, along with many scales (good prices).
<a href="http://lab-supplies.balances.com/lab/7" target="_blank">http://lab-supplies.balances.com/lab/7</a>
NOTE: They have a minimun of $75 order (ok if you are buying a shit load of filters and/or a scale). Maybe this was not as good a site after all.
NOTE 2: I am pretty sure I have seen a bettery with a dry powder inside, not dampened. I can't recall the name, but it was mostly black and had a lightning bolt on it and a cat too I think, maybe this will ease the
process. Only name i can think of is Rayovac or something (may not be the name at all or the neme of something else).
[ August 29, 2002, 08:10 AM: Message edited by: Cricket ]

If you open a normal alkaline battery you will find a carbon grey and hard outer layer and some zinc powder with cellulose in the middle. The trouble would be getting rid of the graphite, the only way I see would be
dissolving in CS2 as only the carbon dissolves into it.
Keep the zinc powder! It's very fine and extremely pure! You just have to remove the grease by dissolving it into toluene or another aromatic.
Machiavelli August 29th, 2002, 03:45 PM

How about heating the stuff until it glows? MnO2 is pretty inert and probably won't do anything, NH4Cl will turn to NH3 and HCl if it isn't washed out before and Carbon will turn into CO2.
And wouldn't it be easier to clean the zinc with acetone, as this is normaly my first choice to (dis)solve dirt related problems. And every forumite worth his/her salt has it standing around.
Btw, Polverone, where did you get the coke info from? I know KMnO4 is usefull for speed synths but I don't see how it could be used for coke extraction.
Polverone August 29th, 2002, 04:58 PM

Vulture: graphite dissolves in CS2?! I find that very surprising. I would suggest that there are better uses for it :)
Machiavelli:
From <a href="http://www.druglibrary.org/schaffer/GovPubs/cocccp.htm:" target="_blank">http://www.druglibrary.org/schaffer/GovPubs/cocccp.htm:</a>
<blockquote>quote:<hr />Potassium permanganate is combined with water. This mixture is
added to the coca paste and acid solution. Potassium permanganate is used in this step to extract other alkaloids and material that is undesired in the final product.
In particular, potassium permanganate is used to break down the alkaloid ciscinnamoylcocaine found in large concentrations in E. novogranatense varieties. If the coca paste has a high concentration of this
alkaloid and potassium permanganate is not used, then crystallization of cocaine HCl will be very difficult.<hr /></blockquote>
kingspaz August 29th, 2002, 05:37 PM

Machiavelli, the carbon, depending on Manganese's reactivity may reduce the MnO2.
MnO2 + C --> CO2 + Mn
not sure how reactive Mn is though...
edit: just found that MnO2 is in fact reduced by carbon.

<a href="http://www.scescape.net/~woods/elements/manganese.html" target="_blank">http://www.scescape.net/~woods/elements/manganese.html</a>
[ August 29, 2002, 05:25 PM: Message edited by: kingspaz ]
irish August 30th, 2002, 07:24 AM

hi all
potassium permanganate is sold in australia under the name condys crystals,price about $17AU per KG.
it's avalable from stockfeed store's along with sulfur,KCl etc.
hope it helps
irish

MnO2 is a pretty strong oxidizer, don't heat it. For example, it will evolve Cl2 when in contact with HCl.
megalomania August 31st, 2002, 08:55 PM

I didnt mean to imply that it was the great and powerful DEA, stealer of freedoms and rapers of children, that caused potassium permanganate to dry up. That seems to be the effect of plain ol commerce. The
water softeners that use it are no longer in favor, with their being better technologies, and there are better products to put in your pond for algae control. Like most pure chemicals out there, they are typically
replaced by something better for their intended purpose. We however have alternative uses for our commercial products :D I would agree that the stuff is plenty available when you can get it. I can get a 5 Kg pail of
the stuff for $20.00 at a place less than 4 blocks from me, but I still want to have answers to those annoying questions, Why dont you buy yourself another water softener? or the Can we have your name
please
As for the potassium ions, nothing has come up in my chemical surveys of the major hardware stores and garden centers, but of course there are many wonderful things in different areas. My point being that it is
far more economical to use wood ash as a source. It certainly is for me with a frequently used fireplace, those without one may find it cumbersome to acquire wood and burn it just for ash. Even most people with
fireplaces rarely use them as the amount of work involved in obtaining, splitting, stacking, and hauling wood is considerable. Of course I happen to have 40 acres of forest to use. In all fairness I am not the one
who cuts and splits all the damn wood, some other fool does that task.
I must check out the local ceramics stores. I have never been to one but recently I have seen several posts talking about all the goodies at one. I opened my new phonebook, which came a few days ago, to see if
there were any. Well there were dozens within a 20-mile radius or so. I never knew the places were that popular. There are a few in my own town and I never heard of them.
I have obtained some diagrams of the inner working of alkaline dry cells. I am a little distressed to learn of the reaction
MnO2 + H2O + 2e- --> Mn2O3 + 2OH-
At the same time I see that the MnO2 is actually coating the outside of the carbon rod and it can be scraped off with little actual carbon coming along for the ride. The mixture of zinc chloride and potassium
hydroxide can be dissolved away. Any Mn2O3 would appear very much like MnO2. Could anything be done with that compound?
Otherwise it seems to me that only new batteries would have much MnO2. Ultimately this is a very ghetto way of going about getting the stuff, but it is one that is applicable to just about any country of the globe,
or for that distant future when all things are banned. It is also nice to fancy yourself some sort of environmentalist by actively recycling :p
PS: There's KOH in those batteries too, sounds like one could kill two birds with one stone.
nbk2000 September 1st, 2002, 07:53 AM

Extraction of KOH from wood ash is very uneconomical. It requires something around a ton of wood to produce enough ash for 10-12 pounds of KOH. <img border="0" title="" alt="[Eek!]" src="eek.gif" />
Whole forests were cut down and burned up to provide the makings of nitre for the black powder used in europes wars during the last few centuries.
KCl, on the other hand, is cheap. 40 pound sacks of it as "Sodium-free Water Softener Crystals" for $10. :) Converting it into something more useful than food flavoring though... <img src="http://
www.roguesci.org/ubb/icons/icon17.gif" alt=" - " />
Pu239 Stuchtiger September 1st, 2002, 02:04 PM

I can't believe you can't find potassium chloride. It has been sold in every grocery store I have ever set foot in. Brand name: "No Salt".
megalomania September 2nd, 2002, 01:10 AM

A ton of wood While that may sound like a lot, I bet I go through 5-6 tons a year, perhaps even more. The fireplace is burned every day from fall through spring (i.e. when its cold out). Of course I admit this is not
a typical usage for a fireplace in this day and age. Most people use their fireplaces a few times a year for company going through a dozen logs. My aunt uses those fake logs on Christmas, just one pitiful little stick
burning away. We make fun of her, yes.
It appears I was a bit hasty when I said there were no potassium compounds out there. This time I actually read my chemical survey and the results are thus:
At a pool and spa store I found potassium carbonate in solution as a pH raiser, and potassium monopersulfate as spa shock (946 mL/$7.99 and 907 g/$14.99 respectively). At a grocery store I found pure potassium
chloride as ice melter (9.08 Kg/$3.99). The other ice melter mix was from Wal-Mart.
jimwig September 30th, 2002, 11:20 PM

recovery of MnO2 from dry batteries
US1192061
a little crusty (1916) but neat stuff on solubilities and recovering the stuff
Alchemist October 1st, 2002, 10:51 AM

Hello all,
just a quick note! I have also seen in several chemistry books that KNO3 can been used in place of KCLO3 for the production of KMNO4. I do NOT have the amounts in front of me, but I believe it was about the
same as for the KCLO3 or just a little more!
megalomania October 1st, 2002, 06:40 PM

I wonder if manganese chloride could be substituted for manganese dioxide in the preparation of potassium permanganate? It is in the wrong oxidation state (II), but the same reaction that transforms the
manganese (IV) dioxide into manganese (VI) in the form of potassium manganate might work the same.
3MnCl2 + 6KOH + KClO3 -> 3K2MnO4 + KCl + 6HCl
(this is the usual rxn: 3MnO2 + 6KOH + KClO3 -> 3K2MnO4 + KCl + 3H2O)
I bring this up because it would seem to me an easy means of separating manganese dioxide, or manganese oxide from carbon in batteries is to react the oxides with hydrochloric acid to form MnCl2. As this is
soluble it can be removed from carbon. A pre-wash with water will remove any hydroxides and chlorides from the battery.
This still strikes me as a good way of getting pure dioxide through the chloride. I have some unconfirmed date here that suggests MnCl2 + Ca(OCl)2 --> MnO2
Could there perhaps be other ways of getting the dioxide from the chloride? I suggested using the chloride earlier to avoid having to go through the trouble.
Some additional notes on the standard procedure may be in order now. The use of a glass fiber filter is necessary because potassium permanganate reacts with regular filter paper, it being an organic substance.
One can avoid the filtering step all together by decanting the solution of permanganate. Sure you may loose a little bit, but that is better than shelling out who knows what for special filter media.
It is not necessary to use CO2 in the preparation of the permanganate. One can use just about any acid that is handy. I have a chemistry text that makes the stuff using HCl to acidify the potassium manganate
solution. In one of the MAO books there is a bit that recommends bubbling in chlorine gas to avoid the formation of manganese dioxide. And wouldnt that be convenient to use the chlorine gas generated by adding
MnO2 from batteries to HCl (assuming that step works).
It is too bad I dont have any potassium chlorate handy, I have a battery that I found, so I could test this out. If someone would be so kind as to direct me to a quick reference on chlorate synthesis so I can verify
my information, I can start experimenting.
Polverone October 1st, 2002, 10:21 PM

MnO2 can indeed be obtained from MnCl2 by hypochlorite oxidation. But why bother with that, or with batteries at all (unless you have a lot of old ones lying around?) Get thee to a ceramics supply outlet, and buy
MnO2 by the pound. Ceramic grade MnO2 can be less than $1/lb in bulk. Of course, if you *do* recycle old batteries into MnCl2 and then into MnO2, the MnO2 should be more active than what you'd get from the
ceramic supplier, since it precipitates in a finely divided form upon aqueous MnCl2 oxidation.
Boob Raider October 2nd, 2002, 12:06 AM

Wish come true Mega .... :p <a href="http://www.poortour.com/build/pyrotechnics/kclox.html" target="_blank">http://www.poortour.com/build/pyrotechnics/kclox.html</a>
This seems to be the most relavent site .... but would someone tell me how to make those damn PbO2 electrodes .... the link on this site doesnt work. I was also thinking ... if a mix of
Mn(NO3)2 and KOH would be heated or distilled (depending on if the rxn works) one should be able to get KMnO4 and H2O and N2O or something like that.
[ October 01, 2002, 11:24 PM: Message edited by: Boob Raider ]
megalomania October 2nd, 2002, 01:04 AM

It has struck me as odd that there is little information on using manganese chloride in chemical operations in the older literature with it being used so much in the preparation of chlorine. In fact I have seen several
references to it being a huge waste product. I knew there must be some soul who posed this question in the 19th century, so I kept digging. I found something:
Various attempts have been made to economize the vast quantities of chloride of manganese formed during the manufacture of chloride of lime. The most successful is one employed by Mr. Dunlop. It consists in
precipitating the manganese as carbonate, and roasting the carbonate at a temperature of about 600 degrees. The crude acid solution of the chloride is treated with milk of lime in quantity sufficient not only to
neutralize the excess of acid, but to precipitate the iron as sesquioxide. The clear liquid is then pumped up into an iron boiler and mixed with a proportion of chalk just sufficient to precipitate the whole of the
manganese, an excess being carefully avoided. The mixture is heated by the injection of steam, which is maintained for about 24 hours under a pressure of from 2 to 2.5 atmospheres; under these circumstances
carbonate of manganese is precipitated, and chloride of calcium formed in the liquid. The solution is run off from the precipitate, and this is well washed, pressed, and partially dried. In this condition it is
introduced in shallow sheet-iron cases on wheels into large vaulted galleries of brickwork heated to about 600 degrees: through these a current of air is maintained. The carbonate is gradually made to pass from
the cooler to the hotter portions of these galleries, being from time to time sprinkled with water. The carbonic anhydride is gradually expelled, and oxygen absorbed: so that at the end of 48 hours about 72% of the
carbonate has been converted into black oxide. The process, however, is expensive.
(Hofmanns Int. Exhib. Jury Report, 1862, p. 36.)
This procedure could perhaps be simplified a bit. First, it is important to note that in the before time of the long long ago the ancients had a considerable amount of iron contamination in whatever process was used
to make their manganese chloride. Apparently the manganese dioxide used in batteries is quite pure, certainly free from iron. Therefore there is no need to add calcium hydroxide solution (milk of lime) to
precipitate any iron. Assuming the contents of a battery is added to water first to remove any soluble material, then to HCl to make the chloride, and finally filtered to remove carbon, the resulting manganese
chloride should be quite pure.
Second, the whole adding steam at 2 atm pressure for 2 days is an industrial process. In the lab we can add calcium carbonate to the manganese chloride solution and boil it, or rather reflux. I cant say how long it
would take all this to go to completion. It may be wise to calculate the precise stoichiometric amount of chalk to add to get this done, a 1:1 mole ratio should do it.
Third, one need not use vaulted galleries of brickwork to cook the stuff. That almost sounds poetic, ahh the good old days when factories were more than just steel beams and concrete slabs. A small improvised
furnace with a blow pipe to force air over or through the carbonate should do the trick. Again I cant say how long this should be done on the small scale.
Polverone October 2nd, 2002, 03:48 AM

Eh?!
<blockquote>quote:<hr />This procedure could perhaps be simplified a bit.<hr /></
blockquote>You can say that again! As I said a bit earlier, hypochlorites will indeed convert MnCl2 directly to MnO2. No need to roast it. And if you do want to
take a detour through the carbonate and from thence to the dioxide, don't use CaCO3! Although the industrialists of yore may have used the extremely inexpensive calcium carbonate, coupled with extended
heating under pressure, on a lab scale you would be much better off using a more soluble carbonate like Na2CO3 or K2CO3. Depending on the strength of the solutions you mix, the precipitate of manganese
carbonate may form a sort of gel. But this gel is easily broken up and made filterable by agitation.
But MnCl2 is so pretty that maybe you won't want to throw it away to make icky brown and black compounds. When anhydrous it is yellow, but hydrated it is a lovely rose color. If you have crystals of it that are
only partially hydrated you get a beautiful hybrid rose color effect.
And of course if you prepare the hydroxide or carbonate from the chloride, you can then make any acid derivative from those. I don't know what use manganese nitrate may have, but I've prepared it nonetheless!
:)

I think its worth explaining a little of the chemistry behind some of the processes in the thread. What we are dealing with are redox reactions and particulaly in the case of manganese the oxidation/reduction
potentials vary considerably with ph. In alkaline solution or fused melt Manganate is very stable and the processes that make it are very easy to do. Any oxide of manganese in fused KOH is very easy to oxidise to
manganate. Oxygen in the air will do it, as will virtually all good oxidisers. Once you have manganate, making permanganate is not a problem as manganata is not stable in acid solution, it disproptionates into
permanganate and manganese dioxide.
eg, Mn2O3 + 4KOH + 3[O] => 2K2MnO4 + 2H2O

3MnO4 2- + 4H+ => 2MnO4- + 2H2O + MnO2
With the chlorate oxidation, the KOH is the base, the chlorate ends up as chloride unable to supply potassium ions. The Manganese dioxide at the end isnt unreacted, its an inevitable result of the conversion to
permanganate. The end product of the addition of carbon dioxide isnt carbonate btw, its hydrogen carbonate, which is a feeble acid, but enough to decompose the manganate. K2CO3 would work in the melt instead
of KOH, but its melting point is too high. Equivalent sodium compounds do not work as well in these reactions.
Ok, using KNO3. Since the end produce of oxidation is essentially K2O and the hot melt is basic from decomposition of the nitrite 2KNO2 => K2O + 2NO + 1/2 O2 you dont need much else to make the reaction
work. In fact according to Chevillot and Edwards fusing a mixture of 1 part manganese dioxide with 1.5 parts KNO3 yeilds a mixture of KMnO4 and K2MnO4 directly. The workup decomposes any manganate to
permanganate and manganese dioxide as before. Since nitre is much easier/cheaper to make/get than either KClO3 or KOH I think this process is likley to be the most useful for recycling KMnO4. I'm very
interested in recycling reagents, particulaly oxidisers.
As far as manganese dioxide from manganese(III) salts, manganese dioxide is synthetically equivalent to manganese (III) permanganate. Use dilute solutions and add the manganese salt to the permangonate
rather than the other way round, particulaly if chloride is present. Concentrated or acid solutions with chloride liberate chlorine, which is another good reason the manganate workups shouldnt be acidified with HCl.
Getting pure salts from mixtures using fractional crystalation is a method well worth learning, essential for these permanganate methods and wipes the floor with any other method of seperating chlorate from
weedkiller. Sieving is next to useless for weedkiller.
megalomania October 3rd, 2002, 07:00 PM

Well, to commerarte my new digital camera I have idly taken some pictures just for my own amusement. Watch as I periodicially attempt to make potassium permanganate from a battery, now in color. I am not
doing a formal writeup, I will just be going on the info in this thread.
Let us begin with the victum, an old 6V lantern battery. This big sucker has served its last electrons, and now I have rather easily peeled away the metal skin. Inside are for D size batteries covered in cardboard.
<img src="http://www.boomspeed.com/mega21/battery1.jpg" alt=" - " />
Next up we have a good view of what is inside the cardboard wrapping. The bottom half is what is left of a zinc metal shell. The zinc metal canister was very fragile and after a few raps with a knife the top half
peeled away exposing a hard solid cylinder of manganese dioxide and carbon black (hopefully that's what it is). Between the zinc and the black is a thin paper layer.
I felt a water bath was appropriate to dissolve any soluable gunk. a lot of the zinc flaked off, it bubbled a bit, and the next day the water was grayish with a skin on the surface of the water.
At this point I used an electric grinder wheel to sand away the excess bits of zinc that I could not scrape off. What was left was more or less a black cylinder.
To kill two birds with one stone I have set up a chlorate making apparatus using the battery insides as the anode. I made a cylinder out of some old screen leaving about a 0.5 cm gap between the anode and the
screen cathode. I attached some copper wire to them and connected the appropriate ends to a battery charger. This damn thing reacted right away. This picture is taken seconds after I turned it on.
Here is a top view, look at those bubbles go! I got a big whiff of something bad :( The oxygen also contains various nasties.
[ October 03, 2002, 06:13 PM: Message edited by: megalomania ]

a n d I m provised C hemistry > My Curious Electrolysis
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View Full Version : My Curious Electrolysis

For the past two months I have had a solution of magnesium sulfate under constant electrolysis in m y flowerpot and plastic
bucket setup . W h i l e I h a v e d o n e t h i s b e f o r e , I h a v e o b t a i n e d a m ost peculiar black liquid. I obtained, as expected, m uch
m a g n e s i u m hydroxide precipitate on the outside of the pot. O n the inside there should be not but sulfuric acid and excess
m a g n e s i u m sulfate. By letting it go for so long I was ho ping for exhaustive electrolytic red uction of all of the m a g n e s i u m
sulfate, but I believe once the concentration goes below certain threshold you get plain water electrolysis.
Anyway, the sulfuric a cid is very very black. I used carbon electrodes, and while I did lose som e, I can account for m uch of the
m aterial. I filtered the liquid to rem o v e a n y c a r b o n r e s i d u e , a n d t h e n I c h e c k e d a s a m ple in a test tube under a strong light to
check for turbidity, of which there was very little.
The black solution itself is pure black, like oil b lack. I held a flask filled with 1 L of the solution up to a very strong light, which
did not penetrate at all. Even a small sample in a test tube under such a light is quite dim . C o u l d t h e r e b e s o m e s o r t o f
reaction goin g on between the sulfuric acid? A sample tested with sodium bicarb did result in considerable effervescence, and a
field pH test (as all I have are test strips) indicated a pH of between 1 and 2.
I wonder if it is possible the black m ay be highly divided particles of carbon from the electrode. I still find that rathe r difficult to
acce pt becau se I can account for m ost of the lost electrode carbon. The only othe r contam inant m ay be a little copp er sulfate
from the copper cladding of the electrode, but then there is very little of that and the solution was already black way before m y
electrode slipped that far in (I needed the stan d, and I actually electrolyzed my damn alligator clam p, grrr).
I was hoping for a little bit greater purity of sulfuric acid. C o u l d i t h a v e b e e n s o m e insect or other organic m atter getting in
there and reacting with the sulfuric acid? My neutralized solution is actually a light brown, or possibly green (m y color deficiency
wont let m e distinguish) without a trace of black. That would seem to rule out a suspension. A good centrifuge would help right
about now...
Boob Raider S e p t e m b e r 1 st, 2002, 11:01 AM

Hey Mega ... what is your flower pot made up o f ? and what did you use to neutra lize the black soln. ?
nbk2000 S e p t e m b e r 1 st, 2002, 11:25 AM

Collodial suspensions of particles are very efficient at scattewring light. A couple of gram s of collodial carbon could cause the
coloring you've gotten. And settling is impossib l e b e c a u s e o f b r o w n i a n m o v e m ent in the fluid keep s the particles suspended.
A centrifuge would seperate it out. Do you have any activated charcoal? A bit of that may remove the coloring.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > The Hunt for Decalin
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megalomania September 12th, 2002, 03:29 AM

I need some Decalin, you know the solvent. Decalin is like naphthalene but without all the double bonds, its like to hexane rings stuck together. Anyway I have heard a rumor
that is is used OTC in turpentine substitute. That's turpentine substitute, not regular turpentine.
I would like to ask anybody and everybody to stop by their local hardware store (at your convenience of course) and check the label of turpentine substitute and see if it
contains any Decalin. Thanks.
I could try and make some Decalin. I am tracking a few synths but they don't look all that promising. Starting with naphthalene, seems easy enough... dissolve in glacial acetic
acid, no problem... add some platinum or rhodium, maybe a bit tough or pricy... add hydrogen to a pressure of 150 atm, aww shit! There is no way in hell I am doing a high
pressure catalytic hydrogenation. I may have a few workarounds up my sleeve, for example you can do the same reaction to naphthalenol (moth ball alcohol) at 4 atm, but
that requires adding and then removing the alcohol.
I have been thinking about trying a Benkeser Reduction. Never heard of it you say? Well I got lucky on this one. saw it in Merck by accident :) Seem I can use calcium metal in
an amine solvent, like methylamine to completly hydrogenate naphthalene. Too bad methylamine has such a low boiling point, I'll need a freezing bath to do the reaction.
Using larger or more substituted amines will not reduce all the way, rather there will be a double bond or two. Of course that double bond will be in such a place as to make
hydrogenation necessary (low pressure at least). Stupid thermodynamics :(
I know, sounds like a lot of work to do this, but I am limiting myself to a special criterion for OTC only applications. Making Decalin seems so easy yet so hard... When I finish
my paper everybody can read all about it.
nbk2000 September 12th, 2002, 09:31 AM

I assume the decalin is intended for some "higher" purpose?
And what may that be? :confused:
kingspaz September 12th, 2002, 06:22 PM

can't you use Ni as a catalyst? i have a vague memory of it being used in the hydrogenation of arenes...
30atm, 300*C, Ni powder catalyst and H2 pumped over it is used to hydrogenate benzene according to a book i've just tooke out my school bag....30atm must be a hell of
alot easier to get than 150!
can't see why the same process wouldn't work on napthalene... but then i don't know much about aromatic chemistry <img border="0" title="" alt="[Frown]" src="frown.gif"
/>
megalomania September 12th, 2002, 06:44 PM

As a higher boiling point solvent for Grignard reactions.
Machiavelli September 12th, 2002, 10:50 PM

Don't you need an ether solvent for Grignards? Like Dioxan or THF? I always thought they were necessary to stabilize the grignard.

Usually, yes, but in this case I have a published ref that says neither ether nor THF will work, and Decalin is specificially requested. I know ether won't work because Grignards
with chlorine require more vigerous conditions, but I don't know why THF dosn't. I intend to try THF anyway.
I also thought of using a nickel catalyst, but abandoned that line of reasoning. Nickel has far lower activity at lower pressure and with more highly substituted aromatics. Nickel
can remove a few double bonds, but it will require enormous pressure for that last double bond (the one the connects the rings) for it is just stabilized too much. The only way
to avoid the pressure is to use a more active cat like platinum or better still rhodium. I believe the presence of the hydroxyl (in naphthalenol) plays a role in the mechanism by
allowing that final double bond a place to resonate thus allowing hydrogenation.
I even gathered up my nickels and was ready to dump them into acid (to begin making Raney nickel) before I realized the chemistry of hydrogenation with nickel would not
work well enough.
[ September 13, 2002, 05:35 PM: Message edited by: megalomania ]
PrimoPyro September 13th, 2002, 04:16 AM

The Beckenser you specify is much like a Birch reduction, and you will have to run it for a long time to get a fully reduced compound.
Look for an electroreduction, with something like DMF as solvent. These are common, since the aromatic systems are easily reduced by systems that have lots of solvated free
electrons.
PrimoPyro
Anthony September 15th, 2002, 08:35 PM

Turps substiute is as common as muck here, and I've checked the back of many a bottle to try and see what exactly it is, but the most it ever says is "contains petroleum
distilates".
A little digging on google and we have a few tid-bits:
UN number is: 1147
From <a href="http://ntp-server.niehs.nih.gov/htdocs/LT-studies/tr513.html:" target="_blank">http://ntp-server.niehs.nih.gov/htdocs/LT-studies/tr513.html:</a>
Decalin is used as an industrial solvent for naphthalene, fats, resins, oils, and waxes. It is also used as a substitute for turpentine in lacquers, paints, and varnishes; as a solvent
and stabilizer for shoe polishes and floor waxes; and as a constituent of motor fuels and lubricants. Other applications include use as a paint thinner and remover, a patent fuel
in stoves, a high-density fuel in submarine-launched cruise missile systems, and in stain removal and cleaning machinery.
The only product I managed to find was "Ceramichrome" - a cermaic overglaze/luster, which contains 5-15% decalin
<a href="http://www.ceramichrome.com/safety/glaze_msds/msds15.htm" target="_blank">http://www.ceramichrome.com/safety/glaze_msds/msds15.htm</a>

I finally made it to the hardware stores today with rather depressing results. I now doubt that Decalin will be listed by name in their products. Those companies are not very
good at labeling their products. I did find a 3 lb container of 98% NaBr for $13, so it wasnt a total loss. Oh, and I found it is cheaper to buy PVC pipe preparer instead of the
adhesive for THF. I forget what the stuff is called, but it is used to get the plastic ready for something (this is not the cleaner which is a similar product, but which has no THF).
I have obtained a high temp little furnace meant for melting metal that I hope to use to make some calcium metal. I finally found a use for that bag of ice melting salt from
Wal-Mart with sodium, potassium, calcium, and magnesium chloride. Originally I wanted to use this as a source of magnesium metal using an alcohol extraction process to get
more or less a mix of calcium and magnesium chloride. Sodium and potassium chloride are not very soluble in alcohol, the common ion effect should keep them out when the
other two chlorides are present. In fact it seems I salted out the water from my alcohol in my sample.
As it turns out the presence of calcium mixed with magnesium will be good as the melt point will be lower. I had hoped to remove the calcium by adding the mixed metals to
water whereupon the calcium would react. Now I can use the mixed metal in the Benkeser Reduction, hoping that the magnesium doesnt react, and collect the pure
magnesium metal.
Polverone September 18th, 2002, 03:54 AM

<blockquote>quote:<hr /> have obtained a high temp
little furnace meant for melting metal that I hope to use to make some calcium metal. I finally found a use for that bag of ice melting salt from Wal-Mart with sodium,
potassium, calcium, and magnesium chloride.<hr /></blockquote>I do hope you will write about your metal
production experiments whether you are successful or not. In theory, it is fairly trivial to produce alkali or alkaline earth metals (at least small quantities) from their chlorides or
mixtures of chlorides. In practice, I have not yet met anybody who claims to have done this successfully (apart from tiny beads of metal, hardly useful quantities).
Also, might you elaborate on the nature, source, cost, and properties of your small furnace? Such an item could be generally useful to the experimentalist of limited means,
especially if it can achieve high temperatures.

Why most certainly I will carefully document all of my experiments. I have heard good things and bad from a varity of sources about the success of the reaction, but I am
confident I can make it work. The furnace is actually my uncles, he used to do metal casting and such, so it is up at the manner house. The making alkali metals is actually a
subproject I have been meaning to try. Now that I have a new 4.1 megapixel digital camera to play with I can take many wonderful pics. As soon as we find the thing (its
packed away *somewhere*) I will elaborate furthur. If that fails there is also a kiln.
I got a new Aldrich catalog today, Decalin is $50 a liter! Bah, I was under the impression that is was cheap. I hadn't bothered to look it up in any of my other catalogs yet.
I have been thinking about trying the Benkeser Reduction with ether. I may have to run the reaction for several days to get that last double bond, and using methylamine
means a constant cold bath for days. I could rig a sealed system, but it seems to me that dissolving everything in ether would be much more conveniant and cost effective.
a_bab September 20th, 2002, 03:17 PM

The decalin they sell is pure, so is expensive. Any analytical grade reagent is expensive. The fact that it cost 50 bucks doesn't mean that the decalin is expensive in general, in
my oppinion.
If there is anyone else interested in isolating alkaly metals and other interesting elements (phosphorus) we may start a new project. One of my wildest dreams is to have most
of the elements in vials. And I want to isolate barium, calcium, strontium, caesium (this one is a bitch as it's compounds are very expensive), and some other metals in
general. I am planning to produce sodium in large quantities in order to use it as a reductor agent for calcium, barium, and other metal compounds.
Mega, I found in one of the MOA books (is the FTP <img border="0" title="" alt="[Wink]" src="wink.gif" /> ) a method for obtaining liquid chlorine, by closing in a glass tube
some chlorine hydrate and by heating the tube. The hydrate will be decomposed and you'll get water and liquified chlorine by the means of pressure. A nice experiment; it
worth a try, isn't it ?
It's funny to see in these old books how they supposed that mixing iodine with some fluorine salt will release fluorine (actually it was a compund between the two halogens).
There are lots of such mistakes but on the other hand there are lots of nice experiments too which are no more encountered in our chemistry books.

Liquid chlorine will be produced from the high pressure produced when the chlorine hydrate decomposes, if that is, the phial doesnt explode which mostly as I recall, they did. I
bilieve this was how chlorine was first liquified by Faraday in 1820, the product was a few 'oily' drops in the liquid of the second arm of the tube cooled in a freezing mixture.
The drops 'vanish' when the phial is opened with the high pressure chlorine doing what is expected. Ammonia can be liquified in a similar way, I bilieve Faraday had got into
the habit of setting the experiment up and then going away for a drink at the local pub. The result when he got back was usually the fragments of exploded tube. If you are
after useful amounts of liquid chlorine by a safer modern method, a peltier pump, all solid state, will produce temperatures as low as -50C when powered and insulated/
heatsinked properly. I hope to have access to the ftp, alas hotmail reports his email as full, hopefully this will be resolved soon. I am fascinated by old methods of chemistry
and I am interested in making an element collection myself. I have a lot of advice from personal experience of making sodium but this isnt the thread for it.
On the subject of decalin wiser minds than mine have suggested the following:-
Napthalene in isopropyl alcohol at reflux will be reduced to decalin by hydrogen with a platinum black catalyst at atmospheric pressure. Flush out the air first several times with
welding nitrogen (for example). Burn off the excess hydrogen. A good bubbler, eg fritted disk is essential. This method has been used successfully.
To make platinum black you can dissolve a few cm of platinum wire in aqua regia, evaporate, dissolve in isopropyl alcohol and reduce with hydrogen. Palladium coated beads
from a car catalyctic convertor should work. Avoid rubber in all connectors/stoppers as the sulphur content will poison the catalyst. Use neoprene or silicone.
Most dissolving metal reductions fail becuase the reaction gets stuck at the disubstituted benzene stage, which is vastly harder to hydrogenate than even benzene. We cant
comment on the calcium in amine solvent method.

From everything I have read about catalytic hydrogenation it requires high pressure. This is the reason I focused my efforts on the alkali metal reduction route. Your words that
a hydrogenation can be done at atmospheric pressure are encouraging. I suspect it would be easier to prepare a suitable platinum catalyst than to obtain calcium metal and
methylamine in ether solvent.
It makes little difference to me what route to use, but I am constrained by the parameters of my study. All materials must be OTC only. The information is intended for the lay
audience, or for the not to distant future when the law tries to ban even more chemicals. Both routes are complex indeed, but if I provide enough information I hope anyone
will be able to reproduce them.
Perhaps, since you seem to know your science Marvin, you may know of other alternative solvents to conduct the Grignard reaction in. That is the reason for the Decalin. I
originally wanted to use the obvious choice of ether as the solvent. As I later found out through literature study and confirmed with organic chemist, ether has too low of a
boiling point to sustain the higher reaction temperatures needed to initiate a Grignard with a chlorinated substance.
Bromines and iodines are easier to react, chlorine requires more heat. THF was the next choice, but I found a reference that said THF was found generally unsuitable for the
reaction. I am not sure what that means exactly. At the same time I found my OTC route for THF synthesis was flawed anyway. It involved a Grignard reaction of an epoxide
with a vicinal halohydrin, namely chloroethanol, which turns out cant be done as the proton on the alcohol prevents the reaction.
The reference specifically requested Decalin. I do wonder if the double bonded version, a-9,10-octalin or something like that, would work just as good. It was my
understanding that you needed an ether to assist in a Grignard. Theory always seems to be contradicted by reality in chemistry.
This has all been good fun for me. I enjoy the challenge of using completely unpopular and frivolous routes to synthesize chemicals that the scientific community regards as
trivial to obtain. Of course those that dont belong to the community get nothing, so it is for them that I work so hard to please.
On that note I could still use some help making THF. I dont like the industrial methods for some reason My current aim involves preparing 1,4-butanediol which could make
THF via a condensation reaction. I can still use chloroethanol, but I have to add a protecting group to the alcohol. Using chlorotrimethylsilane would be an easy quick way of
doing just that. Chlorotrimethylsilane is not an OTC chemical though. I dont suppose anyone knows how to make this stuff? Have not found very much about its synthesis.
a_bab, you might be interested in my notes on phosphorous production (if I can find them). I have been entertaining ways of getting the stuff from triple superphosphate
fertilizer, TSP cleaner, and bone meal. All three of these things are available in most hardware stores. I dont need any phosphorus, but if the distinguished gentlewoman from
Kalifornia senator Feinstein doesnt like it that is reason enough to make sure everybody knows how to make it themselves. Tell me, does your method of sodium preparation
happen to involve sodium carbonate mixed with charcoal and chalk heated high enough to release the metal?
a_bab September 28th, 2002, 04:34 AM

No Mega, it doesn't. I am aware of the dangers using this method (formation of explosives superoxides, and peroxides at least in the potassium case). I want to do it by the
hidroxide electrolysis.
To stay on topic, what about determining WHY other solvents are not suitable for the Grignard reactions, but decaline is ? In this way you may extrapolate other solvents. It
sould be something about Mg reactivity, I guess (in decaline it'll be inert).
Actually I was given to understand that it is the spare electron pairs on the oxygen of ethers that assists the reaction. Ethers are also quite inert under Grignard conditions. I am
not sure, but it could be that the mechanism is not well understood. I have the theory of it in a lab book upstairs somewhere...
PrimoPyro September 28th, 2002, 08:44 PM

What temperature are you looking to obtain? You know glyme or diglyme or tetraglyme might be what you are looking for as for properties. Tetraglyme boils over 200C IIRC.
Check Chemfinder.
As for Grignard Reactions with chlorides, please give more details. Is the chloride aliphatic or aromatic? Are you reacting the Grignard Adduct with the chloride, or preparing the
adduct from the chloride to react with something else?
Ultrasound is the Grignard's best friend. Grignard Reagents of the insanely stable chlorobenzene have been prepared by using ultrasound. Also, using Reike magnesium often
helps VERY much. Reike magnesium is Mg made by reduction of MgCl2 with potassium metal, and this produces and ultra-reactive magnesium.
I recently made a thread at the Hive about Solvents for Grignard Reactions and stability, that went largely unnoticed. I can copy it to here if you like. The mechanisms of
Grignard Reactions are very well understood.
You can also use a crystal of iodine to initiate grignard formation, or addition of catalytic 1,2-dibromoethane.
As for catalytic hydrogenation, there are many atmospheric pressure applications, and not all use platinum and palladium. Research Urushibara Nickel, and Catalytic Transfer
Hydrogenation (CTH) with nickel and ammonium formate as a hydrogen donor. Very powerful reducing systems that are amazingly selective based on reaction conditions.
P.S. I forgot to say that there are reports of using trialkylamines (freebase form) in nonpolar solvents like toluene to assist in Grignard Formation. The lone pair of electrons on
the nitrogen in tertiary trialkylamines (Dimethylaniline was specifically cited, I wonder about the cheaper triethylamine) act in the same manner as the lone pairs from oxygen
ethers.
PrimoPyro
[ September 28, 2002, 07:47 PM: Message edited by: PrimoPyro ]

I thought for a long time about solvents, and it wasnt until I woke up I remebered diglyme. PrimoPyro has quite neetly beaten me to it though (I look forward to reading his
full solvent list) so I can only add a few trivial details. Diglyme is CH3-O-CH2CH2-O-CH2CH2-O-CH3 which Ive written like that for ease of thinking, mainly mine. It can
presumably be made from ethylene glycol and methanol and has a boiling point of 162C, only about 20 degrees below the lowest boiling isomer of decalin (THF is 120C below
not much better than ether). Since its a polyether it might be a better solvent than decalin for the grignard so the slightly lower temp might not make a difference. I dont know
of an OTC use for it, and since you are likley making it yourself you might try making the ethyl version instead, to push up the boiling point a bit. Some simple web searching
revealed butyl diglyme to be a good solvent for grignards of chlorine and has a bp over 250, but not really easy for OTC. Id put my money on diglyme or ethyl diglyme if I was
looking to replace decalin.
I think making decalin using the car catalyctic convertor beads could work well, though I dont know how much new cats cost, palladium coated beads could have a lot of other
uses though in experiments. Decalin does have one advantage I can see, it shouldnt dissolve any water and this leads to something else Ive been thinking about, how are you
going to dehydrate the solvents/reagents. Ether is normally dehydrated with sodium wire and I'm not sure CaO for example will quite cut it.
My final thoughts on this, is this is hell of a lot of trouble just to use a chlorine grignard, is the alkyl chloride you want to use OTC?
Phosphorous can be made much more easily from phosphoric acid or ammonium phosphate, which form glassy metaphosphoric acid (HPO3)n on strong heating. Less hydrogen
to lose as phosphine, no silica required, lower temperature for reduction with carbon, or if desperate for a low temp reaction, aluminium. Excess aluminium will form a
phosphide so avoid this. White phosphorous is very toxic (used to be used as rat poison) make sure you understand the health effects and its properties so you can avoid
problems, in addition to the copious amounts of carbon monoxide the carbon reduction produces. Making monoammonium phosphate should be easy from triple
superphosphate and ammonium sulphate if you cant get it directly.
Polverone September 30th, 2002, 04:00 PM

Ah-ha! It happens you've hit upon one of my pet interests: the production of elemental phosphorus from readily available starting materials. A quick visit to any Internet forum
dedicated to methamphetamine production will reveal that the easiest way is simply to extract red phosphorus from the striker pads on match books. However, this method is
tedious, expensive, and simply inelegant.
I have made a few attempts - all failures - to prepare phosphorus starting with a phosphate and carbon. The phosphate that I used was diammonium phosphate. I suspected,
as you do, that it would be easier to reduce than a phosphate of a reactive metal. I used a vessel made from a steel pipe. One end was capped, and the other had a nipple
with a copper tube going through it, sealed in place by furnace cement. The end of the copper tube dipped slightly into a jar of warm water. Using a large gas lab burner
hooked up to a propane tank, outdoors, I was able to raise part of the tube to red heat. Many noxious gasses were expelled from the tube. I obtained no phosphorus,
however. When I removed the nipple/tube assembly and directly heated the mass of charcoal and diammonium phosphate, I eventually obtained jets of flammable vapor from
the carbon. I suspect they were phosphorus because of the odor of combustion and appearance of the flames, which reminded me of burning phosphorus (which I have seen
on a small scale).
I made one other attempt with similar results. I simply can't apply enough heat to the tube with this burner to make the reaction practical. I've thought of trying again with
aluminum powder instead, or trying to use charcoal and forced air for the heat source, but I haven't tried either yet. The condensed glassy mass inside the tube after the heat
goes away is a pain to chip out. Hot water doesn't touch it. Maybe hot NaOH solution would?
If you've actually tried to make phosphorus yourself, I would enjoy hearing about the attempt.

In fact so far Ive not succeeded in making P yet. The main reasons were I was trying to make the reaction go in a pyrex vessal, quite a tall order. I think this will be possible
with aluminium though it might well wreck it in the process. The whole furnace+clay rhetort buisness was what I was trying to avoid. I was given some advice by the same
chemist I talked to about decalin coincidentally enough. He suceeded with a setup not a million miles from yours. Steel pipe, capped one end, reducer on the other small
furnace setup fired with propane, 80+% yeild. Since you got as far as metaphosphoric acid, why bother chipping it out! just leave it in until the next try, provided all the carbon
wasnt used up (If so that would point to a different cause of failiar, and I know your smart enough to do the math). Metaphosphoric acid is a polymer, which is why its so hard
to dissolve, if you let it soak in water it will depolymerise and dissolve by itself, ending up as fairly pure orthophosphoric acid. The only risk you run is the pipe rusting, so dont
leave it in contact indefinatly.
I plan to try that setup as soon as I can handle the phosphorous safely, splinters get everywhere aparently when you break it cold. I also plan to make the metaphosphoric acid
in a seperate step, so there is no risk of excess phosphine production, and the rhetort will fit more phosphate/carbon in. Ive been advised not to dip the end up the tube in the
water, for a start suckback could cause real problems with the steel rhetort at not much short of 1000C. Cool the copper tube with hot water for a better yeild, the copper tube
shouldnt react *much* with it so that should be ok. Cool with cold water and you risk it jamming up with P. During the reduction you'll have so much carbon monoxide coming
out you wont need to worry about air getting in. Did you attempt to insulate the steel pipe at all during the last attempt or were you just heating the tube? Firebrick insulation
should vastly improve the temp you can get the pipe too. If the worst comes to the worst I suspect a charcol furnace with only minimal air flow will be required to make the
reaction go very well. I wont be trying this for several months at least, I have too much on the go currently so tell us what happens when you next try. As an afterthought, I
might try lampblack instead of charcol, then I shouldnt have to purify the product at all.
Good luck!
snuk5 January 26th, 2004, 12:04 AM

Hi Polverone,
This question is not directed at me, but allow me to oblige.

__________________________________________________ ________________________________________
Also, might you elaborate on the nature, source, cost, and properties of your small furnace? Such an item could be generally useful to the experimentalist of limited
means, especially if it can achieve high temperatures.
__________________________________________________ ________________________________________
I made my own gas furnace. The Design was inspired by a book on pottery kilns
The inside has the volume of a shortened 20 litre paint can. (Thats what I used for the inner mould)
Making Raney nickel with this thing would be a cinch (although I bought my catalyst at the time) They say that freshly prepared R Ni catalyst is better.
I once wanted to cast an Alu ingot. Used a home-fabricated 4 mm thick walled stainless steel melting pot.
Then I wanted to try how hot my new baby could get, as a result the stainless steel pot melted! (In honesty it must have also partially dissolved in the Aluminium) but I had a
nice puddle of funny alloy in the bottom of my kiln that I had to pour out before it solidified!
The furnace was easy to make, but it takes some time. Its based on castable refractory concrete, a squirrel cage blower, which blows through a tangentially inserted 35
mm stainless steel tube in the bottom. and a simple piece of 6 mm stainless steel tube, sealed at the end and drilled with a 1 mm gas orifice, that sticks though a hole as
drilled through the big tube. Light the thing by throwing in a match and the blower does the rest. (gas flow is regulated using a cheap Taiwanese reduction valve) Uses about
1.3 kg of gas per hour, at full blast. Temp should be well in excess of 1400 degrees C. (Did not want to expose my thermocouple to the higher temps.)
Makes one hell of a noise though.
The thing could be scaled down by 40% without much loss in performance.
Estimated cost: less than 65 bucks US. (Depends if you want to make it more energy efficient and lighter by using fire blanket, like I did)
Building time: depends how nice you want to make it; but if you want something that is better than anything you can buy, it is quite a bit of work.
If you want to get more details, drop me a line
megalomania February 1st, 2004, 04:16 PM

I would love to hear the details of your furnace. I myself am interested in building such a thing, but details are hard to come by.
snuk5 February 6th, 2004, 04:54 PM

Hi Megalomania
Been very busy with Other Things
Just read your post. This weekend, I will certainly take full measurements of the furnace and make some CAD drawings that ill GIF.
(I'm one of those who are about to purchase a digital camera too.......)
Ill put the drawings + text on the ftp-site. (Hope to be able to access this myself sometime in the future)
Wonderful site youve got man, wonderful!
Snuk

a n d I m provised C hemistry > Types of Diesel Fuel
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KinePak S e p t e m b e r 1 6th, 2002, 08:30 AM

OK, now as most of you all already know, I have successfully already detonated a 50lb charge of fertilizer grade AN with Diesel
Fuel, and I was very successful to say the least. This pa s t w e e k e n d I d i d t h e e x a c t s a m e c h a r g e , b ut I used Prem ium Diesel
Fuel from Texaco, and I also let the charge sit for about 7 hours before detonation. My results were shit, all it did was throw my
prills all over m y lake , and spray the d iesel out, only the Kinepak went off. OK, the only difference b/w the two charges was
that I used a differen t type of diesel last weekend. The Texaco brand wa s yellow in color, and the diesel I got from m y c o u s i n
was red in co lor. So, m y question is this does it m atter which type of diesel one is to use in successfully detonating ANFO, I
m ean are there different chem ical properties in certain types of Diesel fuel?
mrloud S e p t e m b e r 1 6th, 2002, 10:03 AM

There is no fixed recipe for diesel. The com postion of the stuff you buy as diesel will depend on th e climate you are in and the
refinery it cam e from . In winter, diesel will be m ade so that it vaporises easier. In sum mer the mixture will be changed to
reflect the higher average tem perature. The diesel I buy here in Melbourne won't be the sam e a s t h e d i e s e l o n e w o u l d b u y u p
in Darwin (nearer the equator). Also, we don't get "prem ium diesel" here in Oz so I don't know what that co uld be about.
W hy not try the original experiment again to m ake sure it wasn't just a fluke that it worked? Then try it a third tim e but only
c h a n g e * o n e * parameter (The wait tim e o r t h e b r a n d o f d i e s e l ) . Y o u n e e d t o u s e a p r o c e s s o f e l i m ination to determ ine which
m odification caused the failure.
Anthony S e p t e m b e r 1 6th, 2002, 11:07 AM

If your laws are anything like ours then red diesel is for use in offroad vehicles (farm equipm ent, JCBs, generators, pumps etc)
and is tax free. The only difference between red and regular diesel is a red dye to mark it.
Bitter S e p t e m b e r 1 6th, 2002, 12:00 PM

It produces different em ission ratings too, apparently.
spydamonkee S e p t e m b e r 1 6th, 2002, 08:53 PM

m ayb the other type of desiel burns @ a lower temp and a lower ratio would be needed for it to work with ANFO?
well thats all i could think of as i thort pretty m uch any enegetic fuel could be used for ANFO, desie l was just the best for its
price
CyclonitePyro S e p t e m b e r 2 0th, 2002, 10:01 PM

R e d d i e s e l f u e l i s h o m e h e a t i n g f u e l , w h i c h s o m e p e o p l e i l l e g a l y u s e i n p l a c e o f n o r m al diesel fuel in vehicles, beca use it is
cheaper.
I used the red in an ANFO cha rge and it worked great. I've never used normal diesel though, so I can't make any conclusions
to which kind works better, if it m a k e s a n y d i f f e r e n c e .
Jacks Complete May 13th, 2004, 08:44 PM

R e d d i e s e l f u e l i s h o m e h e a t i n g f u e l , w h i c h s o m e p e o p l e i l l e g a l y u s e i n p l a c e o f n o r m al diesel fuel in vehicles, beca use it is
cheaper.
On a related note, (aware that this might get m e a telling off) does anyone know of a way to split out the colour? Or what the
dye is?
I have tried base, acid, weak oxidiser, and a few other things. Nothing. I am no chem ist, though. I only did A-level.
Of course, th is is just so that I can use it on m y hair, as I love the smell of diesel. ;)
I heard that filtering it through bread would work, but th at would waste th e dye... C ustom s and Excise have a tester kit they
use, and they add a little drop of som ething, and it splits out, and a scale tells them how naughty you have been.
Any ideas?
Dave Angel May 13th, 2004, 09:07 PM

Have you tried activated charcoal? You can get it in the pet's section of W ilko's, 125g for 99p according to my little book of
O T C things. Perhaps distillation, thoug h that's rather wasteful of energy I suppose, and the dye co uld be volatile and have the
s a m e bp. as the fuel.
I rem ember seeing a news report about a police raid recently wh e n t h e y b u s t e d a b u n c h o f p e o p l e r e m oving the dye from
diesel. The were lots of chem ical conta iners around and I was desperately straining m y eyes at the screen to see what they
were using but I couldn't tell :(

L O L . Y e s , s o m e p e o p le I know were doing the sam e thing. R oll on HDTV!
Charcoal might work, but at 99p for a little bag like that, the bre ad would be cheaper.
tmp May 17th, 2004, 09:30 PM

Diesel fuel is prim arily cetane. The only grading difference I've ever heard of is
No. 1 is supposed to have less paraffin than No. 2 and therefore m ore desirable.
I don't know if this grading system is still used or if it would have an effe ct on
your ANFO.
Magas May 24th, 2004, 08:50 AM

Am onium Nitrate, being soluble in water, is not resistant to water-hence, there is a loss of efficiency or failu re when AN/FO is
used under wet conditions. You m entioned near the lake and sitting for 7 hours d id you have it in a waterproof hole or
container?
Also how did you m ix it. Incom plete mixing is characterized by b y reddish -brown fum e s o f o x i d e s o f n i t r o g e n a n d p oor
plasting performance result.
Also what is the com position of your prilled. Prilled FGAN, coated with Kieselguhr redilly absorbes 6% of fuel oil, However, the
kieselguhr coating is inclined to inhibit initiation sensitivity. Some suppliers overcom e this by using surface-active agents
instead of the kieselguhr in the production of p rilled AN
W ith that said the physico-chemical bo nd between AN and fuel oil can be sustantially im proved by use of surfactants & water,
which produce emulsions of fu el oil in water, resulting in greater sensitivity and better explosive qu alities. e g "Quilox" is m i x e d
with fuel oil to form an oil/water/surface-active agent emulsion, this is then addes to a bag of prilled AN in the required
a m ount.
TheArsenist October 3rd, 2004, 11:18 AM

My AN fertilizer prills are 98,6% pure AN and they are about m esh 14. But it seem s t h e y h a v e s o m e s o r t o f c o a t i n g o n t h e
surface because I find it hard to properly "activate" them.
Anyway, if the coating is m ade of wax shouldn't teh diesel dissolve that and if the coating is not wax what else can it be m a d e
of then?
tmp October 9th, 2004, 10:35 PM

TheArsenist, my experience with fertilizer grade AN is that is has been
coated with clay - at least in the past. They may be using wax now.
Personally, I dissolve, filter, and re-crystallize any AN I get - regardless
of source. Dissolve as m uch as possible in boiling water. Don't worry
about the slight am m onia smell. Filter if necessary. Even without freezing,
the AN crysta ls will start to form as the solution cools. After rem oving the
crystals, allow any excess water to drain off in a filter, then dry b y any
m ethod you desire. Just be careful when heating because the AN could
decompose or even explode if heated too high.
Anthony October 10th , 2004, 09:51 AM

Does anyone have any personal experience of the difference in sensitivity between prilled and powdered AN in ANFO ?
Also, has anyone com pared diesel and petrol a s fuels?

a n d I m provised C hemistry > accident (effects)
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andreas S e p t e m b e r 2 5th, 2002, 02:28 PM

I was purrifin g s o m e a m m o n i u m nitrate and when boiling down the solution I went away to grab a bite. Whe n I cam e b a c k m o s t
of m y am m o nium nitrate had turned into thick clouds of smoke wich must have been N2O and whater vapor. I obviously
shouldn't have left it unattended. My question is, do these fum e s h a v e a n y n e g a t i v e e f f e c t s b e c o u se I m u s t h a v e i n h a l e d
quite a bit when opening every window in my house.
NoltaiR S e p t e m b e r 2 5th, 2002, 02:56 PM

If it really its NO2, than by personal experience with inhaling am ounts of it in the past, you will probably have a hell of a
headache in a few hours or with enough of it I have see n p e o p l e p a s s o u t .
vulture S e p t e m b e r 2 5th, 2002, 02:59 PM

Are you telling m e you don't know which gas is being produced when am m onium nitrate de com poses? This is pretty basic stuff
and you shouldn't be fooling around with something if you don't know wh ich reactions it will undergo and what it will produce.
NH4NO 3 -> N2O + 2H2O
N2O is also referred to as laughing gas. It has a euphoric effect in small doses and a narcotic effect in high doses.
spydamonkee S e p t e m b e r 2 5th, 2002, 07:14 PM

i h a v e h a d t h e s a m e t h i n g h a p p e n t o m e, but luckily all the sm oke was restricted to the kitchen so i just held my breath as i
rush e d i n a n d o p e n e d a f e w m ore windows.
did you find a fine po wder spread thinly around the area where you were boiling d own your AN?, like i could run my finger down
the wall and over the top of the oven and their was lots of fine white powder that i think was AN recondensed from the sm o k e
m ayb?
good luck breaking up the rock hard slab of AN you will now have :D
Kettch42mk.2 S e p t e m b e r 2 5th, 2002, 08:14 PM

If th e reactio n g e t s a b o v e a b o u t 2 4 0 d e g r e e s C ( c a n ' t r e m e m b e r the exact numb er) NO 2 is also produced. That's why it's not a
g o o d i d e a t o d e c o m p o s e N H 4 N O 3 t o m ake your own laughing gas.
m ore info he re:

<a href="http://www.erowid.org/archive/hyperre al/drugs/inhalants/n2o.synth" target="_bla nk">http://www.e rowid.org/archive/
hyperreal/drugs/inhalants/n2o.synth</a>
Madog555 S e p t e m b e r 2 5th, 2002, 09:43 PM

yes, some NO2 will fo rm too, but that can be easily disolved in water, m akeing the product "safe". its easie r to get whipits if u
realy wana do nitrous.
i have only h ad it once, at the dentists, it was pretty fun
andreas S e p t e m b e r 2 6th, 2002, 05:13 PM

I knew that the decomp. products were N2O and water but becouse m y "smoke"was so thick I was thinking of more byproducts
from side reactions. But I think it was very fine an particles becouse I had a powd ery layer around m y "coocking" site.A well I'm
still breathing so it co uldn't have been that toxic.

and Improvised Chemistry > Hydrazine
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inton September 25th, 2002, 11:40 PM

Would it be possible to use another inert gas other than nitrogen for the first distillation?
the second distillation you need to use nitrogen though.
??

Any inert gas should work at any stage. The reaction acts badly to oxygen, and presumably other reactive gasses like
halogens, perhaps even CO2. Nitrogen would be the top choice if you can get it for mere economic reasons. Helium of course
would be fine, as would neon or argon. These are a bit pricy, but if thats what you have then use em. I can't really say what
either CO2 or hydrogen would do with hydrazine. The literature says it is "reactive with air." Actually it says it explodes if traces
of air are present... I take that to mean oxygen, but who wants to find out the hard way eh?
[ September 25, 2002, 11:57 PM: Message edited by: megalomania ]
NoltaiR September 26th, 2002, 01:39 AM

How can nitrogen be the top (economic) choice or even a choice at all if the compound reacts with air which is approximately
78% nitrogen? (well I guess maybe it doesn't react to air itself, but rather the oxygen that is in it).. anyways I was just curious.
Microtek September 26th, 2002, 04:34 PM

Well hydrazine is strongly reducing, so likely it reduces the oxygen. Maybe it is strong enough to reduce CO2 to CO but I
doubt it. It would certainly not reduce N2.

Small tanks of helium gas are available at Toys R Us, Wal-Mart, and other places for inflating party balloons. These tanks are
quite cheap too, only about $10. Use one of these for your distillation. :)

Balloon helium is almost always a mixture of helium and oxygen. Try welders nitrogen. If the distillation can be worked under
vacuum this would be much better.
On the subject of hydrazine I am very interested in the xylene method on megas site. From the looks of things the xylene is
being used as an entrainer, to produce a tertiary heterogeneous azeotrope which removes the water and some hydrazine. This
being the case it seems likley that it requires the binary azeotrope as its input, ie 60% hydrazine, rather than 60% hydrazine
hydrate as stated. Any more water will affect the system adversely in terms of yeilds. To be really useful we need more
information on the heteroazeotrope, specifically its composition, and the phases it seperates into for recovery of xylene and
hydrazine.
The page is wildly optamistic in terms of its yeilds from the raschig synth. Raschig was an excellent experimental chemist and
modifying the synth is probably unwise. Ive read the thread that resulted in the adjustments, the product is a small amount of
hydrazine in a very large amount of salt water. Removing the sulphate and treating it with base is likley to save a lot of time
and effort. I will work out some probable yeilds based on existing data and the ammonia - hyperchlorite ratio, but as a rule of
thumb one of my books states this synth will yeild a solution containing up to 2% of hydrazine in the resulting solution.
Assuming you lose no hydrazine in the reduction in volume the maxamum concentration in the resulting brine is 6%
hydrazine. Concentration and seperation from the brine is likley to be non trivial, remebering also that reasonable
concentrations of hot hydrazine attack glass.
Its worth mentioning that the process uses a massive excess of ammonia to get even a half decent yeild of hydrazine based
on hyperchlorite. The excess ammonia is liberated during the boiloff and poses a serious heath hazard. Arguably much more
than the hydrazine the reaction produces.

Stuff a section of glass pipe with copper scrubber, heat to near redness, then pass through the heliox gas. Oxygen combines
with copper to form black copper oxide, leaving pure helium gas. :)
NoltaiR September 28th, 2002, 01:14 AM

Marvin is right about 'balloon helium' being a mixture of helium and oxygen; this is done for two reasons in particular:
1) cheaper.. in fact there are still traces of other gases as well
2) safety.. balloons are most always associated with children, and in the instance that a child accidently or purposely inhales
the mix; the only obvious effect is a momentary high-pitch voice and maybe a few dead brain cells.. but nothing serious
In industrial and lab grade helium, however, if you were to try to inhale it, you would most likely suffucate if you couldn't
exhale all the gas fast enough because it would flush out all the oxygen in your lungs. Also, you would most likely need a
permit or have your own business to be able to purchase industrial grade helium.
the_unbound September 28th, 2002, 09:12 AM

Hi,
I worked in a factory which sells 'balloon helium' and in such
small tanks are normaly only 5%-10% helium the rest is normal air.
xyz October 2nd, 2002, 05:04 AM

I know inton, he was asking to see if he could use the argon based inert gas mixture that is used for mig welding as he (or
someone he knows, I'm not sure) has a mig welder.

I am not too sure if this would work but .... lets say I prepare a batch of Hydrazine Sulfate using NaOCl and NH4OH and
H2SO4 method and let it sit on a hot plate and get the HydraSulf crystals .... Then to a soln of this in anything but H2O ... say
Acetone I add fine Zn dust or Mg or something like that. Shouldn't that remove the sulfate from Hydrazine and form the metal
sulfate and ppt out of soln which can be filtered out leaving behind a soln of Hydrazine in Acetone ..... which can be distilled
rather easily :D . Maybe using ether will work better as it boils at ~35*c but its structure is very similar to H2O which might give
some problems by forming compounds. Well its an IDEA so lets see what the experts think. :p

I can see what you are trying to get at B.R. but a metal wont do that, its in the wrong oxidation state. Metals will kick out
hydrogen in acids to get the right oxidation state, but hydrazine sulphate isnt very acid, its a salt of a strong acid and a half
decent base. Something like zinc hydroxide is probably a much weaker base than hydrazine and is largly insoluable all bad
traits to compete for the sulphate. Secondly, in order to do a metathesis, you need an ionising solvent, water works well, but
you get the hydrate, ammonia works (and doesnt require a base, it is one) but its rather beyond home methods. Alkali
hydroxides work well, being much stronger than hydrazine, but form water in the process. You can distill the product from
(previosly) fused KOH, which is a good dehydrating agent. Theres a sizable loss in this process though and with most other
hydrazine distillation methods.
Acetone isnt a useful solvent with hydrazine, as ketones and aldehydes form addition products (Hydrazones). Carbon dioxide
cant be used because it is an acid oxide, and so forms salts with hydrazine of its own. Anything synthetically useful can be
done with hydrazine hydrate, the difficulty, the extreme loss, not being able to use glass, aluminium, steel or most other
transition metals and the perminant health risks really dont justifiy the tiny amount of astrolite youd be able to make at the
end.

The reason I thought so is the chem formula of HydraSulf is N2H4*H2SO4 and not (N2H4)2SO4. I am not too sure of how
different the bonding is. I might be wrong but thats where the idea originated.
Marvin October 3rd, 2002, 02:55 PM

Ammonia has 3 hydrogen around the nitrogen, but its not planar becuase it has a lone pair, its distorted tetrahedral.
Molecules with lone pairs are lewis bases and can form ions with a proton. H3N: + H+ => NH4+ which is tetrahedral. NH4Cl is
a salt with ions NH4+ and Cl-, though you can write it as NH3.HCl but its not what happening becuase of the lewis base.
Hydrazine is very similar, there is a lone pair on each of the nitrogens and so its a fairly strong mono base, or a rather weaker
di base. You can write the molecular forumla as NH2NH2.H2SO4, but whats really present are NH3NH3 2+ and SO4 2- ions to
all intents and purposes.
Edit: Damn, last in the thread, thus robbing me of my 50th post. <img border="0" title="" alt="[Wink]" src="wink.gif" />
Finally did the math for the synthesis on megs page as promised a short eternity ago.
Based on,
1500 mL of 28-29% ammonium hydroxide
1200 mL of normal sodium hypochlorite solution
Yeild should be about,

1.8% hydrazine after reduction to 1/3rd volume.
2.7% hydrazine hydrate after reduction to 1/3rd volume.
or 78 grams of hydrazine sulphate.
Edit: Clarification, the percentages arnt the reaction yeild, which is actually quite high owing to the larger than normal excess of
ammonia, its the concentration of hydrazine in brine at the end of the reaction.
[ October 24, 2002, 04:03 PM: Message edited by: Marvin ]
Boob Raider October 23rd, 2002, 07:22 PM

Here's a method to prepare anhydrous Hydrazine that I came across.
Anhydrous hydrazine is prepared by heating under reflux 100% hydrazine hydrate with an equal weight of sodium
hydroxide pellets for 2 hours, followed by distillation in a slow stream of nitrogen introduced through a capillary leak.
(Cautio n! Distillation in air ca n lead to explosion.) The d istillate boils at 114 116 and the yield is 95 97%.
++++++++++++++++++++++++++++++++++++++++++++++
This isn't exactly news you know. Anybody who's read the merck index knows this. :rolleyes:
[ October 23, 2002, 07:07 PM: Message edited by: nbk2000 ]

Ive just corrected my use of the word 'yeild' in my last post, Boob, is the 'yeild' in your post the concentration of hydrazine
produced at the end of the reaction, or the total amount produced?
I would expect the process boiling for 2 hours to result in loss of considerable amounts of hydrazine. So I would expect 95-
97% to be the concentration, as over 95% is considered 'anhydrous' in my books.
IVe also read that if the temperature of the distilling flask drops below 60C, NaOH.H2O crystalises out, which is a problem in
vacuum distillation, it does make me wonder if we could form this and then decant to quickly concentrate.
Does the merk say anything about containers? We cant use glass, we cant use aluminium, we cant use steel, silver is damn
expensive. I'm wondering if we could coat the inside of a quickfit system with a layer of silver to try this sort of experiment.
Electroless silver plating is fairly easy and a lot cheaper than solid silver containers.
Boob Raider October 25th, 2002, 12:29 AM

Sorry about that NBK :( ... I for one haven't read the merck index so I didn't know it is there. Anyways Marvin ... I got this
from an organic synth site under the preperation of Acetone Hydrazone. One doesn't heat the NaOH and Hydrazine Hydrate
mix for 2 hrs ..... its just allowed to sit followed by distilation at the specified temp. I don't quite know what is implied by the
word "yeild" but I am assuming it to be yeild. I suppose the last 5% of the Hydrate is destroyed during distillation or remains
in the NaOH syrup.
nbk2000 October 25th, 2002, 01:39 PM

You can use glass, just not ground glass joints. The NaOH will react with the glass flask, but pyrex does so rather slowly. Pure
quartz flasks are very expensive, but are (I believe) immune to attack by NaOH. They're also thermal shock proof. You can
take them red-hot from a furnace and dunk them in ice water without shattering. :o
Polverone October 25th, 2002, 04:29 PM

Quartz isn't immune to attack by NaOH. But in all cases, the rate of attack of NaOH in aqueous solution on glass is relatively
low. Molten NaOH is a different story. Your glassware isn't going to be particularly stressed by this reaction - relatively low
temperatures, no vacuum - so I'd just go with the cheapest vessel you have lying around and if it's somewhat etched by the
NaOH, too bad. Of course that presumes that you already have hydrazine hydrate and that you really want anhydrous
hydrazine. I wouldn't want it. Not even if it were a free gift from DuPont under my Christmas tree. I don't have the facilities to
work safely with anhydrous hydrazine.

My understanding of pyrex is that is reacts faster with sodium hydroxide than soda glass does. I forget where I read this, but
this is presumably due to the boric acid content making the glass more acidic. I havnt tested this yet, I plan to keep all my
pyrex away from concentrated hydroxides.
Also hydrazine hydrate itself attacks glass, and the etched surface of the glass is going to be a much better catalyst for
decomposition of the hydrazine.
Add all of this the high temperature, and I dont think these are suitable conditions to use. I agree with polverone, I wouldnt
try this without much better facilities than I have at home, needs a fume hood with a chimney high enough to get the vapour
out of the way of people.
An easy way of making hydrazine hydrate, which is just as unfreindly but vastly useful would be a big help, and the conditions
are essentially the same. I cant seem to get round needing aperatus that will distill hydrazine. Maybe some sort of teflon
coating would work.
Ive read a few rather old reports of concentrating hydrazine, and even those that used silver aperatus ended up with less than
half of the hydrazine they started with as sulphate.
The organic nitrite process for azide is very clever if you can get hydrazine hydrate. Maybe we need to find a process that
doesnt use it. Preferably one that doesnt require a lot of fractional crystalisation.
Boob Raider October 27th, 2002, 11:10 AM

When the first sample of Hydrazine was prepared .... some dude did a whole bunch of reactions and obtained Hydrazine
Hydrochloride. He then mixed with N2H4*HCl, a soln of CH3ONa in CH3OH. The NaCl precepitated and a mix of N2H4 and
CH3OH was obtained which was later distilled.
And I also read that one of the newer methods of making CH3ONa is electrolytic. And the so called electrolyte consists of NaCl
and CH3OH. There might be some other things in it but the article didn't specify. So one doesn't need Na metal for making
the methoxide. :D
Mr Cool October 27th, 2002, 12:43 PM

There's another method that I found on the Hive, that involves mixing a metal hydroxide with an alcohol and adding excess
CaO, to form the metal alkoxide and Ca(OH)2. CaO shifts the equilibrium towards M-O-R and H2O. Equilibrium is reached
after a few days at room temperature.

Very interesting indeed, and points my books are very much missing on. I suspect forming NaCl is much prefered to forming
sodium sulphate, but I cant think why that would be. I have another fragment I can throw into this puzzle I think. If you take
dry ethanol or methanol and magnesium turnings, add a trace of something to start the reaction, an alkyl halides, eg carbon
tet, the magnesium will react and convert completely to magnesium ethoxide/methoxide.
With this twist, we arnt relient on the hydroxide forming for the effective dehydration (as it loses hydrogen directly), so we
might be able to use this with the hydrazine salt itself, rather than remove magnesium/calcium hydroxide to replace the base.
Alkali earth hydroxides are pretty crappy bases, maybe if you added sodium hydroxide youd get a ppt of the hydroxide or
oxide and sodium ethoxide/methoxide left even though its a stronger base. The same way calcium hydroxide caustifies
potash by exploiting low solubilities. This is almost exactly what MrCool is saying, except you dont have to worry about the
oxide/hydroxide equilibrium to achive the dehydration. This is very confusing, becuase its making a very strong base, from a
strong base, by precipitating a weak base.
As for making sodium methoxide electrolytically, Ive no idea how conductive a salt in methanol would be. I wonder if sodium
hydroxide in methanol would be preferable to sodium chloride, and how youd prevent the oxidation products at the anode
interfering. I read somewhere that the following reaction works for producing sodium oxide, Na2CO3 + C => Na2O + 2CO,
but I dont know what temperature is needed for the reaction to go, and Ive since failed to find any other information. Sodium
oxide should react with an alcohol to produce the ethoxide also.
I'm not sure in my mind how all the bits fit together, but this may well end up as the cunning process we need to produce an
alcohol solution of hydrazine with low water content directly from the salt.
aster January 1st, 2003, 06:26 AM

i had hydrazine hydrate 80%, i can increasing the concentration by dehidrating them using KOH, but what the difference of the
reaction by mixing this with AN, compared to mixing the anhydrous form with AN? anyone knows? thanks
Mr Cool January 1st, 2003, 11:08 AM

Well, it is my understanding that Astrolite explosives have hydrazine nitrate as the explosive component, mixed with Al or
whatever.
This is because
N2H4 + NH4NO3 <--> N2H5NO3 + NH3
The ammonia gas escapes, shifting the equilibrium to the right and producing hydrazine nitrate in high yield, perhaps
dissolved in hydrazine if it is used in excess.
Water will not interfere with this equilibrium, but the product will be hydrazine nitrate dissolved in, or wetted with, water (and
any excess hydrazine). So it will need to be dried out before use in order to make it cap sensitive. This will be quite hard,
since hydrazine nitrate is apparently quite hygroscopic, but leaving it in a warm oven should do it. Don't get it too hot,
obviously...
So the result will be crystals of HN, rather than the traditional Astrolites which are liquids, but it will still be a powerful, cap
sensitive explosive.
A similar method can be used to make hexamine dinitrate, although it is slower since hexamine is a pretty shit base, but it
failed when I tried it with 5-ATZ. Pitty.
[ January 01, 2003, 10:14 AM: Message edited by: Mr Cool ]
nbk2000 January 1st, 2003, 08:02 PM

Making hydrazine salts is fairly simple. It's getting the anhydrous hydrazine from the salt that's dangerous.
Now, if you can react sodium methoxide with hydrazine hydrochloride, to form salt and pure hydrazine in MeOH solution, than
you could probably use that solution as-is in a reaction with ammonium nitrate to form hydrazine nitrate, without previously
distilling it off.
Vacuum concentration of the solution to form a saturated solution of HN in MeOH would be fairly safe to do since it could be
done remotely without heating. The remaining liquid would still be explosive without being too sensitive since the alchol dilutes
it somewhat.
I did a quick Google search but, not surprisingly, failed to find anything about the solubility of HN in MeOH.
PEROMAN February 2nd, 2003, 03:15 AM

I've found a patent( <a href="http://www.uspto.gov/patft/" target="_blank">http://www.uspto.gov/patft/</a> ) about
producing ketazine (and then hydrolysing it to hydrazine) - No 6,482,383
The ketazine is made by reaction of ketone , NH3 and (!)H2O2

in a presence of catalyst( nitriles , amides , and ammonium salt of the acid , and sodium phosfates, or mixtures thereof)
Maybe, because of my bad english, i did not understand some parts of the patent (mostly about catalyst)
But this seems a very easy method - they use methylethylketone(but in another patent they use acetone) , 25%NH3(or less) ,
and 30%H2O2(or less) can be used . The reaction goes in room temperature (also in higher t) The yield is 70-90%
see also pat.: 3,972,878, 3,972,876, 3,948,902, 4,093,656
Ketazine can by hydrolysed by H2SO4(not concentrated) to hydrazine sulphate Then, for example, we add 100ml of water to
30 g N2H6SO4
and add CaCO3 - after the reaction ,we filter off CaSO4 and unreacted CaCO3 , and we get a solution of (N2H5)2SO4
Then we add Ca(NO3)2 (solution) to (N2H5)2SO4 and we get a solution of N2H5NO3 And then we dry the water out . So i think
it is not necessary to destillate hydrazine
Also see patent 5,241,117 - about producing semicarbazide from "manochlorourea sodium salt" and ammonia The catalyst is
Zn(2+) or Cd(2+)
NH2CONCl(-) + NH3 = NH2CONHNH2 + Cl(-)
Monochlorourea is made from sodium hypochlorite and urea
Then , i think, it is possible to add acetone to semicarbazide solution and filter off semicarbazone(NH2CONHN=C(CH3)2)(not
soluble) , and then we add nitric acid to it and obtain NH2CONHNH2*HNO3 (i think it is rather good explosive , but it can be
hydroscopic)
nbk2000 February 2nd, 2003, 05:04 AM

Looks interesting.
Mr Cool February 2nd, 2003, 04:08 PM

Do you have information on semicarbazide nitrate's explosive properties, or is it just supposition when you say it'd be a good
explosive?
While it may be good compared to other salts like AN, I'm sure it will fall behind the common HE's like PETN or TNP. Hydrazine
nitrate is a powerful explosive salt, but it is a somewhat anomalous case. In general, it can be said that the more hydrogen an
explosive contains, the lower its density (this is a very rough rule and is not applicable in all cases). Also, it is almost a
straight chain molecule, and will probably be less dense than the cyclic molecules of aromatic nitrocompounds, cyclic
nitramines etc. Few nitrate salts' VoD's exceed 4 km/sec, which is pretty shabby for a HE.
If you have semicarbazide, it is a MUCH better idea to convert it into NTO. Nitro compounds also have the advantage over
nitrate salts that they are not acidic (well they might be, but you know what I mean).
Thanks for the reference to hydrazine via ketazine, I'll check it out. It could be a very nice procedure...
nbk2000 February 2nd, 2003, 04:44 PM

Helvetica">Then we add Ca(NO3)2 (solution) to (N2H5)2SO4 and we get a solution of N2H5NO3 And then we dry the water
out.<hr /></blockquote>So then, once you have the hydrazine
sulphate solution, you add Calcium nitrate which would form HN + calcium sulphate precipitate?
I wonder, could an aqueous solution of HN be used as a sensitizer, like NM, or would the water render it impotent? I know that
once the HN reaches 95%+, that the solution is explosive, but what about lower concentrations?
Also, I saw urea for sale as a deicer for $12/Kg, at the local hardware store.
[ February 02, 2003, 03:48 PM: Message edited by: nbk2000 ]
PEROMAN February 2nd, 2003, 05:54 PM

No, i dont have any info on semicarbazide nitrate . But i think it is not bad .. For example , the maximum VoD of urea nitrate
is about 5000.
I dont know the VoD of hydrazine nitrate , somebody told me that it is about 8000 (but in some books(as i remember
Urbanski) they write (!)4-5km(!) - i dont believe it , because astrolite , based on HN , has high VoD) .
I think the heat of explosion of semicarbozide nitrate, must be rather close to the heat of exp of hydrazine nitrate, besides,
SN has a better oxygen ballance than HN
So its VoD seems to be at least more then 7000(seems to me) ,
Of course , it is better to make NTO , bust firstly i need to obtain any semicarbazide salt.
About HN:
(N2H5)2SO4 solution can be made by reacting N2H6SO4(called "hydrazine sulphate") with CaCO3(mixed with water) :
2N2H6SO4 + CaCO3 = (N2H5)2SO4 + CaSO4 + H2O + CO2
(N2H5)2SO4 is very good soluble in water (not N2H6SO4) ,

and Ca(NO3)2 too , but CaSO4 is not..
Then it is possible to crystallize N2H5NO3 by drying the solution on the air (without heating) , then mix it with Al
So i think destillation is not necessary
As for HN solution , i think it is not (a good) explosive(not sensinive) , and the VoD is very low
In Russia(Moscow) , urea costs about 50Cents (half dollar) per 1kg

(NH4NO3 is 30-40 cents per kg) - in fertilizer shops

When reading this discussion I get the impression that many of you believe that hydrazine nitrate is unstable at elevated
temperatures or perhaps too sensitive to risk heating. I don't think this is the case.
HN is sometimes used in cast charges with HMX when a very high VOD is desired because these generally have higher density
than the pressed variety. HN melts at about 60-70 C so it can be used as a substitute for TNT but of course has much better
VOD and OB. Anyway, I've seen a comparison of thermal decomposition data for various explosives and I think HN had 260 C
no reaction written next to it. I'm not absolutely positive that that was what it said, but I can say for sure that I have made
some HN myself by reaction of hydrazine sulfate in hot aqueous solution with Pb(NO3)2 soln. PbSO4 was filtered off and the
water evaporated under heating. The HN melted but did not decompose.
PEROMAN February 3rd, 2003, 08:50 AM

Somebody told me that the sensivity of HN is like RDX , but HN (as somebody said) does not decompose till 200c (and at
higher t it decomposes without explosion ) - it is hard to believe this
I read ,that N2H5ClO4 is very shock sensitive and dangerous

Yes I've heard that the perchlorate is quite sensitive too, but that is an entirely different compound. After all, the difference in
anion makes the difference between Pb(NO3)2 and Pb(N3)2.
cutefix February 4th, 2003, 06:18 AM

Hydrazineperchlorate will sensitize the binary explosive made with hydrazine hydrate,ammonium nitrate .
Without the perchlorated hydrazine it will be difficult to initiate a hydrazine nitrate in water solution.
Now to practically do that they will add a small quantity of ammonium perchlorate to the ammonium nitrate/hydrazine hydrate
mixture.
aster June 17th, 2003, 12:38 PM

i got 2 litre of hydrazine hydroxide, because ammonium nitrate is hard and expensive to get in my country, it cost about 20
bucks for 500 gram! damn:mad: for that fertilizer...:eek: , what the difference if i use HNO3 68% to nitrating them, in order to
get hydrazine nitrate? i think i should cooling the hydrazine hidroxide and bring the HNO3 dropwise, will it be safe? because i
think the water content of the 60% hydrazine hydroxide will makes difference from anhydrous hydrazine that stated will
explode in contact with HNO3:rolleyes: thanks for reply:D
vulture June 17th, 2003, 01:13 PM

Carefully neutralize your HNO3 (which is alot cheaper than NH4NO3 were you live I assume?) with an ammonia solution. Collect
the AN by boiling of the water.
That seems alot safer to me than nitrating hydrazine.
BTW, which country are you from? Did you ask for NH4NO3 at the apothecary? Because they'll charge you 500% of the usual
street price.
aster June 18th, 2003, 10:42 AM

yes in my country, HNO3 70%, and the ammonia sol 30% cost about $1 for a litre, i live in "beautiful country" have you ever
been in bali? :D thanks
tmp June 29th, 2003, 03:52 AM

To aster:
I wouldn't mix hydrazine and nitric acid together.

It might blow up in your face.
I understand that during World War II, the Germans

used this mix to power their V-2 rockets.
ANY input on this mixture is more than welcome
aster July 17th, 2003, 10:36 AM

did anyone knows, whether hydrazine nitrate grouped in primary or secondary explosives? since i think it's easy to set off, i
guess the hydrazine nitrate is a primary explosives, right?
knowledgehungry July 17th, 2003, 10:58 AM

70% NA and 30% NH3 for 1$ a liter??? no wonder there are terrorist attacks there:D
EDIT: no Hydrazine Nitrate is not a primary, Hydrazine perchlorate is IIRC.
aster July 17th, 2003, 11:18 AM

yeah, so cheap, but i think terrorist prefer a huge amount and readily build material, nitric acid is a pain in huge amount,
especially when reacting them together in nitration process or concentrating them :D, it's not their first choice, they prefer
potassium chlorat here:D thanks for the info

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Calculating Oxygen
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nbk2000
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Posts: 1091
From: Guess
posted December 09, 2000 12:50 PM
--------------------------------------------------------------------------------
Since I've seen people referring to "oxygen balance" and how it w orks to produce more pow erful explosions I thought it time to post how you actually go about calculating it.
Found this info on a US Navy site.
== ==== === ==== === ==== ==== === ==== === ==== =
Oxygen balance is an expression that is used to indicate the degree to w hich an explosive can be oxidized. If an explosive molecule contains just enough oxygen to convert all
of its carbon to carbon dioxide, all of its hydrogen to w ater, and all of its metal to metal oxide with no excess, the molecule is said to have a zero oxygen balance. The molecule
is said to have a positive oxygen balance if it contains more oxygen than is needed and a negative oxygen balance if it contains less oxygen than is needed. The sensitivity,
strength, and brisance of an explosive are all somewhat dependent upon oxygen balance and tend to approach their maximums as oxygen balance approaches zero.
The oxygen balance (OB) is calculated from the empiric-al formula of a compound in percentage of oxygen required for complete conversion of carbon to carbon dioxide,
hydrog-en to w ater, and metal to metal oxide.
The procedure for calculating oxygen balance in terms of 100 grams of the explosive material is to determine the number of gram atoms of oxygen that are excess or deficient
for 100 grams of a compound.
- 1600 Y
OB (% ) = Mol. Wt. of Compound 2X + 2 + M - Z
where
X = number of atoms of carbon
Y = number of atoms of hydrogen
Z = number of atoms of oxygen
M = number of atoms of metal (metallic oxide produced).
In the case of TNT (C6H2(NO2)3CH3),
Molecular w eight = 227.1
X = 7 (number of carbon atoms)
Y = 5 (number of hydrogen atoms)
Z = 6 (number of oxygen atoms)
Therefore
OB (% ) = -1600 [14 + 2.5 - 6]
227.1
= - 74% for TNT
Because sensitivity, brisance, and strength are properties resulting from a complex explosive chemical reaction, a simple relationship such as oxygen balance cannot be
depended upon to yield universally consistent results. When using oxygen balance to predict properties of one explosive relative to another, it is to be expected that one w ith an
oxygen balance closer to zero will be the more brisant, pow-erful, and sensitive; however, many exceptions to this rule do exist. More complicated predictive calculations, such
as those discussed in the next section (go here), result in more accurate predictions.
One area in w hich oxygen balance can be applied is in the processing of mixtures of explosives. The family of explosives called amatols are mixtures of ammonium nitrate and
TNT. Ammonium nitrate has an oxygen balance of +20% and TNT has an oxygen balance of -74%, so it would appear that the mixture yielding an oxygen balance of zero
would also result in the best explosive properties. In actual practice a mixture of 80% ammonium nitrate and 20% TNT by weight yields an oxygen balance of +1% , the best
properties of all mixtures, and an increase in strength of 30% over TNT.
== ==== === ==== === ==== ==== === ==== === ==== ==
Now get out thoses dusty calculators (oh w ait, you got a computer ) and get to blasting.
------------------
"The know ledge that they fear is a weapon to be used against them"
Go here to dow nload the NBK2000 website PDF.
rjche
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Posts: 52
From:
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very good post.
Really liked that navy manual you referenced in your (here) link. There's another good one
there on lasers.
to get to it hit the index tab at the bottom which takes you to the weapons manual.
When there hit the index tab that takes you to the manuals available. lasers is on that.
tropical6969
A new voice
Posts: 12
From: oz
posted December 11, 2000 01:14 AM
--------------------------------------------------------------------------------
nbk I think that your cock is the biggest one I've ever had the privilage of falling to my knees for. I luv slurping choad. A warm load makes me feel drunk . Cum drunk that is.
[This message has been edited by nbk2000 (edited December 11, 2000).]
Cricket
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Posts: 160
From: USA
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Have you been drinking.....hydrazine?
nbk2000
Moderator
Posts: 1091
From: Guess
--------------------------------------------------------------------------------
Sometimes sarcasm is more fun than deletion.
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PYRO500
Moderator
Posts: 1466
From: somew here in florida
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why doesn't anyone ever change their post? I mean it makes them look like an ass hole so why dont they just edit them?
Jhonbus
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From:
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I made a post ages ago (I think it was my first ever post in fact) wondering if anyone had tried this with AP, I w as thinking of doing it myself at the time, I just never got
around to it... Maybe I will try some experiments and a nice w rite-up for you all these holidays (On my computer simulator.)
------------------
A physicist can make a bigger explosion than a chemist ever did
<a href="http://www .geocities.com/jhon_bus/" target= "_blank">http://www.geocities.com/jhon_bus/</a>
10fingers
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Posts: 411
From: USA
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I think tropical dude pissed someone off. Thanks NBK for posting this method. I did not know there was such a simple formula for figuring this out. Thanx.
firebreether
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From:
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My god you are a genius! That is awesome. That is so simple yet seems very effective. Should be interesting what new explosives people make with it.
Microtek
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From:
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I agree we should have a better theoretical basis for our experiments. There is another site w hich has essentially the same information, but with a more practical ( as opposed
to theoretical ) approach:
<a href="http://www .fas.org/man/dod-101/navy/docs/es310/chemstry/chemstry.htm" target="_blank">http://ww w.fas.org/man/dod-101/navy/docs/es310/chemstry/
chemstry.htm< /a>
It has data on more explosives in terms of heat of formation, and molecular weight.
BTW here are some heats of formation that I found w ith a little research:
Picric acid: -217.88 KJ/mol

Mannitolhexanitrate: -708.8 KJ/mol
Nitromethane: -113.1 KJ/mol
Ammonium nitrate: -366 KJ/mol
I have looked for the values for acetone peroxide and HMTD but I can't seem to find them. Help would be appreciated.
PS. Try calculating relative strength for

84.7 % MHN and 15.3 % NM or 8.2 % NM and 91.8 % nitroglycerine.
[This message has been edited by Microtek (edited January 14, 2001).]
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
It's basically the same for optimising low explosive mixtures to make sure that the fuel and oxidiser are both used efficiently, and also to make sure you don't have an excess of
one component which would decrease burn rate. I know this is kinda in the wrong place, but it's related to this topic so I'll put it here. I've seen so many people use stupid
mixtures that I thought I'd try to help. Just remember that some mixtures, e.g. BP, do not burn to produce w hat you'd expect them to, so w ork out what the proportions should
be using this method and then experiment with the exact composition if you're trying to make things similar to BP.
This will seem obvious to the more experienced among you, but I thought it might be useful to some people.
e.g.:
If you're making an Al / KClO4 flash, work out the balanced equation for the reaction. You'll need to know the valencies of the elements involved to work out the products (Al =
3, K = 1, Cl = 1, O = 2):
8 Al + 3 KClO4 -> 4 Al2O3 + 3 KCl
It must have the same number of atoms of each element on each side.
Then use the mole weight of each reactant (use a periodic table) to work out the weight of each substance needed to produce the mixture with the best oxidiser/fuel ratio. Mole
weight of Al = 27, K = 39, Cl = 35.5, O = 16. Therefore:
8*27 grams of Al pow der and 3*(39+35.5+(4*16)) grams of KClO4 pow der.
That's 216 grams of Al for every 415.5 grams of KClO4.
This would produce 4*((27*2)+(16*3)) grams of Al2O3 and 3*(39+35.5) grams of KCl, but you don't need to know that.
I've tried to make it easy to understand, but I'm not a chemistry teacher so I'm not very good at explaining things like this!
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Yes, very interesting equations but it doesn't allow calculations for everything...let say as examples amongst many others: silver acetylide nitrate (Ag2C2.AgNO3),Chloropicrine
Cl3C-NO2 or trinitroiodobenzene (C6H2I(NO2)3).
Thus in many ways the best idea is to use the chemical equations wich are addaptable to each single case. The idea is simple: find the average oxydation state (the more
extended oxydation state) and combine as much O atoms to it...until no more O are available. Then all the rest needs to be burned by extra oxygen atoms.
In the example Al/KClO4, you have to know that Al2O3 is the more stable Al oxyde and that KCl will be a result but not the K and Cl2 alone or ClO, ClO2, Cl2O3, K2O.....Only a
lot of practice will lead you to fully understand this... so until then use the NBK2000 equations knowing it may not work every time.I also know (because I also have found
those equations from the Navy )that that equation is uncomplete because for M (metal) I remember there to be numbers linked to the valences...Al is +3, Ca is +2, K is +1
and here it only takes in account the 2 valenced metals....
------------------
"Chemistry is all w hat stinks and explode; Physic is all what never works! ;-p :-) :o )"
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Well, I know it's not perfect, but it should work for basic (I mean simple, not high pH) reactions I think.
Do you know what the difference is betw een silver acetylide and silver carbide? Is there one? I suppose silver carbide, if such a compound exists, would be Ag4C or something.
Please tell me if you know because I'm confused! I would have thought that Ag2C2 would be called silver carbide, not Ag acetylide.
PHILOU Zrealone
Frequent Poster
Posts: 479
--------------------------------------------------------------------------------
Following a mail I have send to Uberchlor...yeah you are not the only one to have been confuse by that chemical-drogistery vocabulary....
Ubi:
>School is interesting but my chemistry teacher makes alot of mistakes, for
>ex, he says cuprous carbide is Cu4C because of C-4 charge and Cu+1 charge,
>w here as all of the literature suggests the formula: Cu2C, same mistake for
>calcium carbide (CaC2) he says it is Ca2C because Ca+2 charge and C-4
>charge, when "sw ap" charges gives Ca2C simplified.
My Reply:
>-Actually he may not be wrong since carbides usually are C(-4) as Al
>carbide
>w hat is Al4C3 and Iron carbide is Fe4C3! Carbides usually liberates methane
>on
>contact w ith water what is the proof of C(-4) anion!Also a famous carbide
>is
>Silicon carbide caled carborundum or black diamond used as strong
>industrial
>abrasive, it is SiC.
>Al4C3 + 12H2O --> 4Al(OH)3 + 3 CH4
>But he might confuse acetylide w hat are C2(-2) that often liberates
>acetylen on
>contact w ith water (because of a wrong and comonly used name of Calcium
>carbide
>w ich is actually an acetylide).
>So theorically (for learning purpose of the valences- because I'm not sure
>those
>compounds really exist) carbide of copper(I), calcium and copper (II) are
>follow ing the crossing law of the valences:
>Cu4C, Ca2C and Cu2C
>But the acetylides would be
>Cu2C2, CaC2 and CuC2
Right, because acetylides (or acetylenides) have the anion: C2.sup.-2 or

HC2-
>So he may look stupid to you but might be right on certain points!
Ahhhh... I see! So carbides and acetylides are not the same? Beilstein says
Calcium carbide is Calcium acetylide, i alw ays thought they w ere the same
thing, but i see now. "Carbide" steel: so metal carbide is formed from metal
+ Carbon right, and the acetylide is formed from metal ion and acetylene or
other acetylide reagent.
------------------
"Chemistry is all w hat stinks and explode; Physic is all what never works! ;-p :-) :o )"
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Thanks. That's cleared a few things up for me.

a n d I m provised C hemistry > acid for nitration -Archive File
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megalomania S e p t e m b e r 2 9th, 2002, 06:39 PM

Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
p o s t e d D e c e m ber 28, 2000 10:39 AM
--------------------------------------------------------------------------------
I had an idea some time ago. It was to give SO3, which can be m a d e b y a
rection between a sulfate and sodium tetraborate, to diluted nitric acid (I
can't get the concentrated one). The SO 3 will react with the water, form ing
sulfuric acid. If enough SO 3 is used, both sulfuric and nitric acid should
be around 100%. Could this work? And if it will: W hen I try to m a k e R D X f o r
which only nitric acid is necessary, will the sulfuric acid that is pre sent
"disturb" the reaction?
Thank you
Rhadon
SofaKing
Freq uent Poster
Posts: 392
From : YEAH RIGHT !!
posted Decem ber 28, 2000 11:38 PM
--------------------------------------------------------------------------------
That sounds like a good idea ! However I have no idea if it would work.
10fingers
Freq uent Poster
Posts: 411
From : U SA
p o s t e d D e c e m ber 29, 2000 11:34 AM
--------------------------------------------------------------------------------
This idea has possibilities. But I have never seen a process for m aking RDX where sulfuric acid is used. If it were possible you
think it would be used because you could use a lower concentration of nitric acid, m ix it with sulfuric acid which would a b s o r b t h e
water. This would be sim ilar to the process for m aking nitroglycerin.
SofaKing
Freq uent Poster
Posts: 392
--------------------------------------------------------------------------------
W hat about bubbling N03 thro ugh the nitric to create higher concentration ? Just a thought.
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
--------------------------------------------------------------------------------
How could I synthesize NO3?? Is this p o s s i b l e ?
jin
Freq uent Poster
Posts: 111
From : u k
--------------------------------------------------------------------------------
if yo u heat calcium nitrate you get nitrogen dioxide when added to water you get a m ix of nitric acid and nitrous acid.
ca(n o 3 ) 2 h e a t e d = c a o +2no2+o2
no2+h2o=hn o3+hno2
[ T h i s m e s s a g e h a s b e e n e d i t e d b y j i n ( e d i t e d D e c e m b e r 29, 2000).]
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
--------------------------------------------------------------------------------
I doubt that the nitrous acid can be used for trinitration of methenam ine.
If SofaKing wanted to say NO 2 and not NO 3: I think NO2 doesn't reacts with water until the nitric acid that is formed reaches
100% concentration. Though I don't know the exact con centratio n that can be rea ched I think it's between 65-80%.
My target was to get nitric acid that is free from water, when I ha ve tim e to test it out the next days i'll tell you if the m i x o f
sulfuric and nitric acid can be used for m aking nitroglycerine. W hen I've got enough SO3 I'll also try to m ake TNT, but this
c o u l d t a k e s o m e tim e.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
--------------------------------------------------------------------------------
SO3 to m a k e 1 0 0 % H N O 3...m m m u h h h m m
good idea but very expensive one since let say you start with 70 %HNO 3 1000g will then contain 70 0g pure HNO3 an d 3 0 0 g
H 2 O (16.66 m ole); you will then need 16.66 mole of SO3 (100% dry) what is 80.05g/mole*16.66mole= 13 3 4 . 3 g o f S O 3 .
Yeah it's a lot: 1.34 kg for 1 kg m a k i n g thus a total of 2.34kg with a com position o f 5 7 % H 2 S O 4 p u r e a n d 4 3 % H N O 3 p u r e .
How much does SO 3 cost follo wing you r thoughts? Bette r then invest in the buing of a glass rod distillator (300-500 US$).
NxOy bubbled trough HNO3 to increase the %... nope you will have a lot of NO2 in the mix prom pt to produce a runnaway.
------------------
" C h e m istry is all what stinks a nd explode; Physic is all what never works! ;-p :-) :o )"
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
--------------------------------------------------------------------------------
M a k i n g S O 3 with m y m ethod also will be quite expensive and also pretty difficult. Unfortunately I couldn't try it out up to now
b e c a u s e m y "chemistry fellow" who has the sod ium tetraborate is somewhat busy right now.
Buying pure SO 3 should also be difficu lt and it's very expensive, like you say. But this way's yet easier than obtaining 100%
nitric acid.
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
--------------------------------------------------------------------------------
The concentration is 0.1 m ol/l. 1 m ol HNO3 weighs 65g, that's 6.5g of HNO3 per litre. Hopefully I didn't do a m istak e.
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
If you m a k e y o u r H N O 3 / H 2 S O 4 m ix with your SO3, you could use vacuum distillation to seperate o ut the HNO3 in pure form
(for RDX), leaving 100% H2SO4 and 100% HNO3. I wou ld have thought that 0.5 atmospheres at 50 C would work, but that's
only a sem i-educated guess.
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
--------------------------------------------------------------------------------
Hm , I think this would work but I don't have the stuff necessary for vacuum destillation.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > potassium nitrate
from ammonium nitrate -Archive File
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kingspaz
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Posts: 346
From: UK
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Is it possible to make potassium nitrate from ammonium nitrate?
i was thinking along the lines of using potassium chloride and ammonium nitrate in water to make ammonium chloride and potassium nitrate. i have done this but don't know if
a reaction has taken place or how to separate the products. does anyone know how i could get the two to react?
any input at all would be appreciated as it may get me thinking.
thanx
Rhadon
Frequent Poster
Posts: 95
From: Germany
--------------------------------------------------------------------------------
Yes, it's possible to make potassium nitrate from ammonium nitrate, and the preocess is quite easy. All you have to do it to moisten your ammonium nitrate a bit and give
potassium hyroxide to it. Reaction:
NH4NO3 + KOH => KNO3 + NH3 + H2O
Stir for a while until the reaction begins, then get away from it (not all the ammonia that forms can dissolve in water and thus is available in gaseous form).
I once used this process to make a mixture of NH4NO3 and KNO3 (from fertilizer) to pure KNO3. I heated the resulting solution of KNO3 until it contained no more water (take
a drop of it and bring it onto a cold surface; if it doesn't harden immediately you will have to continue heating).
Mr Cool
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Posts: 991
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Hi
It's easy to make KNO3 from NH4NO3 and KCl. Just weigh out 74.5 grams of KCl and 80 grams of NH4NO3. Put them in a beaker and just cover them in water. Heat the
beaker to boil the water, and add more water slowly until all the crystals have just dissolved, forming a saturated, boiling solution (there will be no obvious reaction). Then just
cool the solution in the fridge, and crystals of KNO3 will form and can be filtered out. NH4Cl is very soluable, so this will stay in solution. If you want to seperate it out of
solution, just boil off most of the water and cool it down again to precipitate it. It will also have a bit of KNO3 in it, and your batch of KNO3 will have some NH4Cl in it, but only
tiny amounts. If you like, you can wash your KNO3 crystals once or twice with ice cold water to get rid of most of the NH4Cl.
Hope this has helped!
kingspaz
Frequent Poster
Posts: 346
From: UK
--------------------------------------------------------------------------------
thanx guys!!!
Mr Cool
Frequent Poster
Posts: 991
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Hi,
It's easy to make KNO3 from those chemicals, you can just mix 80 grams of NH4NO3 and 74.5 grams of KCl, add a bit of water and heat it to boil the water. Add more water
until all the solid has dissolved to form a boiling saturated solution. Then cool it in the fridge, and crystals of KNO3 will form and can be filtered out. While still in the filter paper,
wash the KNO3 twice with a bit of ice cold water to get rid of the NH4Cl solution that is also formed. Dry the crystals in an oven at about 80 C for an hour or two, and powder
them. You should get about 95 to 100 grams of KNO3, allowing for losses.
Mr Cool
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If I've replied to this twice, it's because my computer has gone a bit strange and I wasn't sure if it worked. It's not because I'm weird.
SATANIC
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Posts: 232
From: australia
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would that process work for NaCl to make sodium Nitrate? otherwise , where would you get KCl?
Anthony
Moderator
Posts: 2304
From: England
--------------------------------------------------------------------------------
Sodium Nitrate is crap.
KCl can be had as a salt sustitute or as refills for water softeners.
kingspaz
Frequent Poster
Posts: 346
From: UK
--------------------------------------------------------------------------------
thanx guys
would i be right in saying the same process could be applied to make potassium chlorate from sodium chlorate and potassium chloride?
i think i better get me some chlorate weedkiller from B&Q..........
just a thought but do any of you think a mix of potassium chlorate 70%, vaseline 10% and charcoal 20% would make any sort of half decent smoke bomb?.....does anyone
have any suggestions?
thanx again
Anthony
Moderator
Posts: 2304
From: England
--------------------------------------------------------------------------------
Sure, just make a hot, saturated solution of NaCLO3 and a got saturated solution with twice the weight of KCl, mix them together and let it cool.
Vaseline/chlorate smokes quite a bit, a 50:50 mix of NaCLO3/wax smokes a lot with some NaCLO3/sugar mix to get it going.
MacCleod
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Posts: 215
From:
--------------------------------------------------------------------------------
I know this is kinda reversing the topic,but I read in an Industrial chemicals book about different processes of manufacturing AN;one was simply mixing ammonium sulfate and
sodium or potassium nitrate in solution,then evaporating until the AN crystallized out.It didn't list any specifics,however.Anyone else out there heard of this/tried it/have any
ratios?
------------------
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Isn't it true that KCl is used in lethal injection to stop the heart from working? I think they inject the guy with 2 other things first.
Anthony
Moderator
Posts: 2304
From: England
--------------------------------------------------------------------------------
Yes, I believe it either gives you a heart attack or slows your heart untill it stops.
Stone
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Posts: 140
From:
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Ok... NH4NO3 + KCl, i ended up with the white precipitate but it was pasty like, and testing it, it was not KNO3. Why did the Ammonium Chloride come out first? I assume the
KNO3 is still dissolved in the filtered solution, so it's being evaporated at the moment. I'll test that when it is dry.
Anthony
Moderator
Posts: 2304
From: England
--------------------------------------------------------------------------------
I would have thought that an ammonium salt would have been far more soluble than a potassium one!?
Stone
Frequent Poster
Posts: 140
From:
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Well... I filtered the white "stuff" out, dried it and then powdered it. I mixed it 50/50 with sugar and it would not ignite, the sugar just burnt where i put the flame. But i have
been evaporating the water out of the filtered solution and i took some "sludge" that was nearly dry and mixed it with sugar then put it back in the oven... it was taking too
long so i thought i'd hurry it up and see if it would ignite, so it went in the microwave It boiled the water off and then ignited. So there is a bit of KNO3 in there... But from the
look of the rest of the solution i still have heaps of AN in there. I think buying a bag of KNO3 will be much easier.
[This message has been edited by Stone (edited January 12, 2001).]
Mr Cool
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KNO3 still in solution?
That's weird...
Yeah, it'd probably be easier to buy the KNO3 if you can find a source, but it's getting rarer.
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Anthony, where do you get your KNO3 from? I've tried everywhere, can't find it!
MacCleod
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Posts: 215
From:
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Anthony,blackadder;do you live in the U.S.?.I've found it at most smaller hardware stores as stump remover;'Dragon'brand(small white prills),and 'Green Thumb'brand(tan
powder,slightly impure).It's about 6 or 7 dollars a lb..
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[This message has been edited by MacCleod (edited January 13, 2001).]
Anthony
Moderator
Posts: 2304
From: England
--------------------------------------------------------------------------------
I'm a UKairian I've emailed you Blackadder.
$6 or $7 a pound? That's quite expensive, I can get 25kg fertilzer grade KNO3 for 32.
zaibatsu
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Posts: 403
From: England
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Hey anthony, can u send me an email about it too? thanx
------------------
Handguns don't kill people... Half as well as full-auto
Visit me at <a href="http://www.surf.to/eliteforum" target="_blank">www.surf.to/eliteforum</a>
SATANIC
Frequent Poster
Posts: 232
From: australia
--------------------------------------------------------------------------------
has anyone ever found KNO3 as stump remover in aus? I have found you can buy it at farming stores, 25kg bags, but i can't get it home like that. (i have no car + under 18)
Stone
Frequent Poster
Posts: 140
From:
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SATANIC... how much was the 25kg bag?
Teck
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I have some sources where I buy my chemicals. Although the shipping is pretty expensive check them out. <a href="http://www.sciencealliance.com/"
target="_blank">http://www.sciencealliance.com/</a>
and
Pyrotek
PO Box 300
Sweet Valley, PA. 18656
(507)256-3087 <a href="http://www.pyrotek.org" target="_blank">www.pyrotek.org</a>
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teck are you from oz?
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blackadder
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I know that KNO3 is used as a stump remover (Im guessing people mean tree stumps), but what does KNO3 do, that removes a stump?
Just curious.
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You drill several large (1 in.) holes down into the stump at different angles, fill the holes with the KNO3,then pour water in the holes,let stand for 6 to 8 weeks (until the nitrate
is completely absorbed).Then pour some kerosene,gas,etc.on the stump and ignite it.The stump smoulders until only ashes are left.
jimwig September 30th, 2002, 10:56 PM

nope sodium nitrate is sodium nitrate
crap is that stuff you are supposed to leave behind when you shit
or grow up.
sodium nitrate is very hygroscopic and consequently not near the son
that potassium nitrate his sister is.
but when it comes to making nitric the boys' right there.

Nitrates in general exibit a very large difference in solubility with respect to temperature. Chlorides are mostly flat with temp. When KCl and NaNO3 are reacted to produce
saltpeter, its NaCl that is least soluable in boiling solution, but KNO3 thats least soluable at room temperature.
The reason, for those who are interested is directly related to the absorbed when the salt dissolves in water. Thus ammonium nitrate, which is used in cold packs as most of
you know, has a massive difference in solubility with temperature.
Its difficult to predict what salt crystalises from a mixture of ions at a given temperature. The only relaible way is to experiment, and the given problem is ideal as all 4 possible
salts are easy to identify. The nitrates oxidise, so a few drops of solution on a filter paper and dried and lit can be considered a reliable test, the ammonium salts will leave little
or no residue when strongly heated (this should only be done in small amounts).

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Liquid Oxygen Synth
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Positive Electron October 3rd, 2002, 07:51 PM

This topic is about condensing gaseous oxygen into liquid oxygen.
The boiling point of oxygen is about -184 degrees, and at -184 it begins to condense into a pale blue liquid.
The materials you will need is an oxygen tank with the approiate valves, 2 metal jars, 2 clamps (one big enough for a jar, and one for a test tube), 4 feet of 1/4 inch copper
tubing, a good epoxy, a test tube (size depends on how much you want to make) and enough liquid nitrogen to fill one of your jars three times over. It also helps to have a
dowel to wrap your tubing around.
Take your tubing and wrap it around the dow el in a tight coil, leaving 5 inches on the top and bottom. cut to size.
drill a 1/4 inch hole in the bottom of one of your jars. slide the coil in, and secure and seal with epoxy. Attach this jar 8 inches off yiour working surface with a clamp.
beneath it, place the other jar on the work surface, and position the clamped test tube directly under the tubing.
begin to slowly fill the top jar with liquid nitrogen, adding it very slowly, and letting it boil off until the jar and pipe are -194 degrees. when it stops boiling, fill it to the top, and
repeat the process in the bottom jar.
attach your oxygen tank to the top of the coil, and turn it on very low . the flow should be extremely low.
the oxygen will condense in the coil, and eventually your test tube w ill fill with liquid oxygen.
i don't know much of what you would do with it, most things burn in it explosivly, which is a good thing.
little fun note: hold tw o electromagnets about a quarter inch apart, on, and pour small amounts of the liquid o2 betw een them, adn notice how the oxygen is paramagnetic, and
sticks. i had an idea about a fuel distribution system for a "potato gun" type gun, but it would be to expensive and unruly.
File: A diagram of the coil setup- < a href="http://ww w.angelfire.com/movies/nutsmeller234/chem/coildiagram.jpg" target="_blank"> http://www .angelfire.com/movies/
nutsmeller234/chem/coildiagram.jpg</a>
Ctrl_C October 3rd, 2002, 11:03 PM

I'm not sure how well this would w ork in practice. You only have 10* to play with. It could be used to supersaturate a substance with oxygen though.
Positive Electron October 3rd, 2002, 11:18 PM

it works quite well if you devoid the tubing and jars of all their kinetic energy. in about 22 minutes i have produced 100ml of liquid oxygen
Mick October 4th, 2002, 04:45 AM

basicly, exactly w hats listed on this page... < a href="http://w ww.allatoms.com/LOXpage.htm" target="_blank"> http://www.allatoms.com/LOXpage.htm< /a>
EP October 4th, 2002, 09:45 PM

<blockquote>quote:< hr /> i don't know much of what you
would do with it <hr />< /blockquote>I'd probably give LOX/sprengel explosives a shot if I had some liquid oxygen...
xyz October 5th, 2002, 02:00 AM

I've heard that pieces of charcoal or silicon wafers soaked in liquid oxygen explode violently, it was in the new scientist a while ago.
Jhonbus October 5th, 2002, 12:16 PM

The oxygen tank isn't really necessary, I wouldn't bother using one unless I already had the regulators etc. Normal air can be used, but the production w ill be slower, and you
waste more of your..um, lack of heat.

If you use air you will make liquid air or at the very best a nitrogen/oxygen mix slightly better than air. Useless for LOX explosives and requiring fractionation to seperate,
essentially not possible without a lot of LN2 to waste and dedicated equipment. If you are going to the expense of getting liquid nitrogen (w hich is dirt cheap, but the containers
are very pricey) youd get a source of pure oxygen.

Separating a mix of LN2 and LOX is a simple matter of allowing the LN2 to evaporate.
Besides, I don't think much N2 would condense from the air anyw ay. You can think of it as an equilibrium between LN2 evaporating and N2(g) condensing. Since the
surroundings are at a high relative temperature, LN2 w ill evaporate.
But yes you are right, Dewars are very expensive, so a bottle of O2 shouldn't be any trouble if you've got the LN2 side covered.
[ October 06, 2002, 11:47 AM: Message edited by: Jhonbus ]

I can see why you would think oxygen w ould condense fairly pure from the air, and why any LN2 would evaporate first from a mixture, unfortunatly it isnt that simple. Its
tempting to think that the boiling point of a liquid is the temperature at which molecules leave the solution and enter the gas phase. This isnt true though, its the temperature at
which the pressure of the gas phase of the liquid exceeds atmospheric pressure. Below this point there is a partial pressure of gas phase less than atmospheric pressure, but still
present. Ok, mixtures. Lets assume that the mixture of 2 liquids is "ideal", that is, there is no interaction betw een the molecules of the two liquids. The consiquence of this is
that there will be no eutectic in the vapour phase diagram, w hich makes the thought experiment easier. The total pressure of gas exerted by the liquid will be the *sum* of the
partial pressures from both componants. (While this is alw ays true, one partial pressure is only said not to affect the other if the liquids are not miscable, a state you end up
from if there really is no interaction between the molecules of the two phases). If you boil the liquid, the gas phase you get will be in molecular proportion to the partial
pressures of the gasses over the liquid at the temperature its boiling at. Which in real mixtures, does not have to bear much relation to the boiling points of either one of the
componants as its the sum of the partial pressures of both componants exceeding atmospheric pressure that matters. If a mixture is ideal, you can make your own VLE diagram
based on tables of partial pressures for both componants.
Ok, what does this boil down to. Chemistry humor, my apologies. A mixture (even an ideal one) of liquids w ill only seperate a pure compound by single plate distillation if the
partial pressure of all the other componants is zero.
If you leave liquid air to evaporate, the mixture w ill enrich, becuase the partial pressure of the oxygen in the gas phase will be lower due to its higher boiling point. You wont get
oxygen moving back from gas into the liquid in preference to nitrogen however, as they are both in equilibrium. Blowing atomospheric air over the solution will give you a small
degree of oxygen going into solution, up until the point the partial pressure of oxygen in the gas phase at equilibrium exceeds the content of normal air, at the expense of a
much greater loss of liquid air, unless you have a heat exchanger to swap the energy of the air going in with the slightly oxygen reduced boiloff going out. This would be one
step closer to the dedicated equipment for seperating I talked about. The result of all this is you need to let boil a *lot* of liquid air to end up with a liquid phase that is over half
oxygen, unless you have a refinary setup.
Since condensing is just the reverse equilibrium of boiling exactly the same argument applies to explain why you cant condense pure oxygen from the air. The definations are
simply turned on their heads, and condensing becomes the point at which the *sum* of the partial pressures in the gas falls below atmospheric pressure, and you get the same
choice, simply feed in the air and get liquid air, or let it circulate without a heat exchanger and get a much smaller amount of slightly enriched oxygen in liquid air.
Ordinary 'glass' thermos bottles of the type you keep tea hot in usually work very well for liquid nitrogen. The pyrex they are made from handles LN2 w ith no problems, my
university used these for students. They are vastly cheaper than dedicated dewars but you are usually limited to types under 2 litres simply becuase noone seems to sell bigger
thermos bottles. 2 litres is far too small for any real experiments but you can use these to handle it from the main dewar.

Thanks for correcting me. As you can tell, physical chem isn't exactly my forte... ugh. :cool:
I don't have any experience buying cryogenic gases, will companies sell to you even if you don't have the "proper" equipment? If so, perhaps a discussion on insulating
containers for the purposes of containing largish volumes (say 25 litres) of LN2 is in order.
Would ordinary solid foams such as styrofoam or polyurethane foam insulate well enough? If so a rough and ready container could be made from tw o thinw alled containers, one
inside the other, and a layer of foam between them.
[ October 06, 2002, 02:15 PM: Message edited by: Jhonbus ]
PYRO500 October 6th, 2002, 04:29 PM

The best containers to keep LN2 are vacuum flasks, mainly beacuse the liquid nitrogen is going to cool and freeze anything it touches. I have herd of people taking those coffee
flasks that are vacuum bottles and having them filled although I don't have experience in doing so. One thing you have to keep in mind is that your flask w ill need to vent the
nitrogen gas to keep from exploding. so drill a hole in the cap of your container if it's air tight.
[ October 06, 2002, 04:01 PM: Message edited by: PYRO500 ]
a_bab October 6th, 2002, 06:57 PM

Those flasks will be always air tight because you don't want to spill the hot tee, and are called "Dew ar" flasks.
Positive Electron October 6th, 2002, 09:57 PM

i w as thinking of some sort of application to sabatoge a combustion engine or some sort of application w here it w ould be combined magnesium to ignite thermite
Anthony October 7th, 2002, 11:45 AM

Igniting thermite? Even something like KNO3/sucrose will do that? Why deal w ith the complexity of producing, storing, handling, transporting LOX needlessly?
How would you sabbotage a car with LOX? If you pour it in the "gas" tank all it's going to do is boil off as it touches the comparitevly "hot" contents of the tank. In fact you'd
probbaly burst the tank with the sudden expansion of gas, or shoot the contents out of the filler tube and all over yourself...
Simplify :)

If you pour LOX into petrol, it will instanty ignite, probably quite explosively. Not a good idea.

If I'm not careful Jhonbus will think I have something against him personally, which I assure you isnt the case. I'm not conviced LOX and petrol is a hypergolic mixture though.
Pure oxygen at room temp and petrol doesnt ignite automatically, so I fail to see why pure oxygen at around 100K would ignite it. You wont get the two liquids 'touching' in any
real sense. Pure oxygen gas and petrol vapour w ould ignite very easily and spectaculaly, so the slightest spark is all thats needed.
If its present for a prolonged period, Id expect the petrol to be cooled below its flashpoint (which will be lower w ith pure oxygen than air), and become very difficult to ignite.
The petrol would freeze before the temp drops far enough to let the two phases mix. How to sabatage a car with LOX? Tell the owner if he feeds pure oxygen into the engine it
will go faster, and wait.

I was making my assumption based on reports of petroleum jelly spontaneously igniting in 100% O2 atmospheres. Perhaps petrol wouldn't spontaneously ignite,
but I w ould expect it to, and I certainly wouldn't w ant to pour them together. Boiling oxygen will raise the petrol into a very fine mist, creating an even more hazardous
situation.
Jackotrades January 24th, 2005, 09:48 PM

Exposing a combustible material to pure oxygen only lowers its flash-point (the temperature at which the material w ill spontaneously ignite without flame) so it is safe to
assume that a mixture of LOX and petroleum fuel at cryogenic temperatures would not spontaneously ignite. The flash point of most petroleum based products can, however, be
low ered to room temperature in a pure-oxygen environment (gaseous oxygen, also at room temperature).
Marvin January 25th, 2005, 01:49 PM

Your definition of flash point is wrong. Its the point a fuel can be ignited by a spark or a flame. That is to say its burning will self sustain. You are thinking of the autoignition
point, but I'm not convinces this w ill change much with pure oxygen at room temp anyway.
Jacks Complete January 26th, 2005, 08:11 PM

Hmmm. Not tried with LOX, but for storing LN, I always used a Thermos flask. A two liter one was good, with a pouring spout that could be left open. If you drill a small hole, it
might ice up if it is damp, causing a pressure build-up. I found it would last for about 4 days if you just left it, mostly. Leave it outside in the shade.
Also, don't let some spastic "friend" drop anything in the flask. It is *not* cool.
MightyQuinn January 27th, 2005, 09:54 PM

Those flasks will be always air tight because you don't want to spill the hot tee, and are called "Dew ar" flasks.
I belive you are w rong (or kidding) Dewars are never 'air tight.'
1 cubic foot of liquid nitrogen will expand to 696 cubic feet of gaseous nitrogen at 70 F. Any air-tight container containing liquid nitrogen would surely explode in due time.
I believe most dew ars use something akin to a styrofoam lid to cap the container.
Anthony January 28th, 2005, 02:04 PM

You don't keep hot tea in a dewar, do you? He's talking about vacuum flasks used to keep hot drinks (Thermos flasks), and saying that they are usually sealed (to keep the
drink from spilling), and so would be unsuitable for storing cryogenic liquified gases.
Mumble January 28th, 2005, 08:26 PM

At the lab I worked at over the summer there were two types of LN containers w e used. One was this plastic container with a styrofoam lid. I assume it was a styrofoam
between the inner and outer walls, it didn't seem to top of the line. It has a pressure release notch to keep it from pressurising. The other w as a 4L dew ar with a tapered neck,
down to about 1 1/2". Metal construction with a vacuum betw een the inner and outer. The lid w as basically oversized by about 1/4" all around w ith 3 crimps in to hold it on the
top of the container. It didn't press all the way down and allowed pressure to escape pretty easily.

and Improvised Chemistry > Acetic Acid ------> Acetic Anhydride -archive file
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megalomania October 7th, 2002, 03:24 PM

Detonator
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Can you obtain Acetic Anhydride from Acetic Acid or vice versa??
Anthony
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Yes, you can synthesise acetic anhydride from acetic acid.
Why would you want to make acetic acid from acetic anhydride?
PYRO500
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just add water
ALENGOSVIG1
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Moving to misc.
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technology is a wonderful servant, but a bitch of a master.
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Detonator
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How would you synthesis acetic anhydride from acetic acid?
kv21
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Preparation of acetic anhydride and acetyl chloride
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Acetyl Chloride
===============
Connect a dry 250 ml three neck flask with a distillation adapter,

condenser and addition funnel. Use a 250 ml rb flask for the receiver
connected to the condenser with a vacuum adapter. Use the vacuum adapter
to make a gas trap with rubber tubing to an anhydrous CaCl2 drying tube
exiting to an inverted funnel suspended over a beaker of water. This
important stage is to protect the distillate from water while absorbing HCl
evolved in the reaction.
Place 54 g. (52 ml.) of glacial acetic acid in the three neck flask, close
with a stopper and add slowly through the addition funnel 46 g. (29 ml.)
of phosphorus trichloride. Cool the flask by immersion in a water bath. Mix
the reactants thorougly and, after allowing the mixture to stand for ten
minutes, heat the water bath to 40-50? and maintain it at this temperature
for thirty minutes, with occasional swirling of the flask. During the
heating the liquid usually separates into two layers. Acetyl chloride forms
the upper layer.
Distill the acetyl chloride by heating the water bath to boiling and
maintaining it at that temperature as long as any liquid passes over. Cool
the receiver in an ice bath during the distillation. The syrupy residue in
the distilling flask is phosphorous acid, which is discarded.
--> CAUTION: The reaction mixture must not be overheated since this will
lead to formation of phosphine, which is spontaneously flammable in contact
with air.
To the distillate add two drops of glacial acetic acid, to destroy mixed
phosphorous-acetic anhydrides that would cause turbidity to develop on
standing. Redistill the acetyl chloride from a distillation apparatus
arranged as before except without the addition funnel and with a
thermometer. Collect separately in a dry receiver the portion boiling at
50-56? and transfer it to a dry weighed glass-stoppered bottle. Acetyl
chloride attacks corks and rubber stoppers. The yield is 44-56 g.
Acetic Anhydride
================
The apparatus for this process is similar to that used for the preparation
of acetyl chloride. The same precautions for exclusion of moisture must be
observed but it is unnecessary to provide the inverted funnel arrangement,
since hydrogen chloride is not evolved.
In a 250ml. rb flask fitted as for making acetyl chloride, place 60 g. of

finely pulverized anhydrous sodium acetate.* Arrange in place the
condenser, dry receiving flask and drying tube; the receiver need not be
cooled. Check to insure that all connections are tight. Cool the reaction
flask in a bath of cold water and add dropwise, through the addition
funnel, 40 g. (36 ml.) of acetyl chloride.
After the addition has been completed, remove the water bath and shake the
flask to obtain good mixing of the reactants. Recheck the connections for
tightness.
Dry the outside of the flask with a towel and heat it with a mantle or oil
bath. Continue the heating until no more distillate comes over but do not
overheat the solid residue.
To the distillate add 4-6 g. of finely powdered anhydrous sodium acetate,

to react with a small amount of acetyl chloride that may be present. Add a
boiling chip and redistill the crude acetic anhydride. Collect the product
distilling at 132-138? in a dry flask. The yield is 30-40 g.
* NB: Commercial anhydrous sodium acetate usually contains some moisture.

To remove moisture fuse 70-80 g. in a casserole and stir until no
more water is evolved. Do not overheat! Cool and quickly pulverize.
Store in a tightly sealed container before use.
Detonator
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Thanks guyes, but how to obtain it from Acetic Acid????????????????????????????
Jhonbus
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From the KIPE2:
Acetic anhydride is produced by absorption of ketane vapors in
acetic acid. Acetone is injected into a chrome/iron alloy pipe through one
end equipped with a feed valve and assembly. This pipe is previously purged
with argon or nitrogen. The pipe is heated to 650 to 670 degrees C. This
heating can be done by electric heat with a thermostat or by a coal or gas
fired oven. The injection of acetone into the reaction tube is begun when
the proper temperature is reached. The other end of the pipe is attached
to a stainless steel 3/8" tubing. This tubing is placed through a two hole
stopper in a gallon jar placed in a salted ice bath. This is to collect all
unreacted acetone. In the other hole in the stopper on this bottle is
placed a second stainless steel tubing. This goes to another gallon jar
through a two hole stopper. In this jar is placed the acetic acid. The
second hole in this stopper is placed in line for venting purposes. This
line is placed outside or in a safe place for the poisonous fumes to go.
Acetone is injected slowly into the chrome/iron pipe @ 650 to 670
degrees C. This will react approximately 15-25% of the acetone into
ketane. The vapors from the reactor [are] directed into the first bottle. The
unreacted acetone will collect here. The ketane vapor will continue through
the tubing to the next jar. The ketane vapors are absorbed here by the
glacial acetic acid. These vapors are absorbed until the density of the
liquid is 1.08 @ 20 degrees C. This is checked by a hydrometer placed in
the glacial acetic acid. At the time this specific gravity is reached the
material in the second jar is acetic anhydride.
...CAUTION: Acetone is highly flammable. Great care is needed to

ensure total absence of [oxygen] in the reactor prior to injection of acetone.
Failure to do this can result in an explosion. The whole reaction should be
done with very good ventilation. (don't breathe the ketane!)
[This message has been edited by Jhonbus (edited February 19, 2001).]
Scarecrow
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1) That sounds as a very difficult process to make and one needs some equipemment to make it work!
2) Could you make a diagram for this!!
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dont worry we're faster!!!!!
Jhonbus
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Here's a lovely picture:
<img src="http://www.geocities.com/jhon_bus/Ethanhyd.jpg" alt=" - " />
You would want to purge the whole apparatus with argon or similar before use.
Detonator
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I think it's very hard to be done without a lab!!!!
Don't you think so?
ALENGOSVIG1
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No, i dont beleive that would be difficult. Unless you cant get jars tubings ans ome pipe. Otherwise i beleive it is wuitw feasible.
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Anthony
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Posts: 2304
From: England
--------------------------------------------------------------------------------
The problem I can see is keeping the pipe heated to within the rather narrow window of 20*C at such high temperatures.
Maybe it could be done with a furnance with fine thermostat control, but it's not something you could do with a blow torch
(unless you had a good high temerature sensor).
I take it the system is pressurised by the heating of the acetone expanding into ketane gas. This would require an actual one-
way valve assembly on the heating pipe, you may find it difficult to find valves that will withstand that kind of temperature.
Shame you can't get bottled ketane

H2C=C=O is Ketene, not ketane.
Its extremely toxic, comparable to phosgene, you really do not want to make this with leaky aperatus but at least you wont
miss the smell of this stuff, so you know if its killing you.
Its very reactive, reacts with itself if left alone, which is doubtless why you cant get it in tanks. There is an acceptable synth in
organic synthesis, which now its online is here,
<a href="http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?rxntypeid=292&prep=CV1P0330" target="_blank">http://

www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?rxntypeid=292&prep=CV1P0330</a>
Ive been told there are improvements to the synthesis made after this was put together that involve a copper catalyst instead
of porcelain, its worth looking these up if you plan to try this.

I've just done a run of the ketene process with the apparatus used in this (http://www.roguesci.org/theforum/showthread.php?
p=61896) thread. The only difference being that a litre flask with 800mL of AcOH and the Dreschel head was placed before a
simple gas drying bottle with more AcOH. I'll have to put things on hold for a while though, as one of the ground glass joints I
fitted to the copper tube has cracked quite badly and may need to be replaced.
I found that the rate at which the acetone distills over is really quite important. Initially it came over too quickly and some
even got beyond the reflux condenser (see below). The heated section of pipe could not be maintained at a red hot
temperature and no ketene was formed. The rate at which the acetone came over was lowered and the pipe began to glow red
hot. Some suck back occured temporarily until significant ketene began to form.
I had almost finished the run when the crack occured in the glass and I had to stop it. About 800mL of the 1L of acetone had
been distilled across, that which had not been pyrolysed had condensed and had a yellow colour to it. The total acetone left
over after combining the condensate and that not distilled was 800mL.
The density of the AcOH in the main flask had gone from 1.05g/mL to 1.04g/mL. I'm concerned that no acetic anhydride was
formed and this density change is due to the acetone which got into the acetic acid. Perhaps some Ac2O was formed and the
decrease in density caused by the acetone was limited by this. I have also thought that Ac2O, density 1.08g/mL mixed with
1.05g/L AcOH may result in a lowering of density, in a similar way to how some mixed compounds have melting points lower
than either alone. I would certainly appreciate any information anyone has on this matter.
There is one ray of hope: I saw a slight fuming effect, characteristic of Ac2O, occur as I poured the 'product' into a measuring
cylinder to take a density reading.
Microtek May 11th, 2004, 05:14 AM

I think the best way of testing the purity of it would be via titration. Pure Ac2O consumes 17.7 % more alkali per gram than
AcOH so it would require some accurate equipment or a large sample.
Dave Angel May 11th, 2004, 09:26 AM

Nice one Microtek, I have a burette so the procedure is not a problem, it's this unknown quantity of acetone contaminant that
is. I've repaired the apparatus but it's less than perfect and if it still leaks then I'll have to rethink.
I'll try another run today (providing I have any burner fuel left) and see if I can affect the density again, without further
acetone contamination. Anymore Ac2O formed should help overcome the acetone dilution and, if necessary, a subsequent
titration compared with acetic acid alone will hopefully give the desired result.

Is fractionally distilling the products not an option? This would determine the amounts directly, and non destructivly.
Id suggest adding ammonia, but I cant think of a way offhand to seperate ammonium acetate from acetamide.
I have to say also, I like some of the methods apearing at sciencemadness for acetic anhydride. One method uses sodium
pyrosulphate which is extremly cunning.

I could try fractional distillation, I built a column out of an old condenser and broken glass which isn't perfect but functions,
though I don't have a way of fitting a thermometer to this suitably.
My burners are just about out of fuel so I'm not going to be doing any more runs for the time being. I was thinking that
pumping more ketene through the AcOH would be the way to go as I would get more product with my time as well as
confirmation of product forming.
Thanks for the reference to sciencemadness. The pyrosulphate process looks interesting and I might give it a try once I have
the reagents. I notice it was also suggested there that CO2 could be bubbled through alcoholic sodium acetate solution to
yield Ac2O and Na2CO3. It was also noted, however, that the anhydride would go on to react with the alcohol.
Perhaps if acetone is inert towards Ac2O and will dissolve sodium acetate then one could make the acetate from vinegar, and
bubble welding CO2 through it. It sounds too good to be true but is certainly worth investigating, as it is the simplest of all the
processes I have read about, would save money and make Ac2O a cheap OTC synthesis.
[Edit] I've just done a few tests and sodium acetate is not soluble in acetone. It will dissolve in glacial acetic acid, although
this is not OTC and would react with the CO2 to give carbonic acid as a byproduct which would then decompose to water (as
noted on the sciencemadness forum), bad for acetic anhydride. One could use pure acetic acid but this would only enhance the
amount of carbonic acid produced.
In a closed system I expect some kind of equilibrium would exist as the water from the carbonic acid decomposition would turn
the anhydride back into acetic acid, but more CO2 would also be produced and react with the acetic acid...
I wonder if the addition of anhydrous MgSO4, CaCl2 or CuSO4 to the mix would affect the main reaction at all, as these could
possibly serve to pick up any water formed and prevent it from destroying the Ac2O. This would force the equilibrium to
decompose more carbonic acid but the water would be removed and the extra carbon dioxide formed, without the presence of
the water, would force the equilibrium of the main reaction towards the anhydride side
I really don't see an alcohol as an option for the solvent due to the esterification problem. I can't think of any other solvents
which would be suitable except for a couple of polar aprotics: DMF and DMSO, and they aren't exactly easily available.
Also, whilst I was thinking of closed systems and dissolved CO2, I thought that perhaps a Soda Stream fizzy drinks maker
could be used to add the CO2 to the solution. After all these are designed to dissolve the gas in liquid, rather than just pass it
though.
Finally, I sketched out a possible mechanism for the reaction of CO2 with AcOH to form Ac2O, it still needs transferring to the
computer, though I expect it's of limited interest to most members, and those who are interested are probably capable of
working it out for themselves anyway! It looked reasonable to me, despite the fact that I've never drawn a mechanism
detailing the formation of a carbonate anion before :)

Things are not going well so far I'm afraid. I've repeated my ketene experiment with the same acetic acid and there was not
the slightest increase in density, tested using a hydrometer accurate to 0.002 g/mL in the range of 1.0 to 1.1g/mL. I wonder if
the temperature is too high and all the ketene is decomposing, or perhaps the path after the reflux condenser to the bottle of
acetic acid is too long and the ketene is breaking down, (I think it's polypropylene or polyethylene tubing a foot or so long).
Something flammable (methane?) is definitely getting beyond the condenser as plenty of gas was burning off at the output.
I've also tried the proposed CO2 method, although I'm rather sceptical about it, I can't find any reference to it in patents or
web searches. Approx. 800mL of GAA was placed in a Soda Stream bottle with 200g of anhydrous MgSO4. CO2 was added
multiple times over a period of 2 hours, and the bottle was disconnected several times and gently shaken to mix the contents.
After about 2 hours the GAA began to freeze so it was clear that no transformation was taking place, at least not on a large
enough scale to alter the freezing point. After filtration, density had remained at 1.05g/mL. Perhaps (if this works at all), it
must be done with sodium acetate in aqueous solution. Maybe the formation of large amounts of carbonic acid is critical to the
reaction. I may attempt this at a later date. Nothing much wasted though as both the AcOH and MgSO4 were recovered.
I've kept most of the potassium hydrogen sulphate from nitric acid distillations as I thought it may be useful one day.
Conversion of this to the pyrosulphate is also on my to do list, though I've seen some interesting, however more complex
ways of making it on sciencemadness too.
I believe there is also a route involving acetaldehyde, which I have not looked into fully yet. I hope to make significant
quantities of acetaldehyde soon which should open up this experimental path.
nbk2000 May 15th, 2004, 05:26 PM

Anything madscientist says over at the sciencemadness forum must be taken with a bucket of salt, as his chemistry skills
are...how to say this politely...erm...LAME?!
Yes, indeed, very lame.
Sarevok May 15th, 2004, 05:47 PM

Instead of using ketene + acetic acid method, or acetic acid + phosphorus trichloride (PCl3) method, one can use POCl3 (I
already said how to make it, search - that method probably works) and sodium acetate (buy it or make it from vinegar and
lye) to make acetyl chloride (see A text-book of practical organic chemistry, on polverone's site), and then use acetyl chloride
and sodium acetate to make acetic anhydride (see the same book, or kv21's post). Only a distillation apparatus and some
simple stuff would be required.

Heh, speaking of buckets of salt, I made plenty of sodium acetate yesterday with the intention of using it for the CO2 and the
sodium pyrosulphate processes. If anyone else makes some, I recommend crushing it up and washing with acetone in a
Buchner funnel as this makes much of the sodium acetate into fine, dry sugar-like crystals which can be sieved out.
I've also done a few experiments in trying to make the pyrosulphate and temperature control is certainly an issue.
Fortunately, in the first bit of luck I've had this week, my hotplate set to max seems to produce the perfect temperature for
conversion of the potassium hydrogen sulphate to pyrosulphate without a great deal of decomposition. The hydrogen sulphate
melts and takes on a yellow appearance, and water begins to come off. I hope the same goes for the sodium hydrogen
sulphate as this is more readily available. Despite the potassium salt being a by-product, I don't make quite enough of it on a
regular basis to facilitate a decent scale of acetic anhydride production, should the whole process be a success.
Now that you mention it Sarevok, I remember my organic lecturers speaking of POCl3 or 'poccle three' as they said it. Vogel
looks a very interesting read, I've just skimmed through it so far, and I particularly like his ketene apparatus. Making and
using POCl3 for acetyl chloride, and then making acetic anhydride looks useful too, however the route is a rather long one in
comparison to the pyrosulphate one. Still, knowing how to make acetyl chloride from easy to obtain reagents is handy, so
thanks.
Sarevok May 16th, 2004, 07:29 PM

For those who are concerned, the sodium pyrosulphate method, mentioned by dave, is described here (http://
l2.espacenet.com/espacenet/bnsviewer?CY=gb&LG=en&DB=EPD&PN=GB424573&ID=GB++++424573A++I+).

I've just finished an experiment with potassium pyrosulphate. 130g of crude K2S2O7 was crushed into a fine powder and
mixed intimately with 60g of the fine sodium acetate I made the other day. Such a large molar excess of the pyrosulphate
was used as I am unsure of the actual percentage composition of the mix of sulphates, bound to have been formed.
The mixture, already beginning to cake due to moisture and perhaps some Ac2O formation, was placed in a round bottomed
flask and wetted with a small quantity of glacial acetic acid. This was refluxed for approximately 2 hours and the resulting
liquid was distilled with the recieving flask being a quick-fit separating funnel. 8 fractions of between 14mL and 25mL were
tapped off and rough calculations of density made using their volumes and masses, indicating densities of around 1.07g/mL.
The following fractions were combined such that the volumes were large enough to make the associated hydrometer readings:
3+4 - 1.068g/mL
5+6 - 1.066g/mL
7+8 - 1.062g/mL
Quite pleasing results for such a simple process. What is interesting is that the density actually decreases as the distillation
proceeds, the opposite of which would be expected, due to the lower bp. of the acetic acid. I wonder if any unconverted KHSO4
may have decomposed releasing water as the distillation proceeded and the temperature increased, thus lowering the density
of later fractions.
A simple oxidation of methylated spirits should provide a decent amount of acetic acid. NaOH and NaHSO4 being the other
reagents necessary, makes this process totally OTC as well as simple.
One can recycle the mix of acetic anhydride and acetic acid produced in the first run to wet the reagents in subsequent runs
gradually diluting the acetic acid in the newly forming acetic anhydride. Fractional distillation should also help to purify the
product, once a quantity worth processing is made, the acetic acid being recycled into sodium acetate.
Hinckleyforpresident October 8th, 2007, 06:23 PM

I read that it MIGHT be possible to make acetic anhydride with sulfuric acid and anhydrous magnesium sulfate. Has anybody
tried this? Or is this method completely wrong?

Do you mean using vinegar or glacial acetic acid as a starting base?
Because if all you have to work with is sulphuric acid and magnesium sulfate, no acetic acid (of any concentration), than you're
not going to get acetic anything out of that.

Sorry for the lack of information.
I meant distilling glacial acetic acid with sulfuric acid and anhydrous magnesium sulfate.
Here is the reaction: 2CH3COOH + H2SO4 + MgSO4 -> CH3(CO)O(CO)CH3 + H2SO4 + MgSO4.H2O
Enkidu October 9th, 2007, 12:50 AM

I couldn't tell you for sure whether or not it will work; that being said, I seriously doubt that you will have any success with that
method. Anhydrides are much more difficult to synthesize than ethers or esters, and, IIRC, no one has had much success
trying to dehydrate acetic acid to acetic anhydride.
Where did you see this process? A patent? A post somewhere else? Do tell.
Hinckleyforpresident October 9th, 2007, 12:58 AM

It's from sciencemadness. They also doubted it work well. I figured it's worth asking and maybe trying because if it did in fact
work then we would have OTC acetic anhydride.
nbk2000 October 9th, 2007, 01:28 AM

Sulphuric would carbonize the organic acetic molecule, making it non-acetic. ;)
The only reasonably effective way of making acetic anhydride is a ketene lamp.

Any hope of that generator drawing nbk?

Vogel has a rather descriptive diagram of the setup and explanation on page 373.
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv5p0679

I'm getting a 403 denial message when I click the link.

That method may work, but the yield would be dreadfully poor I would think. If that method was at all feasible, then the good
people at the Hive would have stocked up on salad dressing and epsom salts years ago.
EDIT:
The ? in the link is causing the redirector to throw fits. You can't copy and paste the link either... Copy and paste within the
code tags now.
I had it in code tags to start with, but it parsed as a link, but the code tags were still there when I went to edit it, and now it's
showing in code? :confused:
Anyways, it's working now.
tranquillity October 31st, 2007, 03:03 AM

From wikipedia and the reference: "Eastman Chemical Company Acetic Anhydride Process" Catalysis Today (1992), volume 13,
pp.73-91
***
Acetic anhydride is produced by carbonylation of methyl acetate:
C H 3 C O 2CH3 + CO (CH3CO)2O
This process involves the conversion of methyl acetate to methyl iodide and an acetate salt. Carbonylation of the methyl
iodide in turn affords acetyl iodide, which reacts with acetate salts or acetic acid to give the product. Rhodium and lithium
iodides are employed as catalysts. Because acetic anhydride is not stable in water, the conversion is conducted under
anhydrous conditions. In contrast, the Monsanto acetic acid synthesis, which also involves a rhodium catalyzed carbonylation of
methyl iodide, is at least partially aqueous.
***
I suppose there would be a substitute for the rhodium salt that is more easily accessible. Everything else is quite easy from a
decent lab setup.
The reactions as I see it:

CH3OH + CH3COOH + H2SO4 --> CH3COOCH3 + H2SO4.H2O
CH3COOCH3 + NaI --> CH3I + NaCOCH3 (CH3I Distills off at 42.43 C)
CH3I + CO --> CH3COI (I assume this is where the catalyst is needed)

Not too sure about the specific reaction conditions someone could fill in the blanks if they have the article.
CH3COI + NaCOCH3 --> NaI + (CH3CO)2O

and Improvised Chemistry > Chlorate, Perchlorate production cells -archive file
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PYRO500
Moderator
Posts: 1466
--------------------------------------------------------------------------------
I know production of a chlorate, or perchlorate has been covered and is on a faq that I downloaded. What I want to know is
details on the construction and your experiences you have had with your cells, basicly I want to know the details of your
chlorate/perchlorate cells like the annode,cathode materials effiency success rates production steps etc. the reason I am
asking is that I am thinking of setting a cell up and I want to get all the info available before attempting. I beleve I may be
able to produce this stuff by the 5 gallon paint jug full and I just want some input first. Thanks for any insight any of you may
provide
ALENGOSVIG1
Moderator
Posts: 766
--------------------------------------------------------------------------------
I have been wondering about this for awhile. You get small amounts of sodium chlorate which must be converted to potassium
chlorate but it would be incrediablly cheap to make and run. A small cell runs off of approximately 4.5 volts.
I will be making one of these this week hopefully and will tell you how it goes. Is the anode in a car battery lead dioxide? I
need to find lead dioxide for a good anode. I cant exactly affort a ingot of platinum or titanium.
It is some work getting it all set up but once you've got it running it will be a constant sourve of almost free chlorate or
perchloarate depending what you want.
kv21
A new voice
Posts: 6
From: Berlin
--------------------------------------------------------------------------------
quote:
--------------------------------------------------------------------------------
Originally posted by ALENGOSVIG1:
Is the anode in a car battery lead dioxide? I need to find lead dioxide for a good anode. I cant exactly affort a ingot of
platinum or titanium.
It is some work getting it all set up but once you've got it running it will be a constant sourve of almost free chlorate or
perchloarate depending what you want.
--------------------------------------------------------------------------------
The anodes in car battery's can't be used. It's plated on a lead plate and it's is very porous. The PbO2 will just release after
some time. <a href="http://huizen.dds.nl/~wfvisser" target="_blank">http://huizen.dds.nl/~wfvisser</a> describes the
construction of a PbO2 anode.
You'll be terribly disappointed if it comes to the mainenance of the cell. The connections with the anodes are very easily
broken, and you will notice all sorts of problems after some time. You also need a very powerfull transformer. At least 50
Amps. About 10 V for perchlorates and 5 V for chlorates.
The costs are about 11 USD / kg. But it is essential that your amperage is high, else it will take weeks to make a pound of
KClO3.
ALENGOSVIG1
Moderator
Posts: 766
--------------------------------------------------------------------------------
I can easily get all sorts of transformers for very cheap. pennies to be exact. Im definataly going to make one. Its just the
anode that is the problem. I dont want to use graphite because of its high corrosion rate. And the page you listed has been
down for a couple of days now. I have been told that manganese dioxide works well and it can be found in dry cell batteries. I
have opened dry cells before and sure enough, there was manganese dioxide. but it was a powder. And i am assuming it
needs to be pressed into a rod. I would think you would need a very well build press because the rod would have to stand up
to corrosion. Any ideas on anodes anyone?
------------------
Explosives Archive
vehemt
Frequent Poster
Posts: 580
From: Canada
--------------------------------------------------------------------------------
<a href="http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/chlorate.html" target="_blank">http://
www.geocities.com/CapeCanaveral/Campus/5361/chlorate/chlorate.html</a>
firebreether
Frequent Poster
Posts: 108
From:
--------------------------------------------------------------------------------
Where can you get transformers for that cheap?
PYRO500
Moderator
Posts: 1466
--------------------------------------------------------------------------------
oh come on! you can get transformers anywhere. I am thinking of rewinding the secondary of a microwave oven transformer to
get 12 volts (plus a current limiting circuit) I will probably get that chlorate to be made in a day! (mw transformers are rated at
2000 watts)
angelo
Frequent Poster
Posts: 279
From:
--------------------------------------------------------------------------------
then you can make KNO3 from the KClO3
------------------
angelo's place
have a good link? add it here
ALENGOSVIG1
Moderator
Posts: 766
--------------------------------------------------------------------------------
Why would you bother making kno3 when you can have powerful oxidisers such as chlorates and perchlorates?
------------------
Explosives Archive
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Preparing chlorates
Chapter 1: Introduction
Chapter 2: Electrolytic preparation
2.1 theory
2.2 cell construction
2.3 an example
2.4 cell volume
2.5 cell body materials
2.6 electrode materials
2.7 pH and temperature control
2.8 preparing the electrolyte
2.9 operating the cell
2.10 processing the electrolyte
Chapter 3: Thermal decomposition of hypochlorites
3.1 starting materials

3.2 method
3.3 purifying the product
Chapter 4: Literature
On an industrial scale, chlorates are prepared by electrolysis. Electrolysing a solution of a chloride at elevated temperatures
yields a chlorate. This method can be downscaled quite easily for amateur pyro purposes. Other methods of chlorate
manufacture exist that may be of interest for small scale use. They are usually less efficient but the economy of the process is
not
as important for amateur pyro purposes as it is for industrial setups. A second method for example consists of heating a
solution
of hypochlorite. Sodium and calcium hypochlorite are both quite easily available as bleach and pool chlorinating agent
respectively. Upon heating, the hypochlorite will decompose into both chloride and chlorate. The chlorate is separated and
purified. Although slow and laborous, the method is simple and requires very little equipment. In the past chlorates were
produced even on an industrial scale by bubbling chlorine gas through a hot hydroxide solution. This process is not very well
suited for amateurs since chlorine gas is very dangerous to handle. The process is also extremely inneficient, for which reason
it
was abondoned quite soon after the electrochemical method became feasible at industrial scale.
The electrolysis is carried out in a diaphragmless cell, containing a solution of a chloride. Several chlorides may be used, but
the
use of sodium chloride has many advantages. Sodium chlorate is easily converted to a number of other chlorates by
metathesis
reactions. The most commonly used chlorates in pyrotechnics, potassium and barium chlorate, can both be made in this
manner. Potassium chloride and barium chloride may also be used to obtain the respective chlorates directly, but this has
many
disadvantages as will be discussed below. Only sodium chlorate can be used in the manufacture of perchlorates, due to its
high
solubility.
Ammonium chloride should never be used, and should in fact not even be present in the cells in trace amounts. It could result
in
the formation of two dangerously sensitive and explosive compounds, nitrogen trichloride (NCl3) and ammonium chlorate
(NH4ClO3). The formation of both of these compounds should be avoided at all times. Not only can they explode by
themselves when present in significant quantities, they can also lead to spontaneous ignition of pyrotechnic mixtures
contaminated with even small amounts.
2.1 theory
Mechanism of chlorate formation
The reactions taking place in chlorate cells are not fully understood even today. A summarised description of the process will
be given here, and the interested reader is referred to the literature listed below for a more extensive description.
The theory of Foerster and Mueller regarding the reactions in chlorate cells, developed about 80 years ago, is the most
accepted. The following reactions are said to take place at the electrodes:
At the anode:
2Cl- Cl2(aq) + 2 electrons
At the cathode:
2H2O + 2 electrons H2 + 2OH-
The dissolved chlorine gas can then react with water to give hypochlorous acid:
Cl2(aq) + H2O HClO + H+ + Cl-
From this reaction it can be seen that if the chlorine does not dissolve but escapes to the atmosphere, no H+ will be generated
to neutralise the OH- formed at the cathode and the pH of the electrolyte will increase.
The hypochlorous acid thus formed will react in acid-base equilibrium reactions with water to give hypochlorite ions and
chlorine gas (dissolved). The exact concentrations of dissolved Cl2, ClO- and HClO depend on the pH, temperature and
pressure among other things. In the solution, chlorate will be formed (mainly) by the following reactions:
2HClO + ClO- ClO3- + H+ + 2Cl-
and
2HClO + ClO- +2OH- ClO3- + 2Cl- + H2O
These reactions take place at a rather slow rate. Since this reaction pathway is the most effient one as we will shortly come to
see, the conditions in the cell are usually optimised to increase their reaction rate. The pH is kept within a range where HClO
and ClO- are simultaneously at their maximum concentration (which is at around pH=6). The temperature is kept between 60
and 80 degrees centigrade, which is a good compromise between the temperatures required for a high reaction rate, low
anode
and cell body corrosion and high chlorine solubility (remember the chlorine evolved at the anode has to dissolve in the
solution
to start with). Many cells also have a large storage tank for electrolyte in which the electrolyte is kept for a while to give these
reactions some time to take place.
Alternatively, chlorate may also be formed by oxidation of hypochlorite at the anode as follows:
6HClO + 3 H2O 3/2 O2 + 4Cl- + 2ClO3- + 12H+ + 6 electrons
Oxygen is evolved in this reaction, which means a loss of current efficiency (the energy used for oxidising the oxygen in water
to
the free element is lost when the oxygen escapes to the atmosphere). When the reaction routes are worked out, it turns out
that
following this path 9 faradays of charge are required to produce 1 mole of chlorate, whereas only 6 faradays are required to do
that following the route mentioned earlier. Therefore, optimising the conditions for that route improves current efficiency.
To prevent the products from being reduced at the cathode again, a membrane around the cathode was employed in the past.
Finally, it should be mentioned that the reactions forming perchlorates do not take place untill the chloride concentration has
dropped to below about 10%. Therefore, cells can be constructed and operated in such a way that chlorate is produced almost
exclusively. The chlorate can then be purified and fed into a perchlorate cell. Depending on the type of anodes used in the
chlorate cell, the purification step may also be skipped and the electrolysis continued untill all chloride has been converted into
perchlorate. Although slightly less efficient (and therefore not used a lot in industrial setups), this is much less laborous and
therefore probably the prefered method for home setups.
Cell voltage
The current through a cell is related to the reaction rate. Therefore, to obtain a constant reaction rate that suits the cell design,
a
constant current is usually employed. The voltage over the cell will then fluctuate depending on conditions and cell design. The
power consumed by the cell is the product of current and voltage, according to equation P = I * V. From that it can be seen
that reducing the voltage over the cell results in a lower power consumption, an important fact for industrial operations. The
factors influencing the cell voltage have been thoroughly investigated. Most important are the anode - cathode spacing, the
concentration of the electrolyte, the surface area and materials of the electrodes the temperature and the pH. Without going
into
details, the cell voltage usually lies in the range 3.5 - 4.5 volts. Of this, approximately 3 volts are required to get the
oxidation of
chloride to chlorate to take place (and the hydrogen reduction at the cathode), while the rest is used to overcome the
resistance
of the cell, according to Ohm's law V=I*R. From this law it can be seen that there are two ways to maintain a constant current
through a cell: either the voltage over it may be varied or its resistance may be changed. Adjusting the voltage over a cell to
maintain a constant current can be done manually or with an electronic circuit. If the power supply does not allow voltage
adjustment (such as old PC power supplies or battery chargers for example) or the required electronics are not available,
adjusting the resistance of the cell is another option. This could in principle be done by adjusting each of the factors
mentioned
earlier, the most practical of which is probably the anode-cathode distance. By increasing the distance between the electrodes
the resistance of the cell is increased, which reduces the current through the cell. One thing to keep in mind when doing this is
that it with decresing resistance, the heat generated in the cell is increased. Depending on the anode material used it may
then be
necessary to cool the cell to prevent excessive erosion, more on that later.
2.2 Cell construction
Cells can range in complexity from a glass jar with a nail and a old battery electrode to well designed, corrosion resistant cells
with thermostats, pH control, circulating electrolyte and coulometers. Even the simplest of cells will work, but it will require
more maintanance. If the chlorates are going to be prepared on a more or less regular basis, it probably pays to spend some
more time designing a cell. It will also improve efficiency somewhat, but unlike in industrial setups where high efficiency is
mandatory to be able to compete, the home experimenter can do with less efficient cells. The two main disadvantages of a
low
efficiency is that it takes more time for the conversion to complete, and that more electricity is required. To give some
indication
of the power consumption of the process: typical figures for industrial cells lie in the range 4.5 to 5.5 kWh per kg of sodium
chlorate.
In this section some of the things to consider when building and designing chlorate cells will be discussed. The reader can
design
his own cell based on the information given. An example of a cell, the small test cell I currently use to experiment with, has
been
given but it is by no means perfect, and it is probably better to design your own. The example has merely been given to
illustrate
some principles.
2.3 An example
The example given here consists of a small cell, of 200 ml electrolyte volume. The cell is normally operated with
graphite or graphite substrate lead dioxide anodes. Platinum sheet has also been tried with, unsurprisingly, good
success. The electrolyte consists of sodium chloride with either some potassium dichromate or potassium fluoride
added, depending on wheter graphite or lead dioxide anodes are used. The cathode consists of a stainless steel wire spiraling
down. The wire is corroded where it is not submerged, so it has to be replaced occasionally. The connections to the anode and
cathode are made outside the cell but do corrode from the gasses and electrolyte mist. This is partially prevented by leading
the
gasses away from the connections with a vent tube, as shown in the picture. Covering the connections with hot melt glue also
helps, but the heat generated in a faulty connection may cause the hotmelt to melt.. The temperature is controlled by placing
the
cell in a water bath, which acts as a heat sink. If the temperature is too low, styrofoam isolation is provided. The cell is
operated outside, causing the temperature to fluctuate between day and night. The pH is checked about twice a day and
adjusted if necessary with hydrochloric acid. The power source used is an old computer power supply. The output voltage can
be regulated within certain limits and this is done to maintain a current of about 4 amperes. An other model computer power
supply was used previously that did not allow control over the output voltage. Current adjustment was done by widening or
narrowing the cathode spiral, effectively reducing or increasing the anode-cathode distance.
Theoratically, if 100% efficiency could be reached, the cell would have the capacity to convert approximately 35 grams of
sodium chloride to 64 grams of sodium chlorate per day. Using a methatesis reaction with potassium chloride this would yield
74g of potassium chlorate. In practice the average yield is about 40 grams of potassium chlorate a day from which an
efficiency
of 55% can be calculated.
2.4 Cell volume
This is the main factor affecting a cells capacity, provided the power supply can provide the necessary current. As a rule of
thumb no more than 2 amperes per 100 ml of electrolyte must be passed through a chlorate cell. Under more optimal
conditions a higher amperage may be tolarable, still maintaining reasonable efficiency whereas in less optimal conditions 2
amperes may be too high and a lot of chlorine will be lost, leading to lower efficiency and rising pH. A current of 2 amperes will
convert approximately 0.73 gram of sodium chloride to 1.32g of sodium chlorate per hour (assuming 100% efficiency). After
extracting, metathesis reactions and recrystallising that will yield 1.53 g potassium chlorate. So, for example, to produce 100
grams of potassium chlorate a day at least 100 grams / 1.53 grams / 24 hours * 100 ml = 272 ml of electrolyte are required.
To maintain that rate of conversion the cell will then require 272 ml / 100 ml * 2 amperes = 5.44 amperes. If a cell is less
efficient than 100%, which every cell is, increase these figures proportionally (so at 50% efficiency: 100% / 50 % * 272 ml =
544 ml of electrolyte, consuming 10.88 amperes of current to maintain the same rate of production). The example cell
described above contains 200 ml of electrolyte. Thus, it should be operated at a current of 4 amperes, and the maximum
daily
yield is 100/272 * 200 = 74 g of potassium chlorate after processing the electrolyte. These figures were also mentioned in the
cell description without explanation.
2.5 Cell body materials
One of the main problems in chlorate cells is the corrosiveness of the electrolyte. Only very few materials do not corrode when
in contact with the electrolyte or its fumes. Most metals corrode, many plastics will and even glass does under some
circumstances.
Some metals, such as steel, can be used if they are protected from corrosion in some way. For that purpose it can be coated
with a resistant material such as teflon or some types of rubber, or it can be 'cathodically protected'. This means means the
cell
walls are used as a cathode. The negative potential prevents the steel from being oxidised if the current density (current per
unit
of surface area) on the steel is high enough.
Some metals, particularly titanium, zirconium, tantalum and niobium, form a protective film when they are in contact with the
electrolyte. This prevents them from further corrosion, and they therefore find extensive use in industrial setups (particularly
titanium). For amateurs the difficulties in working with these metals and their high price restricts their use somewhat. In small
scale setups glass and plastics such as PVC are more easily available, easier to work with and much cheaper.
The table below gives some idea of how well a number of materials stand up to corrosion. The column 'protected' lists how
well metals resist corrosion when cathodically protected. The column 'unprotected' lists materials used as is.
material
corrosion resistance
when unprotected
corrosion resistance
when cathodically protected
Iron
--
+
Stainless steel
-
+
Titanium
++
++
Copper
--
++
Brass
--
+
Tantalum
++
++
Platinum
++
++
Aluminum
--
+-
PET
++
X
Poly ethylene
+
X
Poly propylene
+
X
PVC
++
X
Rubber
+-
X
Hot melt glue
+-
X
Styrene
-
X
Graphite
+
+
Silicone rubber
--
X
Concrete
+
X
Glass
++
X
Ceramics
++
X
Wood
--
X
Polyester
-
X
2.6 Electrode materials
The range of suitable electrode materials is very limited. Especially the anode material is critical. The positive charge on the
anode promotes oxidition and the evolving oxygen attacks many anode materials. Several anode materials have been
considered over the years. Todays main options are listed below along with a short description.
Anode materials
Graphite: graphite is cheap and easy to obtain. It does however corrode at a comparatively fast rate. This makes it necessary
to replace the anodes every so often and to filter the electrolyte before further processing which can be difficult and laborous
due to the small size of the carbon particles. Graphite is not suitable for making perchlorates. When the chloride concentration
of the electrolyte drops to the point where perchlorate formation begins (about 10% w/v), the graphite begins to oxidise at a
great rate, yielding no or only traces of perchlorate. Cells operating with graphite anodes must also be maintained at a relative
low temperature to limit anode erosion, which translates to a lower cell capacity. Graphite rods can be found in old manganese
dioxide-zinc batteries or in welding shops where they are sold as 'gouging rods'. They can be treated with linseed oil to reduce
corrosion. A practical method for the home experimenter has been devised by Rich Weaver, and is well described on Mike
Brown's page. Old battery electrodes do not need to be treated with linseed oil.
Platinum: The obvious disadvantage of platinum is its high price. However, platinum anodes corrode only at a very slow rate
and are suitable for perchlorate production. They therefore provide an almost ideal anode material. High efficiency can be
reached with platinum and processing of the electrolyte is greatly simplified.
Lead dioxide: Lead dioxide provides an economical alternative to platinum. Lead dioxide anodes can be made at home. This
takes some work and effort, but the anodes are cheap, fairly resistant to corrosion even at higher temperatures and are
suitable
for perchlorate production. More information on lead dioxide electrodes is given elsewhere on this homepage.
Manganese dioxide: Another oxide that is conductive and resistant to oxidation. It is made by thermal decomposition of
manganese nitrate pasted onto a substrate. This type of anode seems quite promising for amateur pyro use. For more
information, the user is referenced to patents in the literature list below. If anyone has experiences with these anodes and
their
preparation I'd be most interested to hear about them.
DSA: DSA stands for Dimensionally Stable Anode. This is the common term used to refer to anodes consisting of a layer of
noble metal oxides (usually RuO2 and TiO2) coated onto a substrate, usually titanium. This type of anode is finding increased
use in industrial cells because of its comparatively low cost when compared to platinum and its resistance to corrosion. Some
of
the chemicals required to manufacture these anodes (particularly RuCl3 and tetra-butyl titanate, Ti(OBu)4) are expensive and
perhaps difficult to handle safely. However, if the chemicals can be obtained and suitable equipment is available, the
procedure
to make the anode seems fairly straightforward and may be an option. For the preparation of these, the reader is referenced
to
the literature. Again, I'd be most interested in anyones experiences with this type of anode.
Magnetite: This has found use in industry in the past, but is rarely used nowadays. It corrodes, but not very quickly and it can
be used for perchlorate manufacture. The anodes are made by melting and casting FeO.Fe2O3 into the required anode
shapes.
I have little literature available on this material, so it is not further discussed here.
Cathode materials
Both stainless and mild steel find widespread use as cathode materials. Brass and copper may also be used. Each of these
metals is protected to a certain extent by the negative charge present on the cathode as long as they are submerged and the
current per surface area is high enough. Unsubmerged parts of the cathode corrode at a high rate however due to the action of
evolving gasses and droplets of cell electrolyte.
It seems that under some conditions the chromium in stainless steel can dissolve, even though the cathode does not seem to
corrode. A yellow electrolyte is the result from which barium chromate can be precipitated even if no chromate was added,
which will be described later (see processing the electrolyte). The presence of chromates could lower the efficiency of cells
employing lead dioxide anodes.
Finally, contamination of the final product with copper (from brass or copper erosion products) can be dangerous when the
product is to be used in pyrotechnic purposes. Although this is unlikely to be a great problem since the impurities are usually
removed easily and completely by filtration (as will be described later) it is good to be aware of the possibility.
2.7 pH and temperature control
Although not essential for chlorate manufacture, controlling the temperature and pH will increase cell efficiency and therefore
the capacity of a cell. Temperature control can be anything from a sophisticated thermostat and heating element (or a cooling
element) to simple insulation around the cell or a cold water bath. As mentioned earlier, part of the electric energy is lost as
heat
in the cell. Small cells operating at high currents can sometimes reach temperatures of 80 to 90 deg C. Though high
temperatures will improve efficiency, temperatures as high as that will also increase anode corrosion and it is therefore usually
considered better to maintain a temperature in the range 60 to 80 deg C to get the best of both worlds. Graphite anodes tend
to erode faster than other types though, especially at higher temperatures, and cells employing these are therefore usually
operated at 40 deg C to limit anode erosion.
Like temperature control, pH control is not essential for chlorate manufacture. Efficiency is improved greatly however if the pH
is kept within the range 5.5 - 6.5 (slightly acidic) as explained in the theory section. Graphite anodes also tend to erode faster
at
high pH, so maintaining the pH will extend graphite anode life. In commercial setups pH control is done manually by periodic
additions of hydrochloric acid. Automated pH control seems to be difficult and expensive to realise. If anyone devices a
practical method of doing this, I'd be interested to hear about it.
2.8 Preparing the electrolyte
When just starting a first batch of chlorate a fresh electrolyte has to be prepared. When the cell has been operated before, the
electrolyte from the previous cell is available to prepare the electrolyte for a new batch. Also, the material left behind from the
extraction and purification steps can be added to the next cell as it may contain some residual chlorate. That way no product
left in the solution after procesing is lost.
As mentioned, it is common to use sodium chloride to prepare sodium chlorate first, which is then converted to potasisum or
barium chlorate later. Even though both compounds may be prepared directly from potassium or barium chloride, using
sodium
chloride as a starting material has advantages. Mainly, it makes processing of the electrolyte much easier since sodium
chlorate
is very soluble. It is therefore easily separated from insoluble impurities which are almost always present. It will be assumed
that
sodium chloride is used. If for some reason the use of other compounds is desired, the procedure and amounts may need to
be
adjusted.
Preparing fresh electrolyte
1. Prepare a saturated solution of sodium chloride. Take about 40 grams for every 100 ml of solution and bring the solution to
a boil. Then allow to cool to room temperature again. Some sodium chloride will crystalise as the solution cools. The solution is
then filtered to obtain a clear saturated solution.
2. Optionally, 2 to 4 g/l of potassium dichromate, potassium chromate, sodium chromate or sodium dichromate may be
added
to improve efficiency. These compounds are suspected carcinogens, so if you choose to add any, know the hazards involved
and act accordingly. If lead dioxide anodes are used, do not add potassium dichromate as it will only reduce efficiency.
Instead,
2 to 4 g/l of sodium or potassium fluoride may be used. Although not carcinogenic, the fluorides are nasty compounds as well
and should be handled properly.
3. Finally, the pH of the solution can be adjusted. A pH of around 6 is optimal, but anything between 5.5 and 6.5 is
reasonable.
The pH can be increased by addition of sodium hydroxide solution and it can be decreased by adding hydrochloric acid. Do
not use too concentrated solutions for adjusting the pH. A concentration of 2% (w/v) for both solutions is convenient to work
with.
Recycling old electrolyte
When electrolyte from a previous batch of chlorate is available the following steps can be used to recycle the electrolyte.
1. If the electrolyte is not clear but has solid particles in it, filter to remove these. See the section on filtering below.
2. dissolve any impure chlorate from the purification and extraction steps.
3. Now, re-saturate the solution with sodium chloride. The procedure mentioned above in step 1 of 'preparing a fresh
electrolyte' may be used.
4. The chromate, dichromate or fluoride if added is still present so does not need to be replenished. The pH should be
readjusted, like in step 3 for preparing a fresh solution above.
2.9 Operating the cell
Voltage and current
As explained in the theory section the voltage over the cell may vary. The current should be kept more or less constant at a
value determined by the cell design. As a rule of thumb, supply 2 amperes of current per 100 ml of electrolyte. If graphite
anodes are used it is better to supply less current since that will increase anode life (30 mA per square centimere of anode
surface area is typical). A constant current supply is ofcourse the most convenient to use for regulating current, but manually
adjusting the voltage from time to time also works well. The current usually only changes very gradually, and the precise value
is
not very critical. In any case, measure the current at regular intervals and record them. That information is required to
determine
when a batch is complete, as described below in the paragraph 'running times'.
Maintaining optimal conditions
As explained, the pH of the electrolyte will tend to rise. Also, some of the water will evaporate and some will be consumed in
the reaction. The temperature may also vary with ambient temperatures. For good efficiency these variables must be kept
within
certain limits.
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Every once in a while, make up for evaporated and consumed water. This can be done with water, but it is better to use a
saturated sodium or potassium chloride solution. That way, the chloride concentration will be kept at a higher level which
improves efficiency. It will also prevent excessive formation of perchlorate, and in graphite anode based cells it reduces anode
wear.
The pH will rise during operation of the cell, and it is best to lower the pH regularly to a value of about 6. A high pH value is
best corrected by adding hydrochloric acid occasionally. If too much HCl is added, it may be corrected with sodium hydroxide
solution. The pH is self correcting to a certain extend as well, since at very low pH the cell will produce more chlorine gas. This
will then escape, raising the pH again. Measuring the pH of the solution can be done with common pH paper. However, if the
paper is simply dipped directly into the electrolyte the hypochlorite present will usually bleach the paper making a
measurement
impossible. This problem can be overcome by boiling a sample of the solution for 5 minutes and measuring the pH of that.
The
boiling destroys the hypochlorite.
The temperature will usually reach a more or less constant value quickly. If the cell is placed outside, the temperature may
vary
between night and day and between seasons ofcourse, so then some sort of control may be necessary to maintain the
optimum.
Usually, cooling is necessary but it will depend on the specific cell design as explained in the theory section.
Running times
The time required to convert a certain amount of chloride to chlorate depends on the current and the efficiency. The latter can
vary dramatically from cell to cell and it is therefore not possible to state precise running times. It is however possible to
calculate the required running times for a hypothetical cell operating with 100% current efficiency. The calculation will show that
the conversion of one mole of chloride to chlorate requires 160.8 amperage hours. So, for example, a cell containing 100
grams of sodium chloride will require 100/58.6 * 160.8 = 274.4 Ah if it operates at 100% efficiency. For a current effiency
other than 100%, increase the running times in proportion (to convert 100g of NaCl with 80% current efficiency one needs
274.4/80*100 = 343 Ah). So, if a current of 3 amperes flows through the cell, it requires 274.4 / 3 = 91.47 hours (91 hours,
28 minutes) to finish.
2.10 Processing the electrolyte
When done, the product must be extracted from the electrolyte and the electrolyte can be recycled for the next batch (see
preparing the electrolyte).
Filtering
The electrolyte usually contains suspended solid particles, even though they are not always visible. Suspended particles can be
detected with the use of the Tyndall effect. Shine a bright flashlight through the side of a glass container containing the
solution.
If no suspended particles are present the light beam cannot be seen going through the solution. If suspended particles are
present they will scatter the light and make the beam visible.
Usually, the impurities consist of erosion products of the anodes, the cell walls, and the unsubmerged parts of the cathodes.
These particles may be very small and are not always easily removed with common filtering paper. Filtering through a layer of
diatomeous earth (sold in shops for aquarium supplies) in a filter or on a piece of cloth sometimes solves the problem.
Another
great idea for a filter comes from E.S. However, just filtering will not always remove all solid impurities. A common impurity
that is hard to remove is suspended iron hydroxide, originating from corrosion of (stainless) steel cathodes. The fluffy,
voluminous form of the material often gives it a white or yellowish foggy appearance. This is next to impossible to remove
unless
some sodium hydroxide or pool coagulant is added first. This causes the iron hydroxide particles to coagulate, making them
easy to remove by filtration. Another possibility is to add hydrochloric acid to lower the pH to between 2 and 3. This will
dissolve the iron hydroxide. If sodium hydroxide is then added to raise the pH to above 7 again, the iron hydroxide is
precipitated in a more dense form which is easily removed by filtration, even with common filter paper.
In this step, the advantages of using sodium chloride will become evident. When potassium chloride is used instead
potassium
chlorate crystallises during operation of the cell due to its relatively low solubility. To separate the potassium chlorate from
insoluble impurities the electrolyte has to be filtered hot. The solution usually takes quite a long time to pass through the
filter
and if it cools during this time, potassium chlorate will crystallise and block the filter. Alternative methods have been
developed
to separate potassium chlorate from insoluble impurities. For example, the solution may be boiled and sufficient water added
to
dissolve all potassium chlorate. If the solution is then allowed to cool slowly, crystals of potassium chlorate will form on the
suspended insoluble impurites. These will sink to the bottom, usually leaving a clear solution. The clear solution is then
carefully
decanted and allowed to cool further . This method will not remove the insoluble purities as well as filtering will but it is much
less laborous.
Destruction of hypochlorite
Next, the electrolyte is boiled to decompose remaining hypochlorite. 15 minutes of vigorous boiling is sufficient. After that, the
pH of the solution is checked and it is made slightly alcaline by adding sodium hydroxide solution. Bring the pH to between 8
and 9.
Metathesis reaction
At this point, a clear solution of sodium chlorate (with residual chloride) has been obtained. This can be used either to prepare
potassium or barium chlorate (or other chlorates which are not further elaborated upon here), or it can be used to prepare
perchlorates, described elsewhere.
Potassium chlorate is by far the most commonly used chlorate in pyrotechnics. For practical purposes, the preparation of this
compound is discussed here. For the preparation of barium chlorate the amounts will have to be adjusted.
1. Weigh out either 127g of potassium chloride or 355g barium chloride for every 100 g of sodium chloride that was started
with, depending on wheter you want to prepare potassium or barium chlorate. Dissolve this in as little water as possible
(dissolve in minimum amount of boiling hot water, add a bit more water and allow to cool. Nothing should precipitate. If it
does, add some more water and heat again)
2. Add this solution to the electrolyte. A white precipitate of potassium or barium chlorate should form.
3. Bring the solution to a boil. Add 20 ml amounts of water to the solution in 5 minute intervals untill all chlorate has
dissolved.
If all chlorate dissolves upon heating without the addition of extra water, allow the water to evaporate untill a thin crust of
chlorate forms on the surface (indicating that the saturation point has been reached). Then add 20 ml of water and boil for a
minute to redissolve the crust.
4. Allow the solution to cool to room temperature. Potassium or barium chlorate will crystallise. If it has cooled to room
temperature, cool further to 0 deg C.
5. Filter to obtain the crude chlorate crystals. Rinse them thoroughly with ice-cold water. The filtrate can be saved to prepare
the next electrolyte, as is described in the section on recycling electrolyte.
2.11 Purifying the product
The crude product can be purified by recrystallisation. The low solubility of potassium chlorate makes this method very
convenient to use and will greatly improve the purity with a relatively small loss of product. Barium chlorate is somewhat more
soluble and to prevent losses it is a good idea to use the impure barium chlorate 'waste' from this procedure in the electrolyte
of
a new cell. Some treatment is necessary, which was described earlier. If a single recrystallisation step does not yield a
sufficiently pure product, the method can be repeated to further increase the purity. Usually one or two recrystallisations will
yield a product that does not impart the characteristic yellow color of sodium impurities to a flame.
1. Place the crude product in a pan and add 100 ml of water for every 35g of crude potassium chlorate or 50g of barium
chlorate. Bring this to a boil.
2. Add 20 ml amounts of water to the boiling solution untill all the chlorate has dissolved.
3. Check the pH of the boiling solution. It should be neutral or slightly alcaline. If it is acidic, add potassium hydroxide
solution
untill it is slightly alcaline (pH 7..8) again. If this is not done, traces of acid may be included in the product making it very
dangerous to use in pyrotechnic compositions.
4. Allow the solution to cool to room temperature. The chlorate will crystalise.
5. Filter and rinse the crystals in the filter well with ice cold water. The filtrate may be used to prepare the electrolyte for a new
cell, as was described in the section on recycling old electrolyte.
6. The crystals may be dried in an oven at 100 deg C.
Thermal decomposition of hypochlorites
This is an alternative method of chlorate manufacture. It is more laborous than the electrolytic method, and can only be used
for
small batches at a time. The starting materials are quite easily available however as bleach and pool chlorinating agents and
it
only requires the use of simple tools.
3.1 Starting materials
Possible starting materials are sodium hypochlorite and calcium hypochlorite. The former is available in solution as bleach and
antifungal spray for bathrooms. Calcium hypochlorite finds use as a chlorinating agent for pools. However, different varieties
exist. Carefully read the package to make sure you have the right material. It usually states a '85% available chlorine' content
for calcium hypochlorite. A higher available chlorine content may mean it is something else, most likely trichlorohydrocyanuric
acid.
3.2 Method
Depending on the starting material, sodium or calcium hypochlorite, a different procedure must be followed. Each is described
separately below.
Procedure when using sodium hypochlorite
It is assumed bleach will be used, which is usually a 4% solution of sodium hypochlorite in water. If a less or more
concentrated
solution is used, adjust the amounts accordingly.
1. Take 1 liter of bleach, and place this in heat resistant glass or stainless steel container. Bring it to a boil.
2. Boil the solution untill only about 140 ml of solution is left. The exact volume is not critical, a deviation of 10 to 20 ml is
acceptable.
3. Allow the solution to cool. If crystals form upon cooling, filter the solution after it has completely cooled. The crystals are
sodium chloride and can be discarded.
4. In a separate container, prepare a solution of potassium chloride. Dissolve 28 grams of potassium chloride in the smallest
volume of water possible (about 80 ml). This can be done by dissolving the potassium chloride in about 90 ml of boiling water,
and allowing it to cool. If crystals form, add some more water, boil again to dissolve the potassium chloride, and allow to cool
again. If crystals form, repeat. If not, the solution is ready to use.
5. Mix the boiled bleach solution with the potassium chloride solution. A white precipitate should form. This is potassium
chlorate.
6. Bring the solution to a boil and add water untill all potassium chlorate has dissolved.
7. Allow the solution to cool slowly. Crystals of potassium chlorate will form. Cool the solution to 0 deg C.
8. Filter to obtain the raw potassium chlorate. Rinse the crystals in the filter with ice-cold water. The product can be further
purified as described below.
Procedure when using calcium hypochlorite
warning: On one occasion an small explosion occured when I was doing this preparation. I am not sure exactly what caused
the explosion. It seems to have been a steam explosion. I was also not sure wheter I was using calcium hypochlorite or
trichlorohydrocyanuric acid, another common pool chlorinating agent. It seems to be very uncommon that explosions happen
and they can probably be prevented by vigorous stirring, but I thought everyone attempting this method should know so
proper
precautions can be taken. The procedure below has been optimised to reduce the chances of an explosion happening.
1. Place 250 ml of water in a heat resistant glass or stainless steel container, large enough to hold twice that volume.
2. Bring the water to a boil.
3. To the boiling water, add 125 gram of calcium hypochlorite in 10 gram portions. The calcium hypochlorite usually comes in
tablets, which need to be crushed first. Stir vigorously during this step, occasionally scraping over the bottom to prevent the
formation of a cake of calcium chloride. The solution will foam a lot. If too much foam is developed, do not add any more
calcium hypochlorite and boil untill the foam subsides. Then continue adding calcium hypochlorite.
4. When all calcium hypochlorite has been added, continue boiling untill no more foaming is observed. Stir continuously.
5. Allow the solution to cool down, and filter to remove the precipitated calcium chloride.
6. In a separate container, dissolve 68 grams of potassium chloride in the smallest volume of water possible (approximately
195
ml). This can be done by dissolving the potassium chloride in about 200 ml of water, and allowing it to cool. If crystals form,
add some more water, boil again to dissolve the potassium chloride, and allow to cool again. If crystals form, repeat. If not,
the
solution is ready to use.
7. Mix this solution with the boiled calcium hypochlorite solution. A white precipitate of potassium chlorate should form.
8. Bring the solution to a boil and add water untill all potassium chlorate has dissolved.
9. Allow the solution to cool slowly. Crystals of potassium chlorate will form. Cool to 0 deg C.
10. Filter to obtain the raw potassium chlorate. Rinse the crystals in the filter with ice-cold water. The product can be further
purified as described below.
3.3 Purifying the product
The product can be purified by recrystallisation, just like the product of the electrolytic procedure. For convenience, the same
procedure is given again here:
1. Place the crude product in a pan and add 100 ml of water for every 20 g of crude product. Bring this to a boil.
2. Add 20 ml amounts of water to the boiling solution untill all the potassium chlorate has dissolved.
solution
untill it is slightly alcaline (pH 7..8) again. If this is not done, traces of acid may be included in the product making it very
dangerous to use in pyrotechnic compositions.
4. Allow the solution to cool to room temperature. Potassium chlorate will crystalise.
5. Filter and rinse the crystals well with ice cold water. The filtrate may be discarded or concentrated by evaporation and the
residue added to the electrolyte for a next batch.
The amount of literature available is overwhelming. A short list of interesting reading material follows.
1. F Hine, "Electrode processes and electrochemical engineering", Plenum Press, New York (1985)
2. F. Foerster and E. Muller, Z. Elektrochem, 8, 8, 515, 633, 923 (1902); 9 171 (1903); 10, 781 (1904).
3. Webpage of Mike Brown
This list is under construction
Copyright Wouter Visser, May 1999.

Back to main page
Mr Cool
Frequent Poster
Posts: 991
--------------------------------------------------------------------------------
Preparing perchlorates
2.1 2.1 cell construction

2.2 2.2 electrode materials
2.3 2.3 preparing the electrolyte
2.4 2.4 operating the cell
2.5 2.5 Processing the electrolyte
2.6 2.6 Purification
Chapter 3: Preparation by thermal decomposition of chlorate

Chapter 4: Preparation by chemical oxidation
Industrially, perchlorates are exclusively prepared by the electrochemical method. In the past, thermal decomposition of
chlorate has been used but since this process is very inefficient it has been abandoned long ago. Chemical oxidation of
chlorates
is currently not very economical either, but it may become an option in the future. For amateur pyros, each of these methods
may be used as we need not be concerned with the economy of the process as much as commercial operations do. The
electrochemical method is convenient to use if you have a chlorate cell with the right anodes already, since then making
perchlorates is simply a matter of operating the cell for a bit longer. If you can get chlorates in quantity for cheap, for example
as a herbicide, the thermal decomposition method is an option. The method is quick, and requires no chemicals other than
the
chlorate starting material. Perchlorates can also be prepared by chemical oxidation of chlorates. The required chemicals are
relatively expensive, but the method is quick and simple.
Chlorates can be oxidised in an electrochemical cell to yield perchlorates. The prefered starting material for this method is
sodium chlorate, since it is very soluble. Potassium chlorate is seldom used due to its low solubility, and ammonium chlorate
should never be used since it leads to the formation of sensitive and explosive NCl3 in the cell. Sodium perchlorate is
conveniently converted in high yield to a number of other perchlorates (such as potassium and ammonium perchlorate) by
double decomposition (metathesis) reactions. It is assumed from here on that sodium chlorate is used as starting material.
Cell construction
Electrochemical cells for perchlorate synthesis do not differ much from chlorate cells. The most important difference lies in the
anode material. Not all anode materials suitable for chlorate synthesis can also be used for perchlorate synthesis. Most cell
body materials used in chlorate cells may also be used in perchlorate cells. The effect of temperature and pH deviating from
the
optimal values is of much less importance in perchlorate cells. Finally, the voltage at which perchlorate cells operate is
somewhat higher because the potential at which the conversion reactions take place is higher. The general structure of both
cell
types is the same: two working electrodes, and no diaphragm.
Electrode materials
Like in chlorate cells, stainless steel is a suitable cathode material. Mild steel may also be used. While copper and brass will
also work, they may cause problems with copper contamination when they erode.
Anode materials for perchlorate cells should have a high oxygen overpotential. What exactly that means is not further
discussed
here; it suffices to say that if the oxygen overpotential at a certain anode material is not high enough oxygen will be evolved
instead of chlorate oxidised to perchlorate. No perchlorate will be formed, and the anode material is usually attacked
comparatively quickly. This holds also for chlorate cells, but the problem is less severe there since lower potentials are
involved.
Anode materials suitable for perchlorate synthesis are listed below. These are also described in the chlorate synthesis section
but are repeated here for convenience.
Platinum: The obvious disadvantage of platinum is its high price. However, it corrodes only at a very slow rate and therefore
provides an almost ideal anode material. High efficiency can be reached with platinum and processing of the electrolyte is
greatly simplified due to the absence of insoluble anode erosion products.
Lead dioxide: Lead dioxide provides an economical alternative to platinum. Efficiency of lead dioxide anode based cells is
usually slightly lower than that of platinum based cells, but the difference is small. Lead dioxide anodes are not easily bought
and
must be made. This takes some work and effort, but the anodes are cheap, farily resistant to corrosion even at higher
temperatures. More information on lead dioxide anodes of several types is given elsewhere on this homepage.
DSA: DSA stands for Dimensionally Stable Anode. This is the common term used to refer to anodes consisting of a layer of
noble metal oxides (usually RuO2 and TiO2) coated onto a substrate, usually titanium. This type of anode is finding increased
use in industrial cells because of its comparatively low cost when compared to platinum and its resistance to corrosion. The
chemicals required to manufacture these anodes are expensive and difficult to handle. However, if the chemicals can be
obtained and suitable equipment is available, the procedure to make the anode seems fairly straightforward and may be an
option. For the preparation of these, the reader is referenced to the literature. Again, I'd be most interested in anyones
experiences with this type of anode.
Magnetite: This material has found use in industry in the past, but is rarely used nowadays due to its relatively high corrossion
rate and low efficiency for perchlorate manufacture. The anodes are made by melting and casting FeO.Fe2O3 into the required
anode shapes. I have little literature available on this material, so it is not further discussed here.
Preparing the electrolyte
Sodium perchlorate can be made directly from sodium chloride by electrolysis in which case no special electrolyte for the
chlorate to perchlorate step has to be prepared. The preparation of a chloride electrolyte is described in the text on chlorates.
A cell can also be operated purely for the chlorate to perchlorate conversion. An electrolyte has to be prepared before each
batch in this case. If the cell has been operated before, it is best to 'recycle' the old electrolyte and all the impure fractions
obtained during extraction and purification of the product. That way no product is wasted. When the cell is operated for the
first time, a fresh electrolyte has to be prepared which can be done as follows.
Preparing fresh electrolyte
1. Prepare a saturated solution of sodium chlorate. Take about 60 grams of sodium chlorate for every 100 ml of solution and
bring the solution to a boil. Then allow to cool to room temperature again. Sodium chlorate will crystalise as the solution cools.
The solution is then filtered to obtain a clear saturated solution.
2. Optionally, 2 to 4 g/l of potassium dichromate, potassium chromate, sodium chromate or sodium dichromate may be
added
to improve efficiency. These compounds are suspected carcinogens, so if you choose to add any, know the hazards involved
and act accordingly. If lead dioxide anodes are used, do not add potassium dichromate as it will only reduce efficiency.
Instead,
2 to 4 g/l of sodium or potassium fluoride may be used. Although not carcinogenic, the fluorides are nasty compounds as well
and should be handled properly.
Recycling old electrolyte
1. If the electrolyte is not clear but contains suspended particles, remove these by filtration.
2. Dissolve any impure material left over from purification steps.
3. Re-saturate the solution with sodium chlorate, following the same procedure as described in step 1 of 'preparing a fresh
electrolyte'.
4. Like described in step 2 of 'preparing a fresh electrolyte' you may now add dichromates, chromates or fluorides if you
choose to do so.
Operating the cell
Perchlorate cells are operated at a higher voltage than chlorate cells and temperature and pH do not need to be controlled
within strict limits for optimal efficiency. Other than that, operation is much like that of chlorate cells.
Like explained in the theory section on chlorate cells, the voltage over a cell may fluctuate if the current is kept constant. In
typical chlorate cells this results in a cell voltage of 3 to 4 volts, whereas in perchlorate cells the voltage is higher, 5 to 7 volts
usually. The current is kept constant at an acceptable level with respect to anode erosion. A maximum current per volume as
exists in chlorate cells does not exist in perchlorate cells. The current could in theory be increased indefinately to increase the
reaction rate, were it not that anode erosion increases with increasing current density (the current per unit of anode surface
area). The current is therefore usually set by the surface area of the anode. As a rule of thumb maintain a current density of
200
mA/cm2.
The influence of cell temperature is two-fold: anode erosion increases with increasing cell temperature and the cell voltage is
reduced at higher temperatures. The former is obviously unwanted, while a lower cell voltage means energy is saved. In
industry the temperature is ofcourse chosen to get the best of both worlds, depending on what is more expensive: energy or
anodes. We need not be concerned with economy as industry does so the temperature does not matter a lot. Try to keep it
between 40 and 80 deg C. When using lead dioxide anodes, it is probably best to prevent the temperature from going very
high. It can make the lead dioxide crack.
Finally, some wat er should be added from time to time to make up for what has evaporated. Try to maintain a constant
electrolyte volume.
Running times
The required time to operate a cell depends on the current. The higher the current, the less time needed. In fact, the current
is a
measure of the reaction rate. Therefore, the amount of electricity that went through a cell is calculated by multiplying the
current
going through the cell (in amperes) by the time it has been flowing (in hours). The resulting number is measured in
amperage-hours (abbreviated as Ah). To convert 100 grams of sodium to sodium perchlorate 50 Ah are required if the cell
operates at 100% efficiency. In real life a cell will never reach 100% efficiency, and more electricity is needed.
Example: A 200 ml cell contains initially about 100 grams of sodium chlorate (the solubility of NaClO3 in water is about 50
g/100ml at room temperature). Per 100 grams, 50 Ah are needed. So, if a cell operates at a current of 2 amperes, it would
take 50/2 = 25 hours to convert all chlorate to perchlorate in a cell operating at 100% efficiency. If the cell actually operates at
80% efficiency, 100/80 * 25 = 31.25 hours (or 31 hours, 15 minutes) are needed.
If perchlorate is prepared by continuing to run a chlorate cell after all chloride has been consumed, the total run time is
ofcourse
the sum of the time required for the chloride to chlorate conversion and the chlorate to perchlorate conversion.
Processing the electrolyte
When done, raw potassium perchlorate or ammonium perchlorate may be prepared from the electrolyte as follows:
Filtering
The first step is filtration. The electrolyte usually contains suspended solid particles. These consist of erosion products of the
anodes, the cell walls, and the unsubmerged parts of the cathodes. These particles may be very small and are not always
easily
removed with common filtering paper. Filtering through a layer of diatomeous earth (sold in shops for aquarium supplies) in a
filter or on a piece of cloth sometimes solves the problem. However, even that will not always remove all solid impurities. A
common impurity that is hard to remove is suspended iron hydroxide, originating from corrosion of (stainless) steel cathodes.
The fluffy, voluminous form of the material often gives it a white or yellowish foggy appearance. This is next to impossible to
remove unless some sodium hydroxide or pool coagulant is added first. This causes the iron hydroxide particles to coagulate,
making them easy to remove by filtration. Another possibility is to add hydrochloric acid to lower the pH to between 2 and 3.
This will dissolve the iron hydroxide. If sodium hydroxide is then added to raise the pH to above 7 again, the iron hydroxide is
precipitated in a more dense form which is easily removed by filtration, even with common filter paper.
Chromate and dichromate removal
If chromates or dichromates were used to increase the cells efficiency they should now be removed. Adding a solution of
barium chloride to the electrolyte will precipitate any chromate or dichromate as the corresponding barium compounds. Add
small amounts of a 10% barium chloride solution to the electrolyte. A yellow precipitate will form. If no more yellow precipitate
is formed, filter to remove the barium compounds. A white (sometimes clearly crystalline) precipitate may form instead of a
yellow precipitate. This is barium chlorate or perchlorate. If this happens, do not add any more barium chloride solution and
filter to remove the precipitate.
Destruction of chlorate
The next step is the desctruction of residual chlorate. Even when a cell is operated for many times the required running time,
some chlorate is still present in the electrolyte. Since chlorates and perchlorates behave very differently in pyrotechnic
compositions (see the safety page among others) chlorate contamination can be very dangerous. If the cell is not operated
long
enough to convert most of the chlorate to perchlorate the chlorate contamination may be very severe and it is unpractical and
very inefficient to attemp to destroy it all. If this is the case I suggest tthis step is skipped, and the raw product is extracted.
Ammonium perchlorate cannot be made this way, as it would result in the formation of the dangerously usntable explosive
compound ammonium chlorate (also see the safety page). Conversion to potassium perchlorate may however be tried. This
will
ofcourse afford a heavily chlorate contaminted batch of perchlorate, probably even something that can better be considered to
be a chlorate/perchlorate mixture or perchlorate contaminated chlorate. This material could be used to an extremely limited
extend in pyrotechnic compositions when it is treated as a chlorate, or, a better option, it can be used as a starting material
for
the thermal decomposition or chemical oxidation preparations of potassium perchlorate described later.
Residual chlorate is usually destroyed by the action of reducing agents. Sodium sulfite is used for this purpose in industrial
setups. Iron(II)sulfate is another option, and the chemical can be bought in some gardening supply shops as it is used to
supply
plants with iron. A third method destroys chlorates by the action of strong acids. The cell electrolyte is acidified with
hydrochloric acid to a pH of 1 to 2, and the solution is boiled. Chlorates will decompose and yield a yellow gas, chlorine
dioxide. The gas will partially dissolve in the solution, imparting a bright yellow color to it. In high concentrations chlorine
dioxide is dangerously explosive and sensitive but if done using proper ventilation the small amounts evolved in this reaction
are
very unlikely to cause dangerous levels. The gas is however quite toxic and inhalation should be avoided at all times. Never
do
this step inside unless a well functioning fumehood can be used. After boiling for 15 minutes raise the pH to around 8 or 9
again
using sodium hydroxide. This should afford a colorless solution. A qualitative test for chlorate should now be performed to
make sure all chlorate has properly been destroyed. Such tests are described on the product analysis page.
If any other method is used to destroy residual chlorate the pH must always be adjusted afterwards to slightly above 7.
Otherwise, traces of acid may be incorporated into the product in later steps which can make it very dangerous to use in
pyrotechnic compositions.
Double decomposition
A decission will have to be made at this point wheter the intended product is ammonium or potassium perchlorate. Other
perchlorates can be made as well but are not discussed here as they find very little use in pyrotechnics.
If residual chlorate was not destroyed the choice is simple since ammonium perchlorate is not an option. Ammonium chlorate
could be formed in the process which is, as mentioned several times already, a dangerously unstable explosive compound the
formation of which should at all times be avoided (even in trace amounts). If chlorate was properly destroyed, and a
qualitative
test indicates so, ammonium perchlorate may be prepared. 1. If potassium perchlorate is the intended product, take 70
grams
of potassium chloride for every 100 grams of sodium chlorate that was started with and dissolve this in the smallest volume of
water possible. If instead ammonium perchlorate is required, take 50 grams of ammonium chloride and dissolve in the
smallest
volume of water possible.
2. Mix this solution of either potassium or ammonium chloride with the electrolyte. A white precipitate of the corresponding
perchlorate should form.
3. Boil the solution and add small amounts of water untill all the perchlorate has dissolved. Due to the low solubility of
potassium perchlorate a large volume of water may be needed then. If a sufficiently large container is not available the
solution
may be split up in several portions that are later recombined.
4. When all has dissolved, check the pH of the solution. It should be neutral or slightly alcaline (above 7). If it is not, add
some
dilute sodium hydroxide solution to increase the pH to between 7 and 8. When this value is overshot, hydrochloric acid may be
used to lower the pH again.
5. Allow the solution to cool slowly to room temperature. The perchlorate will crystallise during this. Cool the solution further to
0 deg C, and filter. Rinse the crystals in the filter with some ice-cold water. This raw product may be further purified as
described below.
Purification
The product can be purified by recrystallisation. This method is especially suitable for potassium perchlorate due to its low
solubility. Little prodcut will be lost, and the purity is greatly increased. Ammonium perchlorate suffers slightly worse losses
when recrystallised, but still acceptable. The impure ammonium perchlorate should be discarded since recycling could result in
NCl3 formation in the cells. The losses occuring when potassium perchlorate is recrystallised are so slight recycling is hardly
worth the effort (a liter of recrystallisation solution contains only a few grams of perchlorate). Recrystallising is done as follows:
1. Place the crude product in a pan and add 100 ml of water for every 20 g of raw potassium perchlorate, or 100 ml of water
for every 50 gram of raw ammonium perchlorate. Bring this to a boil.
2. After it has boiled for a few minutes, add 10 ml amounts of water to the boiling solution in 5 minite intervals untill all the
product has dissolved.
solution
untill it is slightly alcaline (pH=7...8) again. If ammonium perchlorate is the intended product, use ammonia instead. If this is
not
done, traces of acid may be included in the final product making it very dangerous to use in pyrotechnic compositions.
4. Allow the solution to cool to room temperature. The purified product will crystalise.
5. Filter and rinse the crystals well with ice cold water. The filtrate should be discarded
Chapter 3: Preparation by thermal decomposition of chlorate
Chlorates are thermodynamically unstable. Over time they will decompose into a mixture of chlorides and perchlorates. In
essence, the chlorate will undergo a redox reaction with itself (a so-called auto-oxidation reaction). Due to the kinetic stability
of chlorates however, the process is slow at room temperature. A well known example of the same phenomenon is diamond:
Diamonds are unstable at common pressures and temperatures. They turn into graphite extremely slowly. If a diamond is
heated, the process is sped up. Similarly, if chlorates are heated the reaction rate is increased enough for it to be used as
reaction pathway in the preparation of perchlorates. When potassium chlorate is used, the resulting perchlorate is easily
separated from the chloride by recrystallisation. There may be several other chlorates that this method can be used with, but
potassium chlorate seems to be the most well investigated option. In any case, ammonium perchlorate cannot be prepared
directly with this method due to the explosive and instable nature of ammonium chlorate, as mentioned earlier. In the first
large
scale perchlorate plants this method was used to prepare potassium perchlorate. Ideally, this preparation is performed in an
oven since it involves heating the chlorate for several hours. The chlorate used should be free of impurities that catalyse
chlorate
decomposition (such as most d-block metals). The following description assumes potassium chlorate will be used as a starting
material.
1. Heat pure potassium chlorate to slightly over its melting point. A colorless clear liquid is obtained. Before heating make
sure
no organic material or other fuels are present in the chlorate or able to fall into the molten chlorate. This would result in a
violent
reaction. Do not overheat since this will decompose the chlorate, yielding chloride only.
2. Maintain this temperature for several hours. During this time the potassium chlorate will undergo the auto-oxidation
reaction.
Due to the higher melting point of potassium chloride and potassium perchlorate the melt will solidify slowly during this time.
It
becomes quite hard to judge the correct temperature as the melt solidifies, and if an oven is not used a thermometer is
essential
to judge the correct temperature. Too high a temperature will cause the perchlorate to decompose, a low temperature will
result in incomplete conversion.
3. After the mixture has completely solidified, allow it to cool to room temperature. Test a sample of the cooled residue for
chlorate, as described in the analysis page. If chlorate is present it needs to be destroyed before extraction of the perchlorate.
Destruction of chlorate is described earlier in this text, in the section dealing with processing the electrolyte from the electrolytic
preparation of perchlorates.
4. Recrystallise the residue, as described earlier. Two recrystallisation steps are sometimes needed to separate the potassium
perchlorate completely from the chloride as there is quite a lot present.
Chapter 4: Preparation by chemical oxidation
A third method to convert chlorates to perchlorates is by chemical oxidation. A sufficiently strong oxidiser added to a chlorate
can oxidise a chlorate to a perchlorate. Suitable oxidisers are persulfates and lead dioxide in concentrated sulfuric acid.
Hydrogen peroxide does not seem to work. I must admit my experience with this method is limited and I have not been able
to
obtain much literature about it. It is mentioned in literature however, and it is definately a possible method that can be used
with
good results. If anyone has some experience with it, I would be most interested to hear about it. The experiments I have
conducted involved sodium persulfate as the oxidiser. I will give an account of the general method I used, the ideas behind it
and the results obtained with it. Anyone with comments, results, ideas, anything is very welcome to comment on it. I can
currently not do any further experiments untill july/august this year. Soon after that, this text should be updated. If you wish
to
try this method in the meantime this may be used as a starting point:
Theory
Persulfates are strong oxidisers. They are reduced according to the following half-reaction:
[ REACTION ]
The H+ generated in this reaction will prevent it from taking place below a certain pH. When a base is added to neutralise the
acid generated the reaction may go to completion. All persulfate may be consumed in the reaction. Persulfate being a stronger
oxidiser than perchlorate may be used to convert chlorates to perchlorates according to the following half reaction:
[ REACTION ]
Neither persulfates, chlorates or perchlorates are destroyed at a significant rate at the temperature of boiling water, so the
reaction rate may be increased by boiling a solution containing the reactants.
Oxidation of KClO3 by persulfate
The general procedure I tried:
A solution of 30 g/l sodium persulfate was prepared and the pH raised to 14 by the addition of a concentrated sodium
hydroxide solution. The sodium persulfate was obtained from an electronics supply store, where it was sold for etching printed
circuit boards. A foggy solution was obtained, which was filtered. 5 ml of the clear solution obtained after filtering was added to
a test tube. Approximately 1 gram of potassium chlorate was added to the same tube, and solution heated. The solution was
boiled vigorously for 15 minutes during which time water was added occasionally to make up for what had evaporated. The
solution was then allowed to cool. Upon cooling white crystals formed. These were filtered, washed with ice cold water and
recrystallised. The crystal shape during recrystallisation was observed and found to resemble that of potassium perchlorate
best. As described in the analysis page, crystal shape is not a reliable way to determine the identity of a product however. The
crystals obtained after recrystallisation were tested qualitatively for chlorate with phenylanthranilic acid (as described in the
analysis page). Chlorate was shown to be present. It seems most likely that the chlorate was only partially converted to
perchlorate. Maybe the addition of more persulfate or allowing a longer reaction time will convert more chlorate to perchlorate.
Destruction of the chlorate followed by recrystallisation should afford a chlorate free product.
1. Schumacher, J.C., "Perchlorates", New York, Reinhold Publishing Corp., 1960
2. Remy, H. "Treatise on Inorganic Chemistry", New York, Elsevier Publishing Co., 1956
3. Mike Brown's homepage
list under construction
Copyright Wouter Visser, May 1999.

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Mr Cool
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I hope some of that helped.
PYRO500
Moderator
Posts: 1466
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yep it did, when I get well (I think I have pneumonia, and I know I have strep throat) I will go to the junk yard and get a mw
oven transformer, I'm still thinking of a way to current limit it though
Jhonbus
Frequent Poster
Posts: 345
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I current limited a MOT with another MOT that had the secondary shorted. It got quite hot in continuous shorting of the other
MOT though (Jacob's Ladder) so I put it under oil....which boiled
firebreether
Frequent Poster
Posts: 108
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Could Al be used as an anode or cathode since it forms a protective layer of oxide when electrolized? I dont know if the
oxide(Al2O3) conducts. The reason I ask this is that it says titanium is the perfect cathode ( the positive one right?) because
of its low wear rate because of the protective oxide layer it forms around itself. Aluminum forms this layer so could it be used?
Also many people use a stainless steel cathod, could this be as simple as a kitchen butter fork that is stainless? If it isn't
optimal no big deal, not like I would use that anyway
Also, maybe this is why PbO2 anodes have such little wear.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Ammonium
Picramate for DDNP
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View Full Version : Ammonium Picramate for DDNP
Microtek October 9th, 2002, 03:54 PM

Well here I go again, another attempt at the elusive DDNP synthesis. But this time I have a few promising possibilities to explore; the first and perhaps least interesting is
making nitrite of a better quality using a couple of new methods that I have tried out. I'll elaborate on this later, but at present I'll keep to the second new possibility:
Synthesizing DDNP without nitrite in 90 % yield. The method comes from a patent ( US 1460708 ), and will just outline the procedure here. 100 parts fuming nitric acid is
placed in a beaker and covered with 200 parts of a paraffine oil such as kerosine.
40 parts ammonium picramate is mixed with 10 parts of an alcohol to act as a reducer ( to stop the picramate from being oxidized by the HNO3 ) and is added to the acid.
The mix is heated gradually until gas evolution stops, the acid phase is drawn off and is poured slowly into stirred water,which causes the DDNP to precipitate.
I assume ammonium picramate can be made by acidifying the sodium picramate soln from the reduction of picric acid to obtain pure picramic acid and then react the isolated
compound with ammonia water. Now, does anyone know anything about ammonium picramate?

This is a good find, since making picramic acid is EASY! I'll have to read the patent...
What exactly do you want to know about ammonium picramate? It can be made as you said, probably weakly explosive, flammable, decomposes in alkalis to release
ammonia... but as long as we know how to make it then that's all that matters, right?
kingspaz October 9th, 2002, 06:14 PM

sorry if this is a dumb question (i'm tired again) but could picramic acid be further nitrated (the NH2)? like methylamine?
Microtek October 10th, 2002, 05:56 AM

I have made a batch of picramic acid and reacted it with ammonia and obtained a brown, very fine powder that is very insoluble. When I filtered the mix and then acidified
some of the filtrate with HCl, no preciptate of picramic acid was formed as there should have been if substantial amounts of ammonium picramate was dissolved in the filtrate.
So, my question is if this low solubility is consistent with the properties of ammonium picramate. I haven't been able to find anything useful on the web ( except for an
interesting book which might be worth purchasing - I found it here: <a href="http://www.cannonfuse.com/explosives/" target="_blank">http://www.cannonfuse.com/
explosives/</a> ).
Kingspaz: If the NH2 group was substituted with NO2 I think you would just end up with picric acid again. Was this what you meant?

I guess he meant to form -NHNO2. I don't see why it couldn't be done, but maybe someone who puts more thought into it could see a problem...
Helos October 10th, 2002, 04:57 PM

I use a process for making DDNP that first makes picramicacid(?)
I react a solution of picricacid with NaOH and after that add a solution of Na2S4.
When I do this, do I get Na-picramic acid or pure picramic acid.
If I get the Na-picramicacid, how do I do to get pure picramicacid instead.

BTW my yeilds of this was terrible when i tried it, I enden up with 0,2g (na?)-picramicacid from 6g picricacid.
kingspaz October 10th, 2002, 06:53 PM

basically do this to get picramic acid:
1. make Na2Sx solution by boiling an excess amount of S with NaOH.
2. to this add TNP.
3. this will make picramic acid. you then filter it and wash and its done.
the procedure i've seen in KIBC carries out the reduction of a nitro group on the sodium salt of picramic acid. the only possible reason i can see for this is that possibly the salt
promotes reduction on carbon 2 or 6 some how avoiding rection on 4....maybe i'm talking crap....
also to get from the Na-picramate to picramic acid you simple need to add an acid which is stronger then picramic acid. so you could use HCl or H2SO4. this will result in the
sodium salt of the mineral acid and picramic acid precipitation.

Thats an interesting patent, but it seems to waste a very large amount of anhydrous nitric acid. Enough by my maths, to diazotise the picramic acid. have made the picric acid
in the first place, and oxidise everything organic in the aqueos solution to carbon dioxide water and nitrogen. Unfortunatly there is no such thing in patents as quality control. If
someone actually tries this, I would be inclined to proceed very carefully, the thought of runaway reactions looms heavily on the horizon but its the sheer waste that bothers
me most.
There are aparently a lot of mild oxidising agents that will reduce picric acid, such as glucose. Sodium nitrite is not hard to make, makes me wonder why people are having
trouble. Diazotizing is pretty trivial but its this stage you actually find out if any of the previos reactions have gone wrong.
Microtek October 13th, 2002, 08:50 AM

Marvin: Have you actually tried ( successfully ) to produce DDNP all the way from home made picric acid and home made nitrite ? It would be reassuring to know that
somebody has actually done it, as it is indeed causing no end of problems.
PS. Using about 60 mL HNO3 to produce about 40 grams of DDNP may be wasteful, but it takes perhaps 2 hours and 0.05 dollars to produce 60 mL HNO3 and considering that
40 grams of DDNP is enough for 2000 detonators, I think the excess is acceptable.
[ October 13, 2002, 07:56 AM: Message edited by: Microtek ]
Helos November 5th, 2002, 02:57 PM

You mean that 0,02g is enough for a detonator, it seems way to little.
What are you planning yo use as base charge then??
Myself I was thinking of picricacid, but I dont know if it is sensitive enough. If not, I will use it itself, even if it ofcourse are "a little to valuable" to use by itself. That is ofcourse
if I succeeds with making any DDNP at all. I think 1g will do a good singleloaded #8 cap considering the power of DDNP.
kingspaz November 5th, 2002, 06:17 PM

microtek i believe i got reasonable close using home made nitrite and home made TNP.
i finally, after many attempts (4-5) using varying methods, ended up with some sort of diazo compound. it looks a kind of lemonish brown and darkens in the sunlight. i
initially thought it was DDNP but after drying it in a dessicator and then taking a match to some i was very disapointed to have it just bubble a little and burn smokeily.
then i gave up after wasting 45g of TNP and hours and hours of cooking and experimenting to get a successful method to prepare KNO2 in reasonable purity.
i think the problem is the reduction step. it has to be carried out on the nitro group on either carbon 2 or 6 and not 4. also it must only be reduced once on every TNP molecule
not 3 times on one TNP molecule or similar reactions. there must be some way to reduce it only on the NO2 on carbon 2 or 6....
if anybody finds anything let me know i have an excess of TNP....around 100g <img border="0" title="" alt="[Eek!]" src="eek.gif" />
thats alot of yellow!

Microtek, as it happens I havnt tried to make DDNP. At the time I made a fairly small amount of picric acid, now a long time ago, and I was rather unconvinced as to how pure
it was. I used an asprin method with additional conc sulphuric. Lacking any suitable method of testing at the time I let it sit on a shelf. I will try it again at somepoint, and this
time I will make a stab at DDNP. Ive also found methods of producing as solids a few more common aromatic diazo compounds, most of which are supposed to be explosive
themselves. (Diazotize with an alkyl nitrite in alcohol then add ether to ppt).
Doubtless crappy initiators, but its not what I'm after.
Ive made reasonable quantities of nitrite from nitrate before, but again I have no idea how pure it was, just that it worked fairly well for what I was doing at the time. I need
to revise some of my old experiments. I'm very interested in primaries as novelties / demonstrations, and secondaries only as far as the chemistry goes. Just a matter of
personal preference. Benzene ring chemistry seems to follow much more rational paths than most of the rest of organic chemistry.
I would suggest anyone trying DDNP should test the quality of the nitrite they use first, then increase the amount used accordingly. Even if there is a lot of nitrate in the
mixture it shouldnt interfere as long as the right amount of nitrite is also present.

I've been researching a lot in the university library and found a book on diazotization methods and it seems that there are quite a few to choose from. A number of points were
stressed, including:
- Reaction mixture must be acidic ( below about pH 2 ) during the entire process. This means that dripping acid into the Na-picramate/nitrite soln is probably not optimal.
- There must not be an excess of nitrite in the soln due to unspecified secondary reactions.
- HCl is preferred over H2SO4 due to being more effective.
- Temp must be kept at about 0-2 C for many diazotization reactions, though some diazo compounds are stable enough to endure up to room temp.
- At least about 2.5 mol acid should be used for each mol arylamine to ensure sufficient excess.
- Substance to be diazotized should be dissolved in the acid or in another solvent that is inert towards the reactants in order to ensure rapid reaction ( which is important
because the products are unstable ).
Marvin: do you have a good way of determining the amount of nitrite in a nitrite/nitrate mix? I have had reasonable success making nitrite by reducing nitrate with lead; you
just have to heat it to a much higher temp than is needed to melt the KNO3, and then mix the mass with a metal rod until all lead has been converted.
The nitrate/nitrite is extracted with hot water, the volume is reduced and the soln is cooled to 0 C to precipitate KNO3.

I looked in Beilstein for a synthesis of picramic acid. Here is what I found:
-20 grams picric acid is dissolved in 300 mL alcohol and 125 mL conc ammonia ( soln in water presumably ).
-H2S is added at such a rate as to keep the temperature below 50-55 C.
-The produced ammonium salt of picramic acid is decomposed with dilute acetic acid to obtain the pure compound. Yield is 80 %.

a n d I m provised C hemistry > Styrene-Butadiene Rubber
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View Full Version : Styrene-Butadiene Rubber
stanfield October 11th , 2002, 11:27 AM

These days, my work was trying to plasticize so me PETN...This wasn't an easy task because I wasn 't be able to find a (cheap)
source for polyisobutylene and I asked MANY corporations all over the world. No luck... the only source I found is AC R O S
organics but 100g of polyisonutylene cost 60 + 25 of shipping taxes, so, about 80$ for 100g of rubber ! argh !
Now, I'm thiking... no ! I'm HOPING that "Styren Butadiene Rubber" (used in sem tex A & H) will com e e a s i e r a l t h o u g h a s i m p l e
search on go o g l e g a v e m e lesser results than polyisobutylene. So, where do I need to search ? I know that Styren Butadiene
Rubber is used in car tyres but I know too it's im possible to "extract" it... don't give me th is possibility, please !
thanx for all !
<sm all>[ October 11, 2002, 10:28 AM: Messag e edited by: stan field ]</sm all>

I've just found that SBR is used in thermoplastic elastom er which is (are?) available everywhere bu t, the sam e question always
remains : is there a way to dissolve it ? in toluene/unleaded gazoline/... ?

ok, I've finally found a source for Styurene Butadiene Rubber. In fact, this chemical is VER Y com m o n b u t y o u ' l l n e e d t o l o o k f
for "SBR rubber" (com m o n n a m e), and you'll quickly see there is many sources for this one...
S o , I p h o n e d s o m e o f t h e m a n d t h e y a s k e d m y h o w m uch percentage of styrene do I need (is it correct english?). They said

23,5% is the m ost com m on choice because this SBR is used to m ake car tyres, shoes,...
So, what do you advise m e ? h o w m u c h % f o r s e m t e x ? I n m y acros catalog, they sell SBR rubber with only 5% of styrene, I
think this is too low...
see ya !
nbk2000 October 18th , 2002, 08:58 AM

A s k t h e m for sm all sam ples in 5% steps from 5% to 25 %.
I can't im agine using 23.5% for m a k i n g a plastique if that's the percentage used for tires and shoe soles...way too stiff.
Though for sheet explosive... <im g bo rder="0" title="" alt="[Wink]" src="wink.gif" />
stanfield October 18th , 2 0 0 2 , 1 2 : 4 3 P M

Ok but they will send me a no n polym erised form of SBR so, it will be m odelable... no ? car tyres are SBR with added
polym erisant (is this word exist ?). Furtherm o r e , I ' v e a l r e a d y a s k e d h i m t o s e n d m e 1kg of SBR with 23.5%...so, I'll see !
Another question on SEMTEX :

My reference page is e-detonator sim ply because no other pages on the web are "chatting" about sem tex composition...
So, on this web page, I can see :

n-octyl-phtalate, butyl-citrate: 9% , what does this mean ?
- n-octyl-phtalate + b utyl-citra te ?
- n-octyl-phtalate OR butyl-citrate ?
- 1% n-octyl-phtalate AND 8% butyl-citrate ?...
And my last question :

Antioxidant and dye : (N-phenyl-2-naphtylamin, Sudan IV), Sudan IV is relatively available everywhere... but, N-phenyl-2-
n a p h t y l a m in is a very not com mon chemical ! I didn't found him in m y acros catalog ! which has a dam n huge collection of
chemicals ! Could it b e substitued ? if so, what's the chemical ?
thanx for all ! and sorry for my bad english...
nbk2000 October 18th , 2 0 0 2 , 0 8 : 2 0 P M

n-octyl-phtalate + butyl-citrate = 9% total com position weight. Ratios...who knows.
Sudan IV...why bother. It's not like your going to be sto ring the stuff for decades, right?
I f y o u n e e d a n a n t i - o xidant, you m ight try Vitam in C or EDTA, both cheap and available.

ok, but Suda n IV is the funniest thing in sem te x since it's a colo rizing ! :) Red sem tex, like m ilitary ! m u h a h a h a ! M a y b e i t
could be substitued b y any other polymer "colorizant" (again, does this word exist ?)
EDTA ? There is a lot of EDTA in m y acros catalog, one is 2,2'-Diam innobibenzyl, that's what you m e a n ?
thanx for all !

EDIT : by the way, I have 250 m L of "ethyl hex yl adipate" , could I use it instead of "n-octyl-phtalate + butyl-citrate "
nbk2000 July 17th, 20 07, 11:3 5 PM

Found an article on recovering the polymer faction from discarde d tires, using dilute nitric acid.
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532006000300027
Jacks Complete July 20th, 20 07, 03:1 3 PM

C a n y o u n o t s i m p l y u s e r u b b e r cem ent? The type that sets into rubber once the volatiles are evaporated off?
Also, there are a great m any silicones out there these days, som ething from that range m ight work very well. Or does the
rubber act as a fuel?
Charles Owlen Picket July 21st, 2007, 12:41 PM

T h e O T C t h r e a d h a s a d d r e s s e d s o m e of this issues. I o nce was fascinated by the whole process so I did so m e h u n t i n g
around....SBR is certainly available but not always th best choice depending on what energetic m aterial is being used.
R u b b e r c e m ent is (generally) a comm on latex. Therefore the resultant would not be continually formable and at som e point
would firm up. So if the desire d result is to have a m old able material tha t continu ally stays pliable, it may not be suitable. O n
a n o t h e r p o i n t , I f o u n d o u t s o m e u n i q u e issues with polyisobutylene (m o s t o f t h e g e n e r a l i z e d i s s u e s b e i n g i n t h e O T C t h r e a d ) .
Source m aterial sited is from Los Alam os resea rch in plastic energetics. They start with polybutene (yes, the bird repellent).
Results with polybutene and true sebacates yield som e fantastic "play-doh" like material that shoots at gra m level.
nbk2000 July 21st, 2007, 10:30 PM

SX-2 A m ilita ry explosive which com es in thin sheet form , and contains 88.2% RDX, 8.2% polyisobutylene, 2.2% Di(2-
ethylhexyl)Sebecate
US Patent 6932878, A plastic m o u l d a b l e e x p l o s i v e c o m position
Previous discussion about SBR, polybutadiene, PIB, etc.:
http://www.roguesci.org/theforum/showthread.php?t=2655

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > HC is just a catalyst
right? - archive file
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zaibatsu October 13th, 2002, 09:38 AM

IronWarlock
Frequent Poster
Posts: 97
From:
HC only speeds up the reaction and doesnt affect the overall outcome right?
CragHack
Frequent Poster
Posts: 606
From:
well, two things. what the hell do you mean by "HC"? and what reaction are you refering too?
------------------
...
MacCleod
Frequent Poster
Posts: 215
From:
Do you mean "HCl",for AP production?.The acid allows the reaction to begin,so yes, it does affect the outcome (unless you don't mind waiting a long time!).
------------------
CragHack
Frequent Poster
Posts: 606
From:
HCI... well, i do not know about that man. you people are still just a little off...
------------------
...
[This message has been edited by CragHack (edited January 11, 2001).]
MacCleod
Frequent Poster
Posts: 215
From:
Oops!.Typo.(I'm tired!)
------------------
ALENGOSVIG1
Moderator
Posts: 766
hehe me too, its HCL isnt it?...well anyway mccleod: any luck with the photocopyer?
------------------
Explosives Archive
Stone
Frequent Poster
Posts: 140
From:
MacCleod had it right... HCl. A lower case L. IronWarlock... The Hydrochloric acid is just a catalyst, meaning that it speeds up the reaction between the two
reactants(H2O2+Acetone). The reaction between H2O2 and Acetone starts as soon as they touch each other, but the reaction would take forever, therefore we add the
catalyst(HCl) so it only takes a few hours/days.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > How much lemon
juice for the AP? - archive file
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zaibatsu October 13th, 2002, 09:43 AM

blackadder
Frequent Poster
Posts: 313
From: London
I've heard in the forum that the citric acid from lemons can be used in place of the Hcl in the AP reaction. If true, how much should I use and is it safe? I think it is.
Maddoc
Moderator
Posts: 534
From: Somewhere on this earth....
Yeah, I lemon is enough citric acid for for 100ml of other reactants.
Kool Aid for HMTD mix in place of the HCI, Kool Aid seems to work better in HMTD than AP.
------------------
Whoa, where my fingers?
blackadder
Frequent Poster
Posts: 313
From: London
Did you mean 1 lemon? It looked like I lemon to me. Just a bit confused the way you wrote it. And what are you talking about with Kool Aid and HMTD?
zaibatsu
Frequent Poster
Posts: 403
From: England
Kool Aid is an american thing, i think "gator aid" is the same as lucozade (sp?)
Anthony
Moderator
Posts: 2304
From: England
I believe cool aid is soemthing you add to water to make a flavoured drink.
Gatorade tastes like piss and is the cloest thing you get to concentrated "squash" except it comes ready diluted in bottles
Get this, in the US you can buy pre-poured breakfast cereal! Cellophane wrapped plastic bowls filled with cereal.
Maddoc
Moderator
Posts: 534
In case you didnt get it... I was joking .
Using the juice of a lemon for AP is like using Mud in place of oil in your car.
Buy citric acid from any good chemist.
Gatorade cool man... for some reason I love it .
And those breakfast bowls are the best in the morning... no fuss... no mess.. no washing up .
---
Hell Yeah!!!
[This message has been edited by Maddoc (edited January 01, 2001).]
blackadder
Frequent Poster
Posts: 313
From: London
How much citric acid would I have to put in for 100 ml of other reactants?
Maddoc
Moderator
Posts: 534
Try and tell us... Although I tried once usuing a very concentrated mix of citric acid and got no yield.
Use sulfuric. If you cant buy it... head down a scrapyard, grab an old battery, Pour the acid into an old enameled pan, and heat until you see white fumes coming off, let cool,
and store in a glass jar (Mayo jars are good).
-----
"Ha ha ha, that fucking shotguns straight out of Doom" - Lying Wankers Signature who has since left when his parents found a bb gun in his room.
PYRO500
Moderator
Posts: 1466
i have found that 9ml of h2so4 gives excelent yeilds in batched of ap of up to 650 ml of ingredients
Arthis
Frequent Poster
Posts: 203
From:
I don't know if it's funny to ask many times the same question, but it is not to answer many times the same questions. I said too joking that you could use a lemon. In fact,
you have many other chemicals that may interfer in the reaction. So watch out. And for everybody, the acid is a CATALYST, which mean that it will work with any conc. of acid
but the speed of the reaction may be higher with more acid. So don't tell us "put 9 mL of h2so4" nobody cares since if you put only 4.5 mL it will work, just you'll have to wait
longer. The yield should be about the same.
CragHack
Frequent Poster
Posts: 606
From:
technically you do not need acid at all. but it will take a while for crystals to form.
------------------
...
blackadder
Frequent Poster
Posts: 313
From: London
Thanks for the input!
SafetyLast
Frequent Poster
Posts: 232
From: the cretaceous period
There are these things called bomb bags they are comprised of a thick 3"x5" plastic bag filled with 5 grams of sodium bicarbonate and a smaller bag filled with about the same
ammount of Citric Acid. you can buy them from novelty places and fairs and carnivals for $.50 each they are used by squeezing the smaller bag and crushing it allowing the
citric acid to come in contact with the sodium bicarbonate releasing gasses that pop the bag. I'm still looking for citric acid powder at the supermarket this would cost a lot less
and I think that citric acid should only be used for making HMTD because HCl is a lot cheaper than CA
Anthony
Moderator
Posts: 2304
From: England
Then why not use HCl to catalyse the HMTD reaction?
SafetyLast
Frequent Poster
Posts: 232
From: the cretaceous period
Hmmm I didn't know you could do that!
Thanks Anthony!
Does it have the same power and is the sensitivity any different?
(Im assuming that its not seeing as the acid is just a catylyst, but then why do all of the places like Megas site and other ones like it say to use citric acid?)

a n d I m provised C hemistry > A couple of m isc. questions.,..
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NoltaiR Novem ber 4th, 2002, 01:56 AM

These two questions belong in separate topics but I didn't think that singularly they deserved a thread.. so I am com b i n i n g
them.
Anyways m y first question is concerning store bought su l f u r . A s s o m e o f y o u m a y k n o w , I h a v e m a d e h o m e m a d e B P m a n y

tim es in m y day and usually I use 'dusting sulfur' from gardenin g s h o p s ( 9 0 % p u re) which is cheap.. but th at 10% of extra
crap that is thrown in there seem s to n egatively affect the performance o f the final BP (as compared to the occasional chance
that I will run across some pure stuff to make BP with). So m y question is.. is there really anyway to purify the dusting sulfur..
are there any solvents that might separate it out?
My second question just arose about a n hour ago. In th e past I have usually used AN from 'instant kold pa ks' (they are pure
a n d n o o n e a s k s a n y q u e s t i o n s ) a l t h o u g h s o m e t i m es I will use m y grandfather's account to get sm all sacks of FGAN which has
to have the coating rem oved. Anyways in the past, when I have opened the kold paks, the prills are usually range from dry to
slightly dam p.. but nothing that can't be evaporated of while in the oven for a half hour or so. W ell today I was em ptying som e
p a k s a n d t w o o f t h e m had prills literally soaked in water (some little prick at the store must have been walking by a n d g a v e
t h e p a c k s a g o o d s q u e e z e ) . W ell I am not one to waste so I tried sticking it in a glass pyrex bowl and put it into the oven at
170*F for about 35 m inutes. After this time the prills had com pletely dissolved in the water that was left (it didn't look like
m uch water had evaporated). I was late for work so I just took the bowl out and left it in the open until m y shift ended 10
hours later. It had turned into a solid m ass tha t was a slightly soft in a few spots but nothing m uch. W ell I decided that I was
goin g to break the AN into chunks and put it in a food processor to powder it. But as soon as the b lade starts spinning the
chunks turn into a sludge. So back in the oven it went for about 10 m inutes again at 150*F.. It had begun to harden a little
but not m u c h a n d t h e n I h a d a n i d e a . . m aybe I could m ake cast ANFO ..
It m a y h a v e b e e n a f u t i l e a n d possibly even a rediculous idea but I decided to give it a try. So I m ixed the AN (265g or 91.1%
of the m ass of the final mix) which was quickly hardening as it cooled off with 8g (2.8%) of motor oil and 18g (6.1%) of
gasoline (for those of you who are going to gripe about my percentages because I used * so m uch* fuel, I purposely added a
little gasoline to allow for evaporation). Anyways the m ass is still hardening (very slowly now that the fuel is added but
hopefully it continues until it is a solid block).
So my questions are:
(1) was this just an idiotic idea?
(2) if it is reasonable and I actually do get a solid m ass once all the extra gas is evaporated, should I corn /granulate the
m ass or try to detonate it as a single block?
DBSP Novem ber 4th, 2002, 03:48 AM

Cast ANFO isn't really something new. I's very easy to p repare but good luck detonating it, you'd p r o b a b l y n e e d a 5 0 0 g
b o o s t e r a n d g o o d c o n f i n e m e n t. I can give you a tip though, check the foam ed charges in KIFE, they shuld be very sensitive, if
y o u h o w e v e r m a n a g e t o g e t t h e m dry. You wou ld probably hav to dry the m a t 4 0 - 5 0 d e g r e e s C in the oven for about 3-4
hours. Check "cap sensitive m ixtures in KIFE" in HE.
irish Novem ber 4th, 2002, 05:26 AM

stockfeed stores are the best places to get sulfur in australia. it is used in small am o u n t s i n h o r s e f e e d b y s o m e. its a bit
m ore pure than dusting sulfur m aybe 98%? cost localy is about AU$2 per KG.
s o m aybe yo u can ge t feed grade sulfur in the usa to save the time purifing it.
IRISH
vulture Novem ber 4th, 2002, 01:48 PM

If th e sulfur is being used for gardening purposes, there will be som e salts with it to improve it's effect. As sulfur do esn't
dissolve in water I suggest you try separiting it this way.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > phenol
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zeocrash November 5th, 2002, 01:28 PM

ok so i'd found some ways to make phenol, but one night when i was at the medicine cabinet i found that the caladril lotion i was using contained phenol. closer inspection of
the ingredients revealed that there were very few liquid ingredients: water, gylcerol, sodium citrateaq.
the other ingredient was zinc oxide. which was in suspension.
so to get phenol out of this lotion, i filter it, then distill it, using a hot water bath. (to ensure that a: the phenlo does not ignite and b: that the phenol evapourates considerably
more than the water)
at the moment it appears to be working.
i was wondering if someone knew a test for phenol and a test for glycerol (to allow me to check the purity of the finished product).
also i was wondering if anyone had any ideas for improving the process.
i'll post the results soon
Polverone November 5th, 2002, 04:58 PM

What were the methods you found for phenol manufacture? Decarboxylation of salicylic acid and/or its salts?
I have an extremely hard time believing that there is enough phenol in your lotion to make the extraction worthwhile. I don't see how your use of a water bath for distillation
can possibly evaporate the phenol faster than the water - maybe you meant the other way around?
Glycerol will form the extremely noxious compound acrolein if heated with concentrated sulfuric acid and/or sodium hydrogen sulfate. It might not be a very good test, but I'm
sure your senses will will be able to distinguish between acrolein-containing air and acrolein-free air.
zeocrash November 5th, 2002, 05:57 PM

there was quite a bit of phenol, but it was quite a large bottle. fortunatly the stuff is very cheap. i'll post up details about the finished product some time
A43tg37 November 14th, 2002, 07:49 PM

That "caladril" seems to basically be calamine lotion. I wish I had a bottle of calamine to check to see if it had phenol in it, but I don't. I did find a few things on the 'net, that
had some information about how much phenol was in caladril/calamine, like: <a href="http://bnf.vhn.net/bnf/documents/bnf.2301.html" target="_blank">http://
bnf.vhn.net/bnf/documents/bnf.2301.html</a> . None of the sites mentioned anything more than 1% phenol, though, and most (like the one above) said it only contained
0.5%, which seems to make it not an ideal source. It would probably be better to stic to decarboxylating salicylic acid, or mabye try distilling Campho-Phenique instead.
Campho-Phenique is almost 5% phenol (4.7% to be exact), and basically just contains mineral oil, phenol, and camphor. As the boiling point of camphor is 204C, and the
boiling point of phenol is 183.5C, it shouldn't be too difficult to distill off the phenol (i'm assuming that since Tesla coilers have been known to use mineral oil as insulation at
between 200-250C, it won't be a factor in the distillation. The main disadvantage of Campho-Phenique is its cost, at $2.75-$5 a bottle, but there may be a cheaper generic
version, or one could always "acquire" some more cheaply than buying it, since the bottles are only four or four and a half ounces, and thus aren't too big to conceal on oneself
and walk out of a drugstore...
Alchemist November 14th, 2002, 11:55 PM

Hello all,
A43tg37, do you know the yields for the decarboxylating salicylic acid to Phenol? Aspirin (Acetylsalicylic acid) can be easily hydrolysis'ed to Salicylic acid by refluxing with
Sodium Hydroxide and then acidifying with Sulfuric acid to precipitate the Salicylic acid. Aspirin is really cheap, about a dollar for 250 tablets in the U.S.!
A43tg37 November 15th, 2002, 01:03 AM

Alchemist,
I'm afraid I don't, and even after some searching on the Hive-I thought for sure they would have soemthing on this- I still don't (all I could find was some info on temperatures
and method used when decarboxylating salicylates, I will post the URL if you want it); I guess we'll both just have to wait for Polverone on this, as I have some questions as
well (like what should the decarboxylation take place under? Methanol? Ethanol? Some kind of ketone? And is a catalyst used, or is just simple thermal decarboxylation?) On a
more positive note, I just have to mention, why would I buy aspirin and convert it to salicylic acid? Where I live, salicylic acid can be bought USP pure, OTC, and in powder
form, almost as cheaply as aspirin :) Of course, you're right, for those who aren't in such a situation, aspirin is definitely the way to go.
metafractal November 15th, 2002, 07:18 AM

I'm super happy today, I just stumbled upon a goldmine! I just found that my local hardware store sells several useful chemicals, but the jewel of the find was phenol... not
sold as any strange lotion or antying... just plain, pure phenol! And pretty cheap at that! They also had various semi-rare acids, but nothing to rave about (no nitric :( ). I fear
that they may become suspicious if I purchase too much at one time... anyone from Melbourne, Australia feel free to email me- [email protected] and we can
exchange sources. But everyone around the world, do check your hardware stores again. You'd be surprised how common it is in an available, cheap form.
>metafractal
Edit: undescriptive
[ November 15, 2002, 06:22 AM: Message edited by: metafractal ]
zeocrash November 15th, 2002, 11:32 AM

is the phenol sold as a store specific item, or is it under a brand name, if so what is it called
also the lotion was hopeless for filtering, the particles were far to small and most of them just passed through my filter. when i got the filter thick enough to stop most of them
it was so thick it just absorbed most of the liquid.
i'm trying to order chemicals through my mates company though
[ November 15, 2002, 10:35 AM: Message edited by: zeocrash ]
metafractal December 4th, 2002, 05:11 AM

Oh yes... I remember that clearly, it is a store specific item. As I said i dont like to just spell things out... you know why. But if anyone is in the area... mmm...
(concise and vague all the way :D )
>>Metafractal

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > chlorites from
chlorates
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jimwig November 9th, 2002, 04:35 PM

been reading the nitrites from nitrates post
just wondering if the same methodology could be used to remove an atom of oxygen from chlorates to form the oh so desirable chlorites?
As in NaClO3 ===> NaClO2
i know this works NaClO3 ===> ClO2 =====> NaClO2 (fill in the blanks)
sodium chlorate chlorine dioxide sodium chlorite
just curious a more direct method
maybe using electrochemistry to rip off that O.......????
vulture November 9th, 2002, 06:52 PM

Where do you want chlorites for? Most of them are dangerously unstable and explosive. But if you want, I could look up a synth, but not today anymore....tired....

"Most of them are dangerously unstable and explosive."
What part of this sentance are we not interested in. :D
jim, N (V) is as high as nitrogen goes, and nitrite is the only possible alternative at this temperature which is why it forms.
Cl(V) is not as high as chlorine goes however, and hyperchlorite and chlorite are not stable at elevated temperatures, which is why when you heat it, chlorate disproportionates
into perchlorate and chloride. In the presence of catalysts or at higher temperatures it will go direct to chloride releasing oxygen.
Edit,
Ok, noones continued this, so I'll do it.
The chlorine dioxide method will work, most of the refs I have use hydroxide.
Chlorine dioxide is highly toxic, highly reactive, and oh yes, it explodes when it feels like it. The safest way of prepairing it involves heating sodium chlorate intimatly mixed
with an organic acid (suggested acids are oxalic, citric, tartaric I dont have specific details on each one) which produces chlorine dioxide diluted by up to 2/3rds with carbon
dioxide. There does not seem to be any danger of detonation of the solid or the gas by this process, but bear in mind it could ignite if the heating is not done carefully.
Action of this on a metal hydroxide will produce a mixture of chlorites, chlorates and carbonate/bicarbonate which should be easily seperable by fractional crystalisation.
Absorbing the gas with carbonate from the start will probably work. This may seem like a pain but generating ClO2 on its own is simply not safe. One of the demos I tried
(using another method for fairly pure ClO2) involves filling a glass container with it, and taking a flash photograph at close range.
Edit,
Adding an equation to clarify the reaction of chlorine(IV) oxide with sodium hydroxide (a disproportionation).
2NaOH + 2ClO2 => NaClO2 + NaClO3 + H2O
[ November 14, 2002, 08:38 PM: Message edited by: Marvin ]
jimwig December 20th, 2002, 04:01 PM

thank you sir!!!
i get that same question a lot. but your response is dead on the bullseye as to what this board is all about. and with your permission i am gonna plagerize that very answer.
kabooom January 26th, 2003, 11:00 PM

the following reaction comes from my "industrial inorganic chemistry" :
2ClO2 + 2NaOH + H2O2 => 2NaClO2 + 2H2O + O2
there is sever spontaneous explosion hazard for chlorites, and of course their O is less than chlorates and perchlorates so its salts ain't good oxidizers. if you are looking for
explosives like AgClO2, the chlorate salt should be a better choice.
don't try the composition on ISP explosives <blockquote>quote:<hr /> Sodium Chlorate Explosive(M,AHC): Mix 50% red phosphorus with 50% sodium chlorite(don't substitute with potassium chlorate because will spontaneously
explode when mixed with phosphorous. <hr /></blockquote>from ANAR(Accidents and Near Accident Reports):
<blockquote>quote:<hr /> For God's sake DO NOT mix
Sodium Chlorite (NaClO2) with anything. ESPECIALLY not sulphur, but it is also friction, and I would imagine impact, sensitive to sugar, carbon and probably most other stuff - I
didn't check that far. Burned my hand quite bad with Sulphur (the slightest touch in my mortar set it off) and nearly did so again with the sugar. Should you come into
posession of any, not that it's that common - mine was still a bit 'warm' when I used it - don't bother with it. If it's possible to convert to (per)chlorate, then do it...don't trust
the Chlorite or you'll end up getting burned.
duncan
England
Age: 23, Experience: Educated Novice, - Thursday, June 10, 1999 at 09:21:28 (EDT) <hr /></blockquote>

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Hygroscopicity,
problems, solutions and thoughts
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Arkangel November 12th, 2002, 08:49 AM

Working recently as I have with Sodium Chlorate and sugar the problem of hygroscopicity is in my mind. A rocket ramming tool, left overnight with a small amount of fuel on
the base, by next morning had a wet, transleucent blob of goo instead. Some materials are "thirstier" than others, but keeping things dry can be a problem for virtually every
powder you work with (although some you WANT to keep wet <img border="0" title="" alt="[Wink]" src="wink.gif" /> ).
When working with such materials, I always try to keep the workplace as warm as possible, but is this a good idea? Most materials are far more soluble at higher temperatures,
so does this compound the problem? Lots of people describe heating wet comps to dry them, yet it barely working. Is this because they are able to hold more moisture at
higher temperatures? Heating things further in an oven might evaporate all the water, but then you're at grave risk of a cook off ignition. So maybe a cool dry environment
would be a better idea. Also, I have a gas powered heater (not used when gases or powder could be present in the air). These kick off quite a bit of water vapour, so really I
need to look at an electric heater of some kind.
My solution to drying out comps is to get a dry bag of silica gel, and put it into a sealed plastic tub with the comp.
This
<a href="http://www.geejaychemicals.co.uk/usingsachets.htm#USING%20SILICA%20GEL%20SACHETS." target="_blank">http://www.geejaychemicals.co.uk/

usingsachets.htm#USING%20SILICA%20GEL%20SACHETS.</a>
links to a UK supplier of Silica Gel, and describes the ratio of the stuff needed to keep things dry. Since I'm using 1lb bags in a container of 1lb of comp, I'm fairly certain that
even if I have to change gel bags for new dry ones every now and again, I can dry out even the most soaking wet comp. (I have some testing right now) As long as the
container is sealed, and the silica gel is more hygroscopic than whatever you're trying to dry, it should work. If so, then you might even be able to safely cast a BP or other fuel
grain, then put all your motors in a sealed container like this, and leave them for a couple of weeks to dry?
Once you have dry comps (or if you started with them dry in the first place), you might want to store them for a while. One solution is, again, a sealed container, along with
some dry bags of gel. Another, especially if you want to leave the ordinance in some tactical place for an extended period, would be to construct the device, and then seal it
with varnish, a laquer or even paint. Has anyone an idea of how effective the latter might be? (Or any other thoughts)
Anthony November 12th, 2002, 11:08 AM

I realise what a pain NaClO3/sugar can be. I used to dry it under a radiator and it worked ok. A desk lamp might work well, and you can vary the temperature by how cose
you put it to the comp.
Sealing finished devices is a good idea, a drop of wax over the nozzle of a finished rocket motor would make it storeable and the motor will have no trouble clearing it on
ignition.
I briefly experimented with casting BP grains, they tended to shrink away from the tube walls on drying and subsequently CATO on ignition <img border="0" title=""
alt="[Frown]" src="frown.gif" />

Why would you buy silicagel when you can use cheap CaCl2 or MgSO4 which are available in bulk quantities?
VX November 12th, 2002, 03:05 PM

Yeah,as vulture has said CaCl2 is far more easily avalibe, and cheaper in the UK at least. (Focus and B&Q sell bags of the stuff as refils for those damp trap things).
Magnesium Sulphate is also avalable en mass from garden shops fairly cheaply, but it is sold in it's hydrated form, so to be any use as a desicant it must first be dried out in an
oven, and kept in an airtight container untill it is needed.
Sparky November 12th, 2002, 06:50 PM

In some whistle compositions such as those containing sodium salicylate have vaseline in them. This keeps it dry and lubricates it when it is being pressed.
On that page that talks about Bates in the "Rockets" thread, the author has done some experiments with coating his grains with NC laquer. The conclusion is that it works well
but needs to not have any cracks in the coating. I also have seen a silicone grease/blend on firefox used as a sealant. Maybe you could use vaseline. I wonder if you could get
the fuel wet, while it's still in powder form, with NC laquer then let it dry in a thin layer. Then granulate and use that to make your rocket.
If you work in an enclosed space, maybe a dehumidifier would help (increases static though).
Potassium chloride is incredibly cheap as a water softener. I saw a 20 kilo bag of it in a grocery store right by my house: $5. It might have been a typo or something. Convert
your sodium chlorate to potassium chlorate.
For drying stars I am thinking of using a vacuum oven. My dad brought me one from his office, they were throwing it out. I need a vacuum pump though.
Mostly I try to avoid hygroscopic compositions. For example instead of using sodium chlorate/sugar I would use potassium nitrate/sugar, ball mill it and use a longer core. If I
were to have hygroscopic chemicals that I want to stay dry I would them in mason jars. I guess you could seal with wax it for long term storage.

a n d I m provised C hemistry > Benzofuro x a n a n d d e r i v a t i v e s
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View Full Version : Benzofuroxan and derivatives
Microtek D e c e m ber 3rd, 2002, 11:51 AM

Dinitro benzofuroxan is a dense, powerful HE that is generally re g a r d e d a s b e i n g t o o s e n s i t i v e f o r u s e a s a h i g h e x p l o s i v e ,
however am ino derivatives are being investigated for use and salts such as potassium din i t r o b e n z o f u r o x a n c a n b e u s e d i n
prim ary com positions.
U S p a t e n t n u m b e r 4 1 85018 details the preparation of DNBF by oxidation with NaO Cl of o-nitroanilines which can optionally be
s u b s t i t u t e d a t t h e 4 a n d 5 p o s i t i o n s . T h e y m e n tion som e of the substituents that can be attached at those sites, but NO2 is
not one of them.
o-nitroaniline is not so easy to prepare, as the nitration of anilin e will give both o- and p-nitroaniline.
Now my idea was to d initrate aniline to give prim arily 2,4-dinitroaniline which is then oxidized to m o n o n i t r o b e n z o f u r o x a n a n d
nitrated to dinitro...
The full synthesis from N a - b e n z o a t e w o u l d t h e n b e s o m ething like this:
- Distillation of Na-benzoate a n d C a ( O H ) 2 t o g i v e b e n z e n e .
- Mononitration of benzene with m i x e d acids.
- Re duction of nitrobenzene with Fe/HCl to give aniline.
- Dinitration of aniline to give 2,4-dinitroailine ( does anyone know how much 2,6-nitroaniline woul be m a d e ? )
- O xidation with NaO Cl to give n i t r o b e n z o f u r o x a n .
- Nitration to give DNBF.
O f c o u r s e t h i s a s s u m e s t h a t a nitro substituent does no t interfere with the oxidative ringclosure.
Mr Cool D e c e m ber 3rd, 2002, 01:32 PM

The other com m o n m ethod is by reacting a 1,2 -chloronitrobenzene with NaN3 to form a 1,2-azidon itrobenzene, followed by
elim ination of nitroge n.
T h e . p d f d o c u m ents "New Explosives" and "New Energetic Materials" (which I think I downloaded from the .ftp, but if not I'll e-
m ail them to those that are interested) contain information on quite a fe w f u r a z a n s a n d f u r o x a n s ( b o t h o n b e n z e n e r i n g s , a n d
on their own).
C L - 1 8 , a m inonitrobenzodifuroxan, is a powerful IHE, and I get the im pression that all furoxans are less sensitive th a n t h e
corresponding nitro com pounds. Maybe dinitrobenzofuroxan is just too sensitive compared to things like NTO, TATB and other
IHE's that the military like, but not com pared to TNT, RDX etc?
Mr Cool D e c e m ber 8th, 2002, 07:31 AM

Marvin, I'm having trouble sending that second d o c u m e nt that you asked for to you. I forgot that you can't just select and
copy/paste b its of .pdf's!!
I'll try to find out if I did get it from the ftp, if I didn't then I'll post a link to where you can download it, if I did then I'll try to
figure som ething out...
zaibatsu D e c e m ber 8th, 2002, 08:08 AM

Mr C ool, if you just want to take a sm all am ount of text from a protected PDF just zoom in so it's nice and big on your screen,
a n d u s e t h e " P r i n t s c r e e n " b u t t o n . T h e n , o p e n e d u p a n i m age editor, paste it, crop to desired size and save as whatever.
Marvin D e c e m ber 9th, 2002, 12:06 AM

Thankyou MrCool,
I find winrar to be very useful for com pressing and splitting files. Im a g e p d f s d o n t c o m pre ss much, but Ive found others
compress very well. The compression method in pdfs doesnt seem to be very clever. Ctrl_C was still considering my ftp
application when it went down, I will reapply now it is back up.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Cyalume glowsticks \
liquid glow comppound
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View Full Version : Cyalume glowsticks \ liquid glow comppound
Fl4PP4W0k December 4th, 2002, 07:42 AM

Hey ppl, I have an idea for New Years Eve (and other potential occasions) that involves the use of large quantities of 'glow liquid'.
You have all seen this stuff - in those glow sticks \ jewelry that ravers wear.
What I'm trying to find out, is the exact chemical composition of the damn things!!!
I found this PDF, which seems relatively informative:

<a href="http://216.239.53.100/search?q=cache:V2LJVFNpZ_YC:www.dti.gov.uk/homesafetynetwork/pdf/flouresc.pdf+Dibutyl+phthalate+green+glow+chemical
s&hl=en&ie=UTF-8" target="_blank">http://216.239.53.100/search?q=cache:V2LJVFNpZ_YC:www.dti.gov.uk/homesafetynetwork/pdf/
flouresc.pdf+Dibutyl+phthalate+green+glow+chemical s&hl=en&ie=UTF-8</a>
So far, I have discovered that the main compound is Dibutyl phthalate. Then there is the activator, H2O2. There is some 'oxalate' solution which provides coloring?? This is
where i get confused....
What exactly IS an oxalate solution??? From an old chem book, it says that an oxalate is "a salt or ester of oxalic acid".
Ok then... so something like Barium Oxalate would give me a green glow???
Im confused :S
Does anyone know about the chemical processes involved in these things?
TIA.
Rob
nbk2000 December 4th, 2002, 09:39 AM

A Google search using the words "cyalume" and "patent" would have yielded the desired information.
Marvin December 4th, 2002, 04:45 PM

As a basis for understanding the patents, which are usually intended to be legally binding, rather than informative, I'll run through the main ideas. This is one part of chemistry I
find most interesting.
The contents of the lightstick, is a small glass phial containing hydrogen peroxide, inside a plastic tube containing dibutyl pthalate, an 'oxalate ester' and a fluorescent dye. The
oxalate ester is, like is implied, an ester of oxalic acid (COOH)2 and a phenol with several chlorine or nitro groups on it. The dibutyl pthalate is the major constituant, but its just
a solvent. When broken the peroxide reacts with the oxalate ester producing unstable molecules of the dioxetane type (CO2)2 in an unusually high 'excited' energy state, this
energy is often transfered to the dye which emits light. The oxalate ester provides the power, the dye determines the colour of the light emitted.
The plastic container ends up pressurised from the CO2 the dioxetane breaks down into. If the container is opened, the reaction produces less light, and lasts much less time.
Ive covered a tennis ball with this stuff and the light is much more feeble and only lasts a few mins. It is possible to make these chemicals in a basically well equipped lab, but
the precursors arnt that nice. Buying the chemicals themselves is rather expensive, annoying considering how cheap the precursors are.
Interestingly, the oxalate ester of dinitrophenol and picric acid are supposed to work quite well in these reactions. They are not as I understand it decomposed at the end, only
the oxalate part falls to bits, the electron ring systems are required to stabilise the excited states until the energy can be transfered to the dye.
Edit, Spelling.
[ December 04, 2002, 03:48 PM: Message edited by: Marvin ]
Fl4PP4W0k December 5th, 2002, 06:02 AM

Thankyou Marvin,
NBK - I searched for Cyalume Patent but no useful info was found...
These oxalate esters, can they be purchased as a pre-made compound? Or is there a relatively simple method to synth one yourself...
This dye... there would have to be something special about it? Does it convert UV radiation to visible spectrum or something?
Or does the reaction straight just make a white light.... hmmm
More researching for me

If you searched the USPTO database using "omniglow" or "cyalume" or "lightstick", you'd have more than enough details (chemically and mechanically).
Can't believe I'm having to tell you this.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Making H2SO4 from
HNO3
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I don't know if this is in the right forum but here goes. I can't get small amounts of H2SO4 or HNO3, but I can get 15L of 90%> nitric acid for $115 :D . Is there anyway to
make conc. sulfuric acid out of the nitric acid? I was thinking something like this :
HNO3 + MgSO4 ---> H2SO4 + Mg(NO3)2
Would this work? I read about using a nitrate along side sulfuric acid in nitrations, can I use a sulfate along side nitric acid to nitrate things? Mainly I want to make nitrostarch,
nitrocellulose and other nitro synths. If i were to nitrate cellulose with HNO3 and MgSO4 would I make the nitrating mixture by dissolving as much MgSO4 into the HNO3 as
possible?
Mr Cool December 6th, 2002, 02:38 PM

Oh god, NO!!! Don't use >90% HNO3 for nitrocellulose!! Make RDX!! Then you won't have to make H2SO4!!
You could also use acid of that strength for many nitrations such as NC. If you add a dehydrating agent, for example ANHYDROUS MgSO4, then it will help, but it won't be as
effective as a mixture with H2SO4.
You can't distil H2SO4 from HNO3 and a metal sulphate because of the boiling points of the two acids, and H2SO4 + Mg(NO3)2 --> MgSO4 + 2 HNO3 is favoured over 2
HNO3 + MgSO4 --> H2SO4 + Mg(NO3)2, because H2SO4 is the stronger acid and holds it's H's less strongly than HNO3.
But please, don't waste it :) . Make RDX or PETN.

You should be able to find sulphuric if you look long enough, either acid for car batteries, which you boil down, or some of the more expensive brands of draincleaner. Its an
interesting thought experiment though, assuming something so hard to get as nitric is freely available and you have to make everything else out of it.
If you can get sulphur, and most people can if they try hard enough, burning it and leading the fumes into the nitric will eventually give you mostly sulphuric, which you will
have to boil to get rid of the remaining nitric and water formed. If this is too complicated, simply adding solid sulphur to the nitric will eventually react to give a similar mixture
to above, but with less sulphuric, more nitric, and a lot more water.
Both these should be done outside as they will produce a lot of very toxic NOx gasses.

Ok thanks for the help. But I have no phenol for PETN, but I do have every thing else listed for it, acetone, nitric acid (next week :D ), sodium carbonate and water (this was
so damn hard to find) Hmmm, RDX sounds like a good choice, I got a cheap source of formaldahyde and ammonia. I would rather make the hexamine opposed to buying it
cause if i'm gonna make something like RDX you want to chems to be pure as possible. And doesn't RDX require fumming nitric acid? In Oz sulfuric is hard to come by, I found
it for 98% 500mL for $21 AU. Batteries are expensive. Does any one know how much sulfuric acid you can get out of a standard car battery. Would the old 'dead' batteries
from a car yard have the sulfuric acid still useful in it, cause I got a friend who's dad just collects old car batteries and have about 50 of em he said I could have. If I did boil the
sulfuric down would a plain old borosilicate beaker and a bunsen burner do it?
kingspaz December 6th, 2002, 08:31 PM

you don't need phenol for PETN!!! do a search!
yes a beaker and burner will do for boiling down battery acid. i used to get my acid from car batteries. you get aroun 4-5L of 20-30% H2SO4 (actualy conentration depends
how fucked the battery is). coincidently i used to get my batteries from the scrap yard too. i'd just drive in, load up my car and drive off then bring them back empty the next
day :) . the best way to do it is charge the battery up (raises the H2SO4 concentration to the highest it will go) then take it off charge and remove the lid sealing the cells
('sealed' cell lids can easily be removed with a screw driver). next tip it over wuickly inside a bucket to collect the acid and watch to not get any on you. then pass it through a
filter to remove bits of lead and other crap in there. then you should have a nice clear H2SO4 solution. put it in the beaker and boil off the water. it must be boiled until thick
white fumes come off it (H2SO4 vapour - don't breathe it as it'll burn your lungs out).
by the way greater than 90% HNO3 is fine for RDX. you won't get the best yield but you won't get the worst either. before you do anything do some fucking research!!! it is
quite evident from your post that you don't really have much of a clue. don't just blindly follow instructions have some idea why you are carrying out a particular step.

What type of bucket can I collect the acid in? Not metal cause it will eat it, but will it affect plastic buckets? What type of filter do you use. I only got a small filter funnel
(90mm) and normal filter paper. Flappa tells me he uses a t-shirt over a bucket and pours his AP in it, he reckons it works fine. So can I use a t-shirt (don't think so) to filter
the lead crap from the sulfuric. Or is the concentration of the sulfuric low enogh not to afect the bucket or t-shirt?
CyclonitePyro December 7th, 2002, 12:09 AM

That seems funny to need to make sulfuric acid from nitric acid. Shows how we all have different hard to get and easy to get supplies.
Here we have a store called NAPA auto parts. I asked the guy behind the counter about sellin "battery fluid", to sound ignorant. He said they sell 5 gallons of I'm thinkin around
30% sulfuric acid for $30. It's a little pricey, especially considering I'll only have 1.5 gallons of concentrated acid, after boiling.
He said the 5 gals was for companies that use large machinines like bulldozers and such, so he might wonder why I'm buying it, especially since the area has a little "meth lab
problem."
I'm not going to use drain cleaner acid for sulfuric in explosives synthesis anymore, it's always black after boiling, no matter what brand (probably beacause of the inhibitors
they put in) so it makes it hard to see the true colors and whats going on in a reaction.
I only use drain opener)un-pure) sulfuric acid for making nitric in distillation, due to the process and no added chemicals get into the final and wonderous product.
ALENGOSVIG1 December 7th, 2002, 12:13 AM

Try filtering it through asbestos, glass wool or mabe skarksin in a buchner funnel.
blindreeper December 7th, 2002, 03:10 AM

Thanks for the imput guys but I solved my H2SO4 problem about half an hour ago. My mum went to the dump to err...dump stuff and there is a
special place for car batteries. I went over and started to put the biggest batteries in the car and when I moved one I almost shitted myself. Just there was a 2.5L bottle labled
SULPHURIC ACID. So I picked it up and it was full!!!!! So now I have 5 batteries worth of sulfuric acid and 2.5 L of sulfuric. It is sulfuric acid in there cause my dad had a sniff
and says thats definatly sulfuric acid. What concentration could I expect from this bottle? There was no concentration on the bottle, but it said BATTERY GRADE SULPHURIC
ACID. I will boil it to the point of white fumes. I also got some KNO3 and some ammonium nitrate so I might nitrate some cotton or toilet paper (unused of
course) There was also a 5 L container of 35% HCl so I snatched that up aswell. :D
[ December 07, 2002, 08:26 AM: Message edited by: blindreeper ]
knowledgehungry December 7th, 2002, 10:45 AM

Battery grade is 30%.
Mr Cool December 7th, 2002, 10:56 AM

Nitrated tissue paper makes a good acid filter, that's what I use when I need to filter strong acids.
kingspaz December 7th, 2002, 05:44 PM

blind reeper, don't forget to charge all the batteries for 12 hours each before you empty them. if you don't do that step then you will get barely any acid out of them. you also
must empty them straight after charging incase the H2SO4 content drops. this will happen if the battery is a dud, most batteries there have been put there for a reason. plastic
buckets will be fine because its not high concentration. also you can use a t-shirt or filter paper.

I also read that concentrated sulfuric acid is a very good dehydrating agent. So once I boil the acid down to 98% stuff, will it readily absorb water from the air and dilute it? I
was reading some old posts and one said make sure there are no scratches in the pot/conatiner whilst boiling it down, because it may crack = Bad :( But since I'm using
borosilicate glass (pyrex) will it matter if there are minute scratches on the glass surface? I'm putting the batteries on the charger now. From say 1L of 30% sulfuric acid, how
much concentrated acid can I expect, not much?
CyclonitePyro December 7th, 2002, 11:11 PM

You should get just a little over 300mL of 98% sulfuric acid.
Thats a nice find you got yourself, I'd love to find a heap of car batteries and even more a bottle of the acid conveniently taken out for you.
So asbestos, glass wool and nitrated tissue paper will remove the color from my acid, if this is true thank you ALENGOSVIG1 and Mr Cool very much. As a coincidence I have
purchased a 500mL and 1L filter flask and small and large buchner funnels.
Where might one buy nitrated tissue paper, I'm not about to use my HNO3 to nitrate some kleenex <img border="0" title="" alt="[Eek!]" src="eek.gif" />
ALENGOSVIG1 December 7th, 2002, 11:32 PM

I havent tried any of the methods i posted, but ive been told they work. No promises though.
Sam December 8th, 2002, 02:33 AM

Whoah, your in Australia and you can buy that much >90% nitric acid for that cheap? Where the hell from? I have searched all over N.S.W. and never even seen it for sale
in any concentration!
frogfot December 8th, 2002, 05:27 AM

How would one remove Pb from battery acid? Will electrolysis with carbon rods do it to convert it to PbO2?
EDIT: Sorry, I'll shut up now <img border="0" title="" alt="[Frown]" src="frown.gif" />
[ December 08, 2002, 06:01 PM: Message edited by: frogfot ]

Well in the Brisbane area ( GO QUEENSLANDER!!!!). It's from an agricultural place called Grow Force Australia. The same place where I got my KNO3. I don't
know what it's sold for probably making nitrate fertilizers. I'll have to get my mum to go in and buy it cause if I go in "Son, what do you need 15L of nitric aicd for?" it will look
bad, cause i'm only 13. Their site is <a href="http://www.growforce.com.au" target="_blank">www.growforce.com.au</a> The battery acid wasn't removed from batteries
it's for filling up old ones so it has no impuritis. I think I will boild this 2.5 L bottle down first. Then if I havn't enough I will then boil the stuff from the batteries down.
kingspaz December 8th, 2002, 08:52 AM

frogfot, read the whole topic :mad:
Fukineh December 8th, 2002, 10:05 PM

Oh precious nitric acid. If I could get 90% HNO3 I would be one step closer to utter completeness. I was gonna say don't waste it making H2SO4, but with 15 L its not such a
crime to use some of it up.
VX December 12th, 2002, 11:22 AM

blindreeper It does matter if their are small scratches on the glass, not because of the effect of sulphuric acid or any other chemical on it but because they massively increase
the chance of the glass shattering due to thermal shock or small knocks etc. However if you are careful and heat it slowly and avoid mechanical impacts to the glass you should
be OK. Just remember the last thing you want is boiling conc. sulphuric acid spilt everywhere, or anywhere for that matter.
Also it seems interesting that your dad could conclude that your mystery solution was in fact H2SO4 with such conviction from its smell when H2SO4 has no smell.
Finally H2SO4 is an excellent dehydrating agent and it will quite happily absorb moisture from the atmosphere to dilute itself. As such it should always be kept in a closed
container.
Edit: Spelling
[ December 12, 2002, 10:24 AM: Message edited by: VX ]

Yes the last thing you want is boiling 98% sulfuric acid on your skin. I was takin it off the bunsen and a bit splashed on me finger. That was on tuesday I think and I have a
small hole in my skin = :mad: I tried out that manganese heptoxide, very fun stuff. Also what would be more effective at boiling down the sulfuric acid? A 500 mL beaker or a
500 mL flask? I want to know cause I want the faster method for obvious reasons.
VX December 13th, 2002, 09:18 AM

A heat source would probably be more effective than either of the two <img border="0" title="" alt="[Wink]" src="wink.gif" /> . The safest option though, is whatever has
the larger opening at the top so it's probably going to be the beaker. Be careful not to fill it more than about half full, and with boiling acid you could really do with something
to act as anti bumping granules, try a few tiny pieces of broken glass. Preferably very scratched (sand blasted?)
The only other thing to say is that Manganese heptoxide may well be fun stuff but if you cant even manage to boil sulphuric acid without causing injury to yourself then you
should not be making it for quite a while yet.

Unless, of course, he's willing to share with us the results of his "Mn Heptoxide and the flammibility of human skin" experiment when some gets splashed on him.
<img border="0" title="" alt="[Wink]" src="wink.gif" /> :D
[ December 13, 2002, 08:58 AM: Message edited by: nbk2000 ]

Well I got a cotton ball and mixed it with some very fine KMnO4 and put it on the ground. I dropped some of the 98% sulfuric acid on it and after about a
second it started fizzing and flames shot out of the sides of the cotton ball. It was instantly vaporized <img border="0" title="" alt="[Eek!]" src="eek.gif" /> But the thing that
confused me the most was during the burning stage a brown purple gas/smoke came off, then a bright pink/purple smoke came off. What is this purple smoke from? I'm
guessing it's from the KMnO4 but i'm not sure.
VX December 13th, 2002, 10:28 PM

Right, it's got to be said. Do a Search for manganese heptoxide, and you will see! There has been a lot written about this compound and you are asking the same questions
over again. :mad: To be honest Im surprised that nobody has said this sooner.
Trinitrotoluene January 22nd, 2003, 10:25 PM

I am wondering is it possable to make H2SO4 for NaHSO4? After HNO3 is made with H2SO4 and NaNO3 to get HNO3 and a byproduct NaHSO4. I've heard heating it will cause it
to decompose to SO3 and I guess the So3 can be dissolved into water to produce H2SO4.
rikkitikkitavi January 24th, 2003, 03:40 PM

NaHSO4 decomposes at around 300 C.
2 NaHSO4 => Na2S2O7 + H2O (sodium pyrosulfate)
Sodium pyrosulfate decomposes at 350 C and higher
Na2S2O7 => Na2SO4 + SO3
Beware that these salts are very corrosive when molten, they are used to dissolve metal ores for analysis!
Ps NaHSO4 decomposes into Na2SO4 and H2SO4 by extraction with 80 % EtOH. The former is insoluble in the liquid and the latter goes into solution. There are some patents
covering this (I have forgotten the numbers)
/rickard

a n d I m provised C hemistry > Acid recycling/recovering
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stanfield D e c e m ber 10th, 2002, 06:09 PM

I usually make PETN. At the end of the reaction, you ha ve to precipitate the m ix in 5L of water then filter the dilute solution, ok
but it there a way to filter out the PETN directly from the concentrated acid for, after, distilling it with sulfuric acid to get back
s o m e 98-99% "new" acid ?
This step is im possible with normal filter paper... is there a technique ? I know the industry do this...
thanx !
nbk2000 D e c e m ber 10th, 2002, 09:58 PM

Have you ever tried u sing a buchner funnel with vacuum ? That's how the pro labs do filtrations of thick solutions.
stanfield D e c e m ber 11th, 2002, 03:04 AM

ok, but, on the buchner funne l, you have to place a *filter paper* and th e concentration o f the acid is about 70-80% (don't
r e m e m ber exactly), what the vacuum do ? Acid will "hea t" paper, no ?
bye !
<sm all>[ Decem b e r 1 1 , 2 0 0 2 , 0 2 : 1 0 A M : M e s s a g e e d i t e d b y : s t a n f i e l d ] < / s m all>
nbk2000 D e c e m ber 11th, 2002, 03:27 AM

That's why you use "acid resistant" filter paper. Or, you could nitrate a regular paper filter into nitrocellulose and use that
instead.
W hat happens when you suck on a straw? That's what the vacuum does. :rolleyes:
stanfield D e c e m ber 11th, 2002, 07:55 AM

yeah, I found this filter paper in one of my catalog ! A bit expen sive but producing nitric acid always takes m e m any hours !
This will help m e...
All I have to do now is to invest in a buchner fu nnel... and a little pump.
thanx for all !
zaibatsu D e c e m ber 11th, 2002, 02:07 PM

For cheap acid-resistant filter paper try woven glassfibre m atting from GR P (glass reinforced plastics (Fibreglass)) suppliers.
stanfield D e c e m ber 11th, 2002, 03:43 PM

I f s o m e m illigram s of PETN passed through the filter, what effect will it have when redistilling with sulfuric acid ?
(sorry for m y bad english !)
thanx.
aster D e c e m ber 31st, 2002 , 08:50 AM

i h a v e a n o t h e r q u e s t i o n a b o u t H 2 S O 4, m y 98% H2SO 4 turn dark on storage, i think it form some carbon that crust at the
inside of the plastic b ootle, how to prevent this happen? i closed the bottle tight and store them away from light. is the acid
b e c a m e w e a k e n e d s o m uch from t h i s c h a n g e s ? t h a n k s
Mr Cool D e c e m ber 31st, 2002 , 09:58 AM

It sounds like it m igh t be atta cking the plastic, H2SO4 doesn't g o brown if pure (I once got some 98% H2SO 4 on th e plastic
h o u s i n g o f m y scales, which turned it slightly brown in a few seconds).
I'd move it into a glass bottle if I were you, in case it does eat all the way through the plastic.
I doubt the concentra tion of your acid has been significantly affected.
aster January 1st, 2003, 06:11 AM

thanks, i will changes m y container to glass, actually i have try to made picric acid with aspirin disolving in this (Brown)H2SO 4,
it's OK

By filtering out PETN directly from concentrated HNO3 at the end of the reaction with such buchner funnel, I have
to know if PETN is soluble in concentrated nitric acid...
I wasn't able to find any inform ation all over the net about this subject.
This is a m a j o r p r o b l e m b e c a u s e :
when you've filtered out your PETN, you get back your nitric acid which has a concentration of about 80-85%. Ok, but to
concentrate it again, you'll have to distill it with sulfuric acid and if som e PETN still remains in the b oiling fla sk, what will
h a p p e n d u p o n h e a t i n g ? :confused:
thanx...
rikkitikkitavi February 5th, 2003, 04:16 PM

m ay I suggest the following:
vacuum distill the HNO3/H2O /PETN mixture until alm ost dryness (or rather a thick slugde in the flask. Low temperature will
probably not trigger a reaction with the PETN, and the PETN will o f course not distill over.
T h e r e m a i n i n g s l u d g e i n t h e f l a s k c a n b e d i s p e red, burned or something sim ilar suitable to do with it (really I have no clue how
to do this safely :)
If you search there are m any patents covering recovery of nitration acids, m ost of them considering a m ixture of HNO3/H2SO4/
H 2 O /nitrationproducts.
Generally the idea is to heat the m ixture so that any organic m atter is decomposed by the nitric acid but th e p a t e n t s d o e s n t
cover the possible dangers involved .
/rick ard

ok, thanx, I'll search...
Do you think I could loose m any grams of PETN by filtering it out with this method ? The yield is im pressive each time I m a k e
PETN but anyway, I don't want to loose too m uch product !
EDIT : huh... I did som e search and it's hard to find som ething... I goto this site : <a href="http://www.uspto.gov/p atft/"
target="_blank">http://www.uspto.gov/patft/</a> then did m any search with word s like "recovering " "recycling" "nitration
acids"...
So, if you already fou nd/know a patent cevering the subject, cou ld you give m e the num b e r p l e a s e ?
thanx.
<sm all>[ February 05, 2003, 04:32 PM: Message edited by: stanfield ]
rikkitikkitavi February 7th, 2003, 02:03 PM

Stanfield I recom m e n d :
< a h r e f = " h t t p : / / e p . e s p a c e n e t . c o m / e s p a c e n e t / e p / e n / l e v e l 1 . h t m " target="_blank">http://ep.espacenet.com / e s p a c e n e t / e p / e n /
level1.htm </a>
e u r o p e a n p a t e n t d a t a b a s e s i n c e i t i s m uch better than uspto
Unfortunately I dont have any patents right now but,
it covers all patents world wide,and is searchable for keywords back in tim e (which usptp isnt only 1975 onwards, they are slow
scanners :)
you can also search for classification (click on classpat), i e you can find all patents covering a topic
C01B17/94 Recovery of sulfuric acid from nitration acids

C01B21/46 Nitric acid , purification, separation
C 0 6 B 2 5 / 3 2 e x p l o s i v e s , c o m position... the com pound beeing nitrated pentaeritritol
a s a few exam p e l s .
/rick ard
edit/ a quick search for "nitric acid + recovery + nitration" gave 30+ answers :=
<sm all>[ February 07, 2003, 01:07 PM: Message edited by: rikkitikkitavi ]

a n d I m provised C hemistry > C a r b o n F o a m
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nbk2000 D e c e m ber 19th, 2002, 06:19 AM

W as browsing around when I ran across this interesting new m aterial.
<a href="http://www.industrialheating.com/CDA/ArticleInform ation/features/BNP__Features__Item/0,2832,87444,00.htm "

target="_blank">http://www.in dustrialh eating.com /CDA/ArticleInform ation/features/BNP__Features__Item/
0,2832,87444,00.htm </a>
From the website:
</fo nt><blockquote>quote:<hr /> T h e b l a c k f o a m f e e l s l i k e f o a m i n s u l a t i o n , b u t i s a t h o u s a n d t i m e s s t r o n g e r ; o n e s q u a re inch o f the ma terial could
support the weight of a full size autom obile without crushing. It also is possible to have a flame (from an a cetylene torch, fo r
e x a m ple) im pinge directly onto the foam without initiating combustion of the m aterial.<hr /></blockquote><im g src="http://www.industrialheating.com /IH/FILES/IMAGES/75221.jpg" alt=" - " />
E x p o s i n g c a r b o n f o a m to a tem perature of 1650 C from an acetylene torch results only in very slight oxidation.
It is basically fireproo f carbon.
There's a whole list of m aterial properties better describ ed at the site, but I think there's got to be uses for our "hobby" that
this material could be put to use for.
For instance, since it is a hollow cored foam, it could be used to absorb a n energetic m aterial in its pores. The foam would
provide mechanical strength a nd therm al shock resistance, while still be insubstantial to explosive propagation.
It m ight even be useful to provide fuel to an oxygen rich explosive since it IS pure carbon .
Ideas?
Microtek D e c e m ber 19th, 2002, 07:33 AM

Probably would be useful for absorbing shock from an e xplosion which co uld be useful for silencers ( depen d i n g o n p o r e s i z e )
or as mufflers in test tanks for blasting test in urban en vironm ents.
Crow D e c e m ber 19th, 2002, 10:48 AM

I think this would be an excelent m ate rial to store explosives in NBK. A custom m a d e t a n k o u l d h o ld 50 gallons of explosive s
without fear of it igniting spontaneously.
T h i s f o a m c o u l d a l s o b e p u m ped into walls for insulation/bullet proofing. The carbon is 1000 tim e s s t r o n g e r a s y o u s a i d t h e n
regular insulation and it wont absorb heat so none is lost into the insulation.
Arkangel D e c e m ber 19th, 2002, 12:27 PM

Huh? Why 50 gallons? Igniting....?
It doesn't m atter how strong it is, if it DID blow, som eth ing's going to give. It would just go like a giant firecracker casing.
For non sparking storage (if that's wha t you m eant), read up on explosive storage regulations in your area. The rules for
m agazine construction are pretty clear in most cases, and will let you store explosives safely without using an EXPENSIVE
m aterial like this.
Btw, did anyone read Tom Cla ncy's "Clear and Present Danger"? In that, they have a fibre b o d i e d 1 0 0 0 k g l g b s o i t c o u l d b e
used and folks would think it was a car bom b.
kingspaz D e c e m ber 19th, 2002, 06:39 PM

this stuff cou ld be very useful for the construction of a model plane/flying bomb :)
it's light and strong which m akes it ideal.

W ell there's an idea. An RC glider bom b constructed from carbon foam i m p r e g n a t e d w i t h e x p l o s i v e . W h e n i t e x p l o d e s , t h e
entire thing is consum ed, leaving only bits of the electronics rem aining.
I wonder how "stealth y" carbon foam is? W ould it show up on the millime tric radar used in anti-assassination system s to detect
incom ing bullets?
Perhaps a bullet could be constructed out of carbon foam and fired at hypervelocity via rail/light gas gun?
Positive Electron D e c e m ber 27th, 2002, 01:13 PM

I got one, filling a casing with this foam, then using its porous properties to absorb liquid oxygen for a sm all, but powerful,
explosive. Cost would be a problem though...

You can do that with regular charcoal.
Thin k o f s o m e t h i n g t h a t u s e s t h e f o a m s u n i q u e p r o p e r t i e s t o b e s t a d v a n t a g e .
A-BOMB D e c e m ber 27th, 2002, 05:05 PM
I would use it with epoxy to m a k e g u n c o m p o n e t s .
Yak D e c e m ber 27th, 2002, 08:10 PM

Because of its extream ly strong propertys you could like som e o n e s a i d m a k e a b o m b casing because when it blows the
pressure would build up and its strong so would leave a rather large "dent" in the earth/people aro und it, bullet proofing things
with it could help because its light so it would be portable (but i dont know how lig ht).
Also they say its a "foam" but does that m e a n l i k e a s q uirty foam that you squirt and then it sets or would you need somthing
indu strial because if it was (I doubt it is) but if it was a squirty thing like that would be handy filling in holes and such and easy
m aking of casings.

if its any sort of foam wouldn't that fuck absorb a hell of alot of the shockwave from the explosive? each little pocket of air
requiring energy to crush. i rem e m b e r a n o l d t h r e a d n b k p o s t e d a b o u t u s i n g p u m ice to stop sym pathetic detonation. the air
pockets in th e p u m ice fuck up the tran sm ission of the shockwave.

Ah, but this is (or, rather, can be) OPEN celled foam, un like the CLO SED cells of p umice.
Guns might benefit from it. It's certainly very light, strong, and heat resistant. Though it couldn't withstand the cham b e r
pressures of a conventional slug thrower, it would make an excellent frame for a gyrojet weapon since these produce intense
jets of flame from the rockets.
I t ' d a l s o s e e m p o s s i b l e t o m a ke rocke t nozzles out of the m aterial, thou gh the carbon m a y b e e r o d e d b y t h e i n t e n s e o x i d i z i n g

flam e of the burning propellant.
<sm all>[ Decem b e r 2 7 , 2 0 0 2 , 0 8 : 1 6 P M : M e s s a g e e d i t e d b y : n b k 2 0 0 0 ] < / s m all>

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > chemistry question,
reactivity stuff.. maybe..
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FadeToBlackened December 22nd, 2002, 06:03 PM

Ok.
Some oxidizers release oxygen easier than others, and some fuels burn hotter than others, right? Where are the numbers? I mean, nitrates are a lot easier to use than sulfates
as oxidizers, but why is this, and where may I learn more about it?
We all know magnesium burns hot, thermite hotter, while KNO3 + charcoal, not as hot. I've also heard KMnO4 + Fe goes pretty hot. What is the idea behind why this
happens?
Anthony December 22nd, 2002, 06:50 PM

Heat of decompostion - the amount of chemical energy required to make an oxidiser release its oxygen:
KClO4: -0.68
NH4ClO4: -108.3
KNO3: 75.5
Sr(NO3)2: 92
Ba(NO3)2: 104
KClO3: -10.6
Ba(ClO3)2: -28
A negative number means that the compound gives off heat energy whilst decomposing. Compounds with large negative figures (like NH4ClO4) mean that they can, under
certain conditions, self-oxidise.
Heat of combustion for various fuels (Kcal/gram):
boron: 14
napthalene: 9.6
stearic acid: 9.5
carbon: 7.8
aluminium: 7.4
silicon: 7.4
hexamine: 7.2
magnessium: 5.9
phosphorus: 5.9
titanium: 4.7
PVC: 4.4
dextrin: 4.2
red gum: 4
sucrose, lactose: 3.9
glucose: 3.7
zirconium: 2.9
sulphur: 2.2
iron: 1.8
zinc: 1.3
parlon: ~0
Volcano December 23rd, 2002, 10:31 PM

It's all down to the molecular structure of the compounds. Without going into the realms of quantum chemistry, exothermic (heat releasing) reactions release the stored energy
within the compound itself.
KNO3+S+C react to give SO2, CO3 etc and these products of the reaction have a lower internal energy level than the original reactants themselves. The difference in energy is
emitted as the explosion you see and hear.
You can get a big book on chemistry or maybe learn part-time at college etc. What you are interested in is called Thermodynamics.
vulture December 24th, 2002, 07:50 AM

Redox potential indicates the strenght of oxidizers and reducers in solution and usually this can be used for dry comparison with a few exceptions.
Please don't make the mistake that the more oxygen atoms, the more powerful the oxidizer is.
simply RED January 9th, 2003, 02:28 PM

What is delta Q of the equilibrium
NH4NO3 = N2 + 2H2O + 1/2O2
vulture January 9th, 2003, 03:02 PM

At which temperature?
I don't have any exact figures but this reaction will go to the right above the melting point obviously.

a n d I m provised C hemistry > Nitration of Acetone
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knowledgehungry D e c e m ber 24th, 2002, 04:48 PM

As i posted earlier i tried to separate HNO3, which i synthesized, from t h e a m m onium sulfate it was mixed with . I
did this by m ixing acetone in with the m ixture then decanted it off. The first tim e i tried th is it worked and the aceto n e
evaporated off and i was left with relatively pure HNO3. When i tried to do it in larger quantities i got runaway
nitration of the Acetone. I was wondering if anyone had any idea what the resulting com pound would be called or look like. I
could not test the pro perties of my nitrated ace tone as i had to quickly dum p the reacting mixture down the sink to spare
m yself from NO 2 poisoning.
Also if this compound h a s a n y u s e .
W hen i get b ack from visiting my relatives i will try a m ore controlled synthesis of whtever the hell it was that i created.

Maybe it's not a nitration. It could also b e a n o x i d a t i o n .

wouldn't it just be eth anoic and m ethanoic (ace tic and formic) acids?
l i k e n b k s a i d , its possible the acetone got oxidised. releasing NO2 as a result. i don't know m uch about oxidation of things
using nitric but i'd guess it would be for a sim ilar reason as to why dissolving Ag in nitric releases NO2. Ag is hard
to oxidise and so is acetone because its a secondary aldehyde (known as a ketone :p ).
just my alm ost random guesswork answer to it.
simply RED D e c e m ber 25th, 2002, 03:46 PM

Once i tried to m ix acetone with HNO3 and H2SO 4 (i don't know why) and also a runeway occured.
Theoretically if you m ake low temperature nitra tion the next reaction is p o s s i b l e :
C H 3 C OCH3 + 2HNO3 = C H3-C (O NO2)2-CH3 + H2O
C H 3 - C ( O N O 2 ) 2 - C H 3 m u s t h a v e t h e s a m e properties as nitroglycerine
megalomania D e c e m ber 27th, 2002, 02:21 AM

I don't think you can nitrate an aldehyde or ketone, but I just m entioned in the FOX-7 thread about reacting acetaldehyde, an
alde h y d e , i n t o g l y o x a l , a d o u b l e a l d e h yde. There is no reason why a ketone should not work in the sam e way, probably
o x i d i z i n g b o t h e n d s o f a c e t o n e i n t o s o m ething... som ething quite weird which I have no idea what the name m ay be. I have
m y m olecular modeler and FTP already open so lets draw a picture:
<img src="http://www.roguesci.org/im ages/tricarbonyl.gif" alt=" - " />
I found nothing in Merck, Aldrich, Chemfinder, or O rganic Synthesis that m atches this m olecule. It may also becom e a diol or
carboxylic acid, like so:
<img src="http://www.roguesci.org/im ages/acediol.gif" alt=" - " />
Of course we all wish this would happen:

<img src="http://www.roguesci.org/im ages/fancypoly.gif" alt=" - " />
NoltaiR D e c e m ber 27th, 2002, 02:55 AM

Of coarse the priming shockwave itself would have to super-powerful just to get a result even close to the theoretica l (which I
a m not sure how m e g a c a m e u p w i t h t h e i d e a o f 2 7 k m / s ) . A n d I a m n o t t o o f a m iliar with the idea of how a NO2 wo uld be split
to releaste the nitrogen needed to for the pressure blast effect and how the oxygen would t h e n b e u s e d t o m a k e a c o m p l e t e
combustion...
megalomania D e c e m ber 27th, 2002, 05:56 PM

I was actually joking with this com pound. My "wish" is th at nitrating acetone would form a s u p e r h i g h d e n s i t y e x p l o s i v e m ore
powerful than anythin g in existance :D
knowledgehungry D e c e m ber 31st, 2002 , 11:54 AM

W ell the m ixture of Acetone and HNO3 has been sitting around for about a week, it looks like the attempted
phorone(dark red) but that could just be NO2conta m i n a t i o n . I t o o k a s m a l l a m ount of it and lighted it, it burned
but it was just the acetone burning. As the m ixture started to heat i got more of the runaway nitration/oxidation with large
a m ounts of NO2fum es com ing off there was only a sm all am ount of product left in the beaker, less th an 1/2 m l.
I m g o i n g t o h e a t s o m e m o r e o f t h i s m ixture to day outside, and see what is left in my flask.
Pu239 Stuchtiger January 1st, 2003, 01:44 AM

Generation o f NO2 gas is evidence that oxidation is occuring.
Mega: Acetone can be nitrated. And I believe that the first comp ound you drew is very unstable. Two adjacent carbonyl groups
are unstable; three adjacent are very unstable. That also rules out the possibility of the carboxylic acid that you diagramm e d
a s b eing stable. CH3 gro ups aren't oxidized as readily as CH2O H groups, so the diol would only be
form ed in sm all am ounts. This is probably what is happening:
CH3--(C=O)--CH3 ---(oxidation)---> HO CH2--(C =O)--CH3
And then lots of relatively com p l e x s h i t h a p p e n s, but I'm too fucking lazy to boot in W indows and draw diagrams. O h well.
Ta-da. *band plays*

nbk2000 January 1st, 2003, 02:43 AM
Knowledgehungry, you say that you evaporated off the acetone and was left with concentrated nitric. How do you know it W AS
nitric, and that it wasn't just traces of sulphuric acid and not concentrated nitric?
knowledgehungry January 1st, 2003, 01:02 PM

The first tim e i am not sure that it was pure nitric( except that it gave off the choking odor and when heated it decom p o s e d
into NO2 gas)
In m y s e c o n d a t t e m p t which resulted in the rea ction which we are currently discussing I used an excess of NH4NO3so i believe that all the sulfuric was reacted. I'm quite sure now that this m ethod will NOT work for
obtaining pure nitric(m y first attempt was in such a sma ll am ount that it was im possible to tell whether all the acetone had
evaporated)
drednort January 10th , 2 0 0 3 , 0 4 : 1 7 P M

S o m ething I have done before to clean particularly dirty glassware is to put conc nitric and a bit of ethanol together. It is pre tty
e x o t h e r m ic with the e volution of brown fumes. I once swapped the ethanol for THF and no t h i n g h a p p e n e d f o r a f e w m i n u t e s .
Then the whole fumecupboard flashed luckily the visor was down . Anway, the nitric acid / a cetone sounds a bit like that. It is
probably oxidative degradation that you saw.
BASF January 10th , 2 0 0 3 , 0 5 : 0 6 P M

Maybe the following patent is of interest.
It describes the form ation of an energetic material from acetone and dilute (or concentrated) HNO3.
United States Patent 5,043,488

Schulz , et al. August 27, 1991
Greets to all being curious
nbk2000 January 10th , 2 0 0 3 , 0 7 : 5 9 P M

It would seem , from what I gathered from the patent, that you could make this explosive by m ixing sulphuric and potassium
nitrate, lettin g that fo rm nitric in situ, then dum p it into a filter and wash the nitric out from t h e i n s o l u b l e s u l p h a t e u s i n g
acetone.
T h e n s i m ply reflux on a hot water bath.
Since there'd be no water in the process (unless it's formed), you wouldn't have to bother with a distillation. Simply use as is as
an explosive.
Though it bothers m e that they didn't m ention anything about detonation velocity. They just compare the nitrogen content to
other explosives. That in itself doesn't give any m easure of its power.

a n d I m provised C hemistry > C olor of Fe2O 3
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mongo blongo D e c e m ber 26th, 2002, 03:40 PM

I m a k e m y F e 2 O 3 u s i n g A m m o n i a ( 9 % ) a d d e d to a solution of Iron II Sulphate. I then filter and cook the ppt which is
o x i d ized by the air.
Each batch of the fully dry Fe2 O3 ends up as a slightly different colour. I have had from light brown to dark red to bright
orange.
Does anyone know why this is?
I was thinking that maybe a d ifferent % of the ppt is oxidized in each ba tch which could m e a n d i f f e r e n t a m o u n t s o f i r o n i s
produced in a thermite reactio n?
Any ideas?
Marvin D e c e m ber 26th, 2002, 06:58 PM

T h e r e a r e q u ite a few factors that might affects the result. How much water is in the final product, how hot are you cooking it?
also how much of the m aterial actually oxidises, FeO is pretty stable and I'm not sure how m uch roasting, or at what
temperature is required to oxidise it. The partical size o f ppts has a lot to do with aparent colour and how this is affected by
the roasting Ive no idea. Add to that a ny am monium sulphate/ferrous sulphate left in after filtering, the amm onia would
probably be driven off leaving an acid to attack the oxide, which at a higher temp would itself be driven off. A lot of things
c o u l d b e g o i n g o n t h a t m ight affect the product, and without testing you cant be sure if its superficial or not.
russian_chemist D e c e m ber 26th, 2002, 10:57 PM

T h a t s t h e t h i n g w i t h m a k i n g a c o m p o u n d , t h e r e a r e s o m a n y v a r i a b l e s t h e o u t c o m e o f t h e e l e m e n t s h a s t o play against it
could be anything.
The only thing that is a certain for m e in colour is when i deal with one Elem ent. Be it AN o r whatever.
with fe203 i always see it come out the sam e colour as the brine of prilled Amm onium Nitrate after a good crystalisation. That
is always the same for me.
Good luck
mongo blongo D e c e m ber 27th, 2002, 12:04 AM

AN is not an element and it should be white. :)
There is no particle size until it's dried (the ppt is like a slurry). There is little water in the ppt as I squeeze as m uch water out
b e f o r e c o o k i n g . I u s e a cast iron pot on a cam ping gas burner.
This still leaves the m istery of what factor changes the color.
Heat is m ost probably the factor. I say this because bits of the ppt land on the floor (cold) and it always seem s to turn out
bright orange stain rather than a darker red fro m t h e s a m e b a t c h .

a n d I m provised C hemistry > Nitration without th e use of acid?!?!
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zeocrash January 10th , 2 0 0 3 , 1 2 : 1 4 P M

OK i'm trying to m anufacture chloropicrin. i'm planning to use the nitratin g chlorinated hyd rocarbon s m e t h o d . u s i n g
dichlorom eth ane (from paint srtipper)
6CH2Cl2 + 4HNO3 ==> 4C Cl3NO 2 + 4H2O +C2H4
but upon closer inspe ction of m y source (a US army field manua l on chem ical warfare agents) I discovered that Chloropicrin is
broken down by acid to form CX a blister agent. which i'm not prepared to handle yet.
is th ere any way that i can nitrate the dichlorom ethane, without using acid. or doe s anyone know how i could use acid but
prevent the production of CX.
----------------------------------------------------------------------
the PDF file of the field m a n u a l h a s b e e n u p l o a d e d t o t h e F T P a n d i s n o w i n t h e r e c e n t s e c t i o n , s o t a k e a l o o k t h e r e i f y o u
want
MrSamosa January 10th , 2 0 0 3 , 0 4 : 1 3 P M

T h a n k s Z e o , y o u h a v e j u s t g i v e n t o l d m e of a new, seem ingly easier way to prepare CX :D .
Although for your little problem, might I suggest that you try the Nitrome thane/Sodium Hypochlorite Method? The chem icals
s e e m so much easier to obtain than Nitric Acid. Any concentration of the Hypochlo rite works; although lower concentrations, as
f o u n d i n b l e a c h , m a y r e q u i r e s o m e heating. Th e entire reaction only takes about 20 m inutes, and the yields are great.
From my personal experience with this m ethod, it works wonderfully. But, if Nitrom ethane is difficult for you to obtain, then this
m ethod may not be helpful.

where would i find nitromethane
no i chose th e nitrating chlorinated hydrocarbons m etho d because i've got a whole load of nitric acid. but th e m e t h o d a p p e a r s
im p o s i b l e a s a n y P S m ade is instantly converte d to CX by the acid as i've m entioned previously. i was thinking that bubbling
nitric oxide through the dichloromethane
____________________________
the paint stripper that contains dichlorom ethane is called nitromors. it also contains methanol so it m ay need to be distilled
the field m anual is in the rece nt directory of the ftp as fm 3 - 9 . p d f
kingspaz January 10th , 2 0 0 3 , 0 7 : 1 5 P M

dichlorom eth ane doesn't react with nitric acid. it is inert towards it, hence its use in solvent extraction of HNO3 from x H S O 4 /
HNO 3/H2SO 4 m ixtures. do a search for a topic called solvent extraction.
nbk2000 January 10th , 2 0 0 3 , 0 8 : 4 2 P M

From my inform ation, the PS to CX conversion needs to be done with Tin m etal (though you could likely use cheaper zinc or
iron) and acid, to reduce the PS to CX. Acid alone would likely achieve on ly trace am ount conversion.
The NM/Bleach process is m uch easier and efficient than trying to nitrate anything. Pool bleach is 10%, m ore than a d e q u a t e f o r
the process.
MrSamosa January 11th , 2003, 05:45 AM

Zeo- Nitrom e t h a n e c a n b e o b t a i n e d f r o m a l o c a l H o b b y S h o p . I t ' s s o l d a s R ace Car Fuel (the RC type). If not, I'm sure you can
find it from some online hobby dealer. The only problem with it, however, is that it is so bloody expensive pure. Usually it is
sold in m ixtures of Methanol and Castor O il, as m ine is.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > phosphorus
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zeocrash January 13th, 2003, 03:07 PM

Ok i was looking for a method to manufacture phosphorus, i searched the forum and archives and found an old post by NBK about the manufacture of phosphorus from an old
19th century chemistry guide. one of the replies though mentioned the production of phosphorus by heating with coke and sand.
the reinhold chemical dictionary says that phosphorus is produced industrially using this method. in an electric furnace. the phosphorus is then apparently driven off and
condensed under water. I was wondering if anyone had any ideas about how to do this practically in the lab. I was thinking of using a condenser, but the phosphorus would
solidify in the condenser and bung it up. another idea i came up with was to use a column of water or something similar and pass the vapour up through the column to cool and
condense, where i would skim the solid off the top (i think phosphorus floats). i could also use an inert gas to pass through the equipement to make sure the phosphorus does
not combust. I was wondering if anyone knew anything else about this method, or knew an easier way of doing this.
a_bab January 13th, 2003, 05:42 PM

The WP won't float, it's heavier then the water. And assuming that your mini-furnance it'll be isolated from air, and it should be, there will be presure built in it because of the
WP vapors. All you have to do is to drive these vapors in cold water; the vapors will be hot enough to heat the tube so there will be no problem concerning the solidification of
WP in the tube.
FadeToBlackened January 13th, 2003, 05:58 PM

I'd just like to clarify something, heating coke+sand will not yield phosphorus, the sand is an addition to the coke+phosphate, which nbk (I think) said combines with residual
calcium after the phosphorus has been driven off.
THErAPIST January 13th, 2003, 06:44 PM

I once read something in book at school that had the discovery and such of all of the elements on the table. When I read about phosphorous i remember something being said
about a 5 gallon bucket being filled with urine and then it was set outside for a week or two untill worms and stuff started to crawl around in it. Then it was boiled untill all that
remained was a crude form of phosphorous which had to be treated with alcohol or something of the sort. I'm not too sure about it so I'll find the book and post what it says if i
can.
Sparky January 13th, 2003, 07:13 PM

There is a book called "The 13th Element" on the FTP. Phosphorous being the 13th element discovered. I think it is in the uploads section though. It is also on the Mad Science
FTP. If you have a place to put it I can upload it somewhere. It is a bit over 1.8 megs.
Edit: I 'found' it on this webpage:

<a href="http://pyropage.cyberarmy.ca/13thelement/" target="_blank">http://pyropage.cyberarmy.ca/13thelement/</a>
[ January 13, 2003, 08:26 PM: Message edited by: Sparky ]
nbk2000 January 13th, 2003, 09:08 PM

All that "fermenting till worms..." crap is unneccessary. Just set the piss out in shallow trays to evaporate and collect the phosphate salts the remain. Mix with carbon and sand,
heat to over 1000*C, and collect the vapors in warm water.
A furnace capable of melting copper should be hot enough. The furnace is the hard part.
megalomania January 13th, 2003, 11:10 PM

There have been other threads concerning this matter not so long ago. I believe it was Polverone who tried an experiment very much like the one you have described.
Obtaining P from urine is another matter we shall not concern ourselves in this thread.
The industrial reaction is more efficient in terms of producing more P from the same chemicals than using more laboratory means. There is another thread I believe that
describes the production of P from ordinary chemicals.
I have given some thought in the past on improvising an industrial based setup, along with other methods. The first problem is making the electric arc. This is necessary to
provide the high temperatures needed to initiate the reaction, but an electric arc is not essential, just more convenient to industry. You will have to have some type of high
temperature furnace, which I do believe can be improvised. There are a few documents on the FTP that seem to indicate they are about making such furnaces, but I have not
checked them out yet. You can use an iron or steel pipe with pipe caps screwed on to make a reaction flask (like a pipe bomb). The reactants are mixed in the pipe which is
placed in the furnace.
The top of the pipe can be connected to an adapter letting you run a length of metal tubing under water. You may need a reducing adapter or two along with a pipe thread to
flair fitting adapter to use a small diameter copper tubing that can bent, or use steel pipe with some elbows. Either way the intent is to lead the exhaust gas into a container of
water.
The equipment is rather simple, the reaction not complex, the only problem will be getting it hot enough. Solve the furnace step first, and the rest should be easy. You do not
need to use a regular condenser, and inert gas, or indeed any standard lab equipment. Any air in the setup will not last long. The only problem I foresee is the possibility of a
suckback of water into the very hot metal pipe, a trap can stop this, but it may get filled with a little P. P may also condense on the insides of a tube if it cools off enough
enroot to the water. These are problems that only experience with using such a setup can resolve, if indeed they happen at all.
nbk2000 January 13th, 2003, 11:29 PM

I don't think water suckback would be a problem if you placed the condenser tube just under the water. Any water that did get sucked back up would be turned into steam in
the hot condenser tube long before it got into the actual retort.
I don't see why it's so hard to make WP. They managed it back in the 17th century for Gods sake!
Polverone had the problem of the mix forming a glass in the retort. Perhaps if the retort was rotated along the horizontal plane, the reaction mix wouldn't be able to solidify
into a solid cake, and would increase surface area for vaporization of the P.
THe_rEaL_dEaL January 14th, 2003, 03:50 AM

An idea! (holy shit!!!) :D
To keep the vapor from condensing on the inside of the metal tube on the way to the condenser you could just keep the tube at elevated temps.
This could be achieved with a resistance coil around the tube or a gas BBQ burner (the long narrow burners used on BBQS)
Polverone January 14th, 2003, 04:30 AM

There is hardly any problem keeping the metallic venting tube warm if it is emerging from a furnace and not terribly long. Resistance heating is not necessary. The glassy
reaction products are a real bitch to remove mechanically and I didn't find (in my short search) any reagents that would attack the crap without attacking the reaction vessel
itself. I have collected some documents and performed some preliminary experiments that indicate aluminum is a significantly better reducing agent than carbon for phosphorus
production. Don't try using fine aluminum powder; it's too reactive and could present a real hazard if it were heated in confinement. Aluminum reduction wouldn't be cost-
effective on an industrial scale, but I don't need 50000 kg/month of phosphorus. Another good idea, suggested by Vulture I believe, was to try using CaC2 as a reducing agent
for phosphates. I have not yet tried this method. Oh, BTW, it seems to be a much better idea for the home experimenter to use metaphosphates as opposed to plain old
phosphates, as they have much more reasonable melting points (to mingle them with the reducing agent). My horrible sticky-then-glassy something-or-other phosphate (some
sort of metaphosphate, I would think) was produced simply by strongly heating diammonium phosphate (used as a nutrient in brewing).
I imagine (imagine, mind you) that phosphorus production would be pretty simple if I had a decent furnace on hand. But I don't have a decent furnace on hand, this rental
didn't come with a machine shop (pity), and a gas burner just doesn't give the heat that I need. If I were out in the boondocks I would build a nice big fire in a pit and feed it
air from a hair drier or the like. Does anybody here live out in the boondocks? Sure you do. C'mon, be a pioneer.
Edit:
See
SOME RECORDS OF THE YEAR'S PROGRESS IN APPLIED CHEMISTRY.1

Wm. McMurtrie;
J. Am. Chem. Soc.; 1898; 20(12); 967-987.
Tantalizing bit:
"Franck has likewise utilized the high combustion temperature of aluminum for the reduction of oxides both metallic and non-metallic and particularly the production of
phosphorus. For this latter purpose he mixes the metaphosphate with silica and aluminum, and heats the mixture to start the combustion when the reduction proceeds quietly;
the phosphorus distills readily and yields an excellent product particularly when the lime compound is employed."
Now to find out who this Franck was, learn the details of his process, and see if it's practical on a lab scale.
[ January 14, 2003, 04:03 AM: Message edited by: Polverone ]
nbk2000 January 14th, 2003, 04:58 AM

So you think chunks of aluminum metal would be better than carbon? It'd certainly be easier to make a furnace capable of melting aluminium than one capable of melting
copper (or iron).
I'd also think that having a large surface/volume ratio would help in allowing the P to volatilize off as fast as it was formed. If I remember correctly, your pipe retorts were
vertically oriented?

Not chunks, more like coarse powder or perhaps shredded foil. Something with decent surface area that can be mixed with the other materials prior to loading in the reaction
vessel but that isn't so fine as to be dangerously reactive. Just after I edited that post I realized that I had (unknowingly) referenced Franck before in one of my other
phosphorus posts. Sadly, the original article is in an old German journal. But I think there are enough details to try some experiments. Phosphorus from shredded foil,
homemade calcium metaphosphate, and diatomaceous earth? This could be more fun than homemade cyanides if it works out :D :D
nbk2000 January 14th, 2003, 05:29 AM

Think you could make a "jelly" roll out of reynolds foil and metaphosphate? Toss the roll into the pipe (horizontally, of course) and roast.
At the time of that journal reference, it was probably prohibitively expensive to use aluminium since it wasn't till the 20's or 30's that tha Alcoa process was discovered to make
it cheap to make. Which is NOT a problem nowadays.
Machavelli is in Germany. Perhaps he could call some local universities and obtain a copy of the journal article and translate it? :D
Last I heard, RP was going for $1,000/Kg for use by meth cooks. Being able to whip it up yourself could put you in good finances. :)
With OTC cyanide and WP production processes in hand, you've got one of the (un)Holy Grails of IW...Nerve Gas. :D Ah, nothing like a whiff of Tabun in the morning to get the
ol' juices flowing, eh? <img border="0" title="" alt="[Wink]" src="wink.gif" />
[ January 14, 2003, 04:35 AM: Message edited by: nbk2000 ]

I imagine that using aluminum as an intermediate would still be industrially undesirable since it represents another step, produces more waste, and takes a lot of electricity but
such economic considerations are of little importance to the home chemist. I spoke too hastily about the journal article. It appears to actually be in English and was posted on
Usenet some months ago as part of a long discussion about thermite. Search for Franck in the "new adventures in cyanide" thread to find the text. It is fairly detailed, though
not meticulously so.
Phosphoric anhydride, phosphorus halides, phosphorus as a catalyst, phosphorus as a reducing agent... Phosphorus opens up many synthetic possibilites. I doubt I'll ever be
trying for homebrew Tabun, but there are many things I would like to use phosphorus for. At one time I believed that phosphorus production would very much ease the task of
methamphetamine synthesis, but I now believe that HI reduction is a method whose days are numbered. Eventually the pills will no longer be OTC and the dumbest of the
cooks will have to find an entirely different hobby. The better ones will just go after P2P as they have for years. In the short term, you are very correct that you could make a
good living just peddling RP (if you're not caught).
The jelly roll idea isn't bad. The powder would need something to stick it to the aluminum while it was rolled up; maybe just a light misting of sugar water, spray-on adhesive,
or the like. Dampen, coat, roll, dry at low heat, place in reaction chamber, heat intensely... and hopefully reap white phosphorus. That would make my day. It would make my
whole month.
Alchemist January 14th, 2003, 11:03 AM

Hello all,
several years ago I had several grams of RED Phosphorus and tried to convert it t YELLOW by distilling it. I use a glass retort and put the end into warm water. After heating
started the YELLOW Phosphorus started comming over just fine. After all the RED was converted I removed the heat. A lot of YELLOW Phosphorus had collected on the neck of
the retort and as the system started to cool down the water did start to suck back into the retort. As I did not want to break my retort I (NOT THINKING) removed it from the
water. As air rushed in and hit the hot Phosphous there was a load explosion and the retort went everywhere. I had glass cuts all over my face, but my eyes where ok (thank
God).
The point here is to use caution, be aware of air leaks, metal pipes(etc) could be a real danger!
Good luck to everyone with this research, Phosphorus is a VERY needed element with many uses.
P.S., for a arc furnace see my upload to the FTP on making Calcium Carbide!
Mr Cool January 14th, 2003, 01:49 PM

Furnaces are easy to make, a google search will turn up loads of references, both on charcoal and gas burners. Even a bunsen burner can be converted into a little mini-furnace
quite easily.
The simplest way would be to have a large flower pot full of crushed charcoal, with your reaction vessel inside, and blow hot air in the drainage hole at bottom from a paint
stripping gun. These are available at DIY stores, and are GREAT. The one I have blows out air at something like 400*C (hot enough to ignite wood on its own, so it must be
pretty hot), and when I blew it into a coal fire it got the temperature high enough to melt the end off a cast iron rod that's about 1cm diameter. Plenty hot enough for all your
phosphorous/cyanide/CaC2 etc needs.
Checking my garden centre catalogue I see that monoammonium phosphate is 5/kg, which I'm sure is cheaper than buying it as a brewing nutrient, which I've never seen in
more than 50g tubs. If you could get a 50% yield that'd be a fiver for 300g of WP, then sell it at $1000/kg to Hive bees... :D :D
The biggest problem that I see is how would you disassemble your apparatus for the next batch? You'd have to use metal with screw threads, which would get gummed up
with this phosphate glass and Al2O3, forming a nice adhesive, and if you did get it off it'd immediately burst into flames!
Maybe you should have a pipe through which you can blow [insert any inert gas here] into the vessel, then you could get everything very hot, blow CO2 through, and this
would vapourise and blow out the last of the phosphorous which, if there was enough, could be collected, or otherwise allowed to burn off. And you could then unscrew it while
hot... so maybe it wouldn't be a problem after all.
"and heats the mixture to start the combustion when the reduction proceeds quietly"
Something like this would be nice - basically a mild pyrotechnic mixture that yields phosphorous during combustion. Then no furnace would be necessary, just an ignitor!

I tried using calcium carbide to reduce sodium metaphosphate. It didn't work, at least not with a gas burner as my heat source. I still need to make another attempt with
aluminum (hopefully silica too, next time).
<blockquote>quote:<hr />Something like this would be
nice - basically a mild pyrotechnic mixture that yields phosphorous during combustion. Then no furnace would be necessary, just an ignitor!<hr /></blockquote>No kidding. It would be another proud step on the path toward World Domination (or whatever it is at the end of this path I'm
walking).
knowledgehungry January 18th, 2003, 10:20 PM

I read somewhere that the insides of flourescent lights were coated with P. I am not sure whether that was elemental P or a compound containing P. I doubt that this would be
a cheap or efficient way of obtaining P but i thought that you might like to know.
A43tg37 January 18th, 2003, 11:07 PM

knowledgehungry,
The insides of fluorescent lights are coated with phosphors, not phosphorous itself. The phosphors are chemical compounds (oxides, fluorides, and vanadates, to name a few,
with some of the higher efficiency fluorescent lights using rare-earth compounds), not the element phosphorous. There may be some fluorescent lights that utilize phosphorous
compounds (but it seems rather dangerous to put these compounds inside one, given that they can burst if hit by water, and the resultant mess would probably be toxic), but
I've never heard of any. Even if there are lights that use phosphorous compounds, it seems better to stick with the production from phosphates or phosphate derivatives, as
that method would yield larger amounts than could conceiveably be obtained from a reasonable number of fluorescent bulbs.
[ January 18, 2003, 10:17 PM: Message edited by: A43tg37 ]
Machiavelli January 19th, 2003, 05:06 AM

Polverone, if you give me the reference, I'll see whether I can get it.

I was wrong about it being in German - sorry. The text can be found in the "new adventures in cyanide" thread, which drifted off-topic (as threads have a habit of doing) and
started being about phosphorus production.
FlaAlchemist June 18th, 2003, 02:01 AM

For lab scale quanities, all you need is the iron pipe setup described in this thread . Instead of the furnace just heat the iron tube with the propane torch. It will work, but be
very careful with the white phosphous obtained..and be sure to remove the receiver before blowing out the torch or the water will get sucked back into the pipe. The yield is
not that great but it does work..
I do all my experiments on a semi-microscale 1st...then scale up after i get all the bugs worked out.
nbk2000 June 18th, 2003, 05:48 AM

So then you'll post pictures of your WP? Because we'd all like to see this very much, as it's been such a hassle that none of us have succeeded at it yet.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Boron - only useful
for ignitors?
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A few quick sums will show the following energy releases, per gram of fuel burning in excess oxygen:
WP: 24.3 kJ
Al: 30.9 kJ
C: 32.8 kJ
B: 57.5 kJ - <img border="0" title="" alt="[Eek!]" src="eek.gif" /> a full ten times that of a decent HE detonating!
(Beryllium beats it at 67.9 kJ, but would make clouds of toxic oxides and isn't commonly available)
And yet it seems to only be used in ignitors and as a green colourant :confused: .
Well, I think it deserves a bit of experimentation.
I intend to make some next time I have a bit of free time.

Na2B4O7 + 2 HCl --> H2B4O7 + 2 NaCl
H2B4O7 -(heat)-> 2 B2O3 + H2O, I think
B2O3 + 3 C -(heat)-> 2 B + 3 CO
Should be easy, right? We'll see...

And it'll give me another reason to set up some sort of furnace for large batches if it works. I've been wanting a furnace for a while, but have never had enough reasons for me
to actually decide to try and make one, so I always end up using the fire in the house!
Even if it isn't great for pyro things, it'd be a neat experiment. I'd try to make crystalline boron too, it's almost as hard as diamond and looks kinda pretty.
<a href="http://www.theodoregray.com/PeriodicTable/Samples/005.2.JPG" target="_blank">Crystalline Boron</a>
[ January 14, 2003, 04:33 PM: Message edited by: Mr Cool ]
firebreether January 15th, 2003, 12:15 AM

The problem is that saying that it has a lot of energy per unit mass fuel is misleading, because if you tried to do it in terms of total mass, then B would be less than something
like Al. So for pyro comps, where it is the ox+fuel that matters, Al is a better choice(cheaper too) No doubt its always good to try new things though :D
nbk2000 January 15th, 2003, 02:27 AM

There's a green mineral that's fairly cheap (I think it's called "beryl") that's mainly beryllium oxide. Crush it into a powder, reduce in H2 atmo., and proceed form
there. Or simply disperse the powder as is, since beryllium is very toxic.
I remember reading that boron "whiskers" are used in ceramic armor to prevent crack propagation.
irish January 15th, 2003, 06:49 AM

beryl is beryllium aluminium silicate, it's not toxic due to being practicly insoluble .
it's also the main commercial source of beryllium I will try to find out how they extract it .
Flake2m January 15th, 2003, 09:28 AM

Beryllium Oxide is not toxic, but it turns into Beryllium Hydroxide which is very toxic.
I went to a universtity open day last year and I saw a reaction with boron, the really wierd thing about it was the fact that the flame was completly green <img border="0"
title="" alt="[Eek!]" src="eek.gif" /> .
Boron is also used in some weed killers aswell as in Ant killer, but the concerntration is quite small.

Where I live they sell this stuff called Borax in the supermarket
From memory its like a compound containing boron
Something along the lines of boric acid
Not fully sure if its an acid but this is cause I'm too lazy to search cause I'm tired as shit
Its made by Hovea or Diggers I think
So if anyone can be fucked then they could find the MSDS or go down to the supermarket and check it out!!
This isnt a question so I'm not breaking the rules, only a statement with a sugestion. :cool:
rikkitikkitavi January 15th, 2003, 01:11 PM

well asbetos isnt toxic either, but not something you want to inhale.
BeO is worse...
gives you beryllosis (as asbetosis) and you can sign up for a lungtransplantation you you live that long.
soluble Be-compounds are toxic.
/rickard

Damn, I hate it when you type out a reply and your computer fucks up and you lose it :(.
firebreether, yes you are right! I overlooked that fact [*hangs head in shame*]. I worked it all out and in a mixture with KClO3, Al just beats boron. But that was lost when my
computer screwed up :(.
THe_rEaL_dEaL, borax is Na2B4O7, which is what I intend to make it from.

Mr. Cool, You don't need the intermediate steps, you can produce boron from borax, by heating it with carbon:
Na2B4O7 + 7C -> 4B +2Na + 7CO
I don't know if the sodium metal will cause problems. Could be a bonus.
Boron oxide can of course be reduced by magnesium

B2O3 + 3Mg -> 3MgO + 2B
The first samples of boron were made by reacting boric acid with potassium metal, but that is impractical for us.
In case you care, I got this quote from a Exploring Chemical Elements and their Compounds (I have found this book so useful you can watch for it appearing on the ftp,
possibly next month):
"High-purity boron, on the order of 99.99% can be produced by the electrolysis of a molten mixture of potassium flouroborate and potassium chloride."
The same book has this reaction in it (This reaction must be heated):
Na2B4O7 + 2HCl + 5H2O -> 2NaCl + 4H3B04
So maybe the first reaction you described would be impractical.
BTW borax comes as Na2B4O7.10H2O

<blockquote>quote:<hr /> you can produce boron from
borax, by heating it with carbon:
Na2B4O7 + 7C -> 4B +2Na + 7CO <hr /></blockquote>That equation seems right in theory but in reality the Na
would form a salt (maby NACL or Na(CO3)2 wouldnt it?
I find it hard to accept that such a highly reactive element (reactive to air and water) in its pure form, would just exist in the presence of water or oxygen without causing a
further reaction to create an Ionic salt of some sort.
I think I'm mostly correct.....? :)
I'm guessing that Boric Acid produced form Borax is further reacted to yield elemental Boron?
Microtek January 17th, 2003, 06:47 AM

I have been contemplating using boron as fuel in incendiaries. My resoning was that while Al does give a slightly better output per gram of thermite, boron is a lot harder and
therefore probably easier to pulverise so it might be easier to prepare boron powder than Al powder. What I found when I did some calculations on the kinetics of discouraged
me however so I never did the experiment.
I considered this method:
- Reacting borax with HCl in H2O to convert to boric acid and then reducing with carbon. 2H3BO3 + 3C --> 2B + 3H2 + 3CO2.
This reaction require about 930 C to run assuming that deltaS standard and deltaH standard does not depend on temp ( which they probably will but hopefully not too much ).
There is a problem though; H3BO3 boils at a much lower temp, something like 180 C IIRC.
So, I considered this method instead:
- Burning borax and leaching out the Na2O with water to obtain B2O3 then 2B2O3 + 3C --> 4B + 3CO2. B2O3 is not easily evaporated so that should take care of that
problem. This rection requires a temp of more than 2500 C to be thermodynamically favored which is optimistic for any non-electric furnace.
Reduction of B2O3 with Mg is spontaneous ( except for activation energy ) at all temps so this can be done, just keep the amounts small as this is a thermite reaction itself. All
in all I think it would be rather messy so I haven't tried it.

I think I might use a mixture of Mg and C to reduce B2O3, in a crucible with a lid or something similar. That way, hopefully the energy released
from the Mg + B2O3 "thermite" reaction will supply the energy needed for the C to reduce B2O3. MgO can then be
removed with dilute HCl, and I expect any excess C would easily be removed by crushing it up and decanting from water (C having a low density will take longer to settle, so
it could be poured off from the B as a suspension, maybe).
I'll let you know if it works when I try it, which will hopefully be this weekend. I might start off just using Mg as the reducing agent.
Edit: I don't think it will be this weekend, I'm feeling very hungover...
I hate tequilla.
[ January 18, 2003, 08:08 AM: Message edited by: Mr Cool ]

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Hydrogen Peroxide
decomposition data
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rjche January 20th, 2003, 10:47 AM

Those working with HP need to know how much it deteriorates with time.
This data is from a HP mfg page. It states deterioration is about 1% per year.
It also gives data on the usual type HP avaiable to experimenters.
Note that this technical grade may contain some non organic stabilizing chemicals. Nothing more is said about that.
(In my opinion is they would be trivial quantities, and apparently from its successful use for AP production, they have not shown any interference.)
The MFG data:

-------------------------------------
Technical Grade hydrogen peroxide is used in the pulp and paper industry in bleaching chemical and mechanical pulp and in waste paper recycling. In the textile industry, it is a
bleach for natural and synthetic fibers and a desizing agent. It also safely detoxifies many industrial wastes,including phenolics and reduced sulfur compounds. Technical Grade
hydrogen peroxide is also used in the extraction and finishing of metals.
Technical Grade hydrogen peroxide is also available in concentrations of 35% and 50% in truckload drum shipments. Less than truckload shipments of hydrogen peroxide are
available from distributors.
(Small (gallons) amounts are available from local chemical supply houses. Last I bought was about $usa 10 per gallon 50%)
Physical Properties: Hydrogen peroxide is a clear, colorless, slightly viscous liquid. It is slightly denser than water but is miscible with water in all proportions. Hydrogen peroxide
decomposes exothermally to water and oxygen with no toxic residues.
The decomposition is normally slow (<1%/yr) with no temperature rise but is accelerated by heat and decomposition catalysts, such as transition metals and their
compounds, strong acids and strong alkalis.
Typical Analysis 35% 50% 70% Concentration in water,

Appearance Clear, colorless
Storage and Handling* Store hydrogen peroxide in the original vented container, upright, in a cool, ventilated area where it is protected from damage.
Water is the preferred method for extinguishing fires in which hydrogen peroxide is present.* Spills and leaks should be contained, diluted with copious amounts of water.
First AidIn case of product splashing into the eyes and face, treat eyes first.
Eye contact:Flush eyes immediately with water for at least 15 minutes. Call a physician.
Skin contact:Immediately flush skin with water while removing contaminated clothing andshoes. Call a physician if irritation persists.
Inhalation:Remove the victim from the contaminated area to fresh air. Call a physician incase of respiratory symptoms.
Ingestion:Consult with a physician immediately in all cases. DO NOT induce vomiting.If victim is conscious, rinse mouth and give fresh water.In case of ingestion, sit upright,
drink large quantities of water to dilute the stomach contents and seek immediate medical attention.
Danger:Hydrogen Peroxide solutions are strong oxidizers and corrosive to the eyes, mucous membranes and skin.
My comment: treat HP solutions above about 15% as carefully as your would similar concentrations of nitric acid.
The 1% concentration decay per year in normal room temp storage is of particular interest.
Also, the warning to store it with the lid not air tight is worth notice. It may be able to burst plastic containers in time, and if concentrated, could start a fire as it soaked
combustibles.
They DO NOT allow concentrated HP containers to be stored on wooden pallets for that very reason. Same may go for wood floors...
Be safe and avoid being astounded. A HP fire may accellerate like a gunpowder contaminated floor, giving NO time to fight it, while small. I store gallon HP jugs in a 5 gallon
plastic bucket outer containment vessel which has a non gasketed lid.
Go forth and make a joyous noise...
rjche January 20th, 2003, 01:19 PM

Further notes on HP
I checked a gallon of 50% stored 4 years and it was still heavy as hell meaning it has not lost much strength.
I don't have the sp gr figures, but sp gr would be a good way to judge the concentration of the stuff, and especially the concentration decrease over prolonged storage at room
temp. If anybody finds sp gr versus concentration data please post it.
That will make a world of difference in conserving chemicals when making AP with unknown concentrations.
At the url (down below) you will find a very informative FAQ on hydrogen peroxide.
Of particular note to us is that it can be concentrated by freezing, up to 30% rather easily and up to 62% as the limit, WITHOUT DANGER.
Boiling is risky, see below.
This faq is very informative and a must read for AP tinkerers.
<a href="http://webhome.idirect.com/~earlcp/FAQs/FAQ.html" target="_blank">http://webhome.idirect.com/~earlcp/FAQs/FAQ.html</a>
It contains links to people who have had accidents with HP, etc.
Roughly, as you get past about 30% in concentrating it by anything but freezing, it gets dangerous for tinkerers.
Basicly when freezing lower concentrations of HP, it's the water that freezes and leaves concentrated HP as a liquid.
In boiling (not recommended for strong solutions) it's the HP that remains and the water that boils off. It can run away when the conc gets above about 50% or so (my
estimate, don't bet on that) if there is any contamination at all, or if the heat added by HP decomposing causes uncontrollable (in the time available) temp rise. This can spray
HP around the room or explode.
( I expect if temp was being watched when it started to ramp up there MAY be time to drown it in cold water as one does NG that turns yellow during making. Haven't got
experience on runaway hot conc HP so can only give my speculations. Wisely suit up if you try it.)
IF you are going to play with HP do get the FAQ on your computer and consult it before doing anything with it. Read it at least once a year to restore your respect for it.
Remember some mistakes can happen in a tenth of a second or so. Others not so drastic can cause you to cream yourself running into stuff in an unplanned speedy exit.
Don't mix stuff with concentrated HP without consultation. Most things mixed with it go badly (dents in armor and/or scorched spots).
Making a fog of it in a room can cause lethal (delayed) lung damage before you can exit, IF YOU DON'T HOLD YOUR BREATH. Its harm is not apparent for several minutes on
the skin or inhaled or ingested.
Only some mixtures with it are peaceful. Many pretend peace, but later, when you ain't looking they do their thing, like chlorate phosphorus mixtures.
Kinda like having a pet adult boa constrictor. It may grow so fond of you that one day the idea comes that "dang I like you so much I could just eat you", and in keeping with
its single track mind, it promptly does.
Later it will probably form another idea "dang I miss him".

Gonna have to find me another friend. That one didn't last hardly at all.
If those, who have stories to tell how HP abused them, will post here they will be enjoyed by all.
rjche January 30th, 2003, 04:12 PM

Testing the concentration of HP using a battery hydrometer.
strength hydrometer reading
0% 1000
3% 1011
6% 1022
12% 1045
15% 1056
20% 1075
25% 1094
30% 1113
35% 1153
40% 1174
45% 1195
50% 1190
55% 1216
60% 1237
70% 1279
80% 1321
These data from specs on page at <a href="http://www.kencro.ca/HPSPECMSD.htm" target="_blank">http://www.kencro.ca/HPSPECMSD.htm</a>
There it gives the data for 35% and 50%.

35% 9.45 lbs per gallon, sp gr 1132 from that we get water =9.45/1.132 =8.3480 lbs/gal
50% 9.98 lbs per gallon, sp gr 1195 9.98 lbs/gal / 8.348 =1.195 sp gr.
From those two points the above sp gr readings for a battery hydrometer were interpolated. There appears to be a slight non linearity or error in the specs given in that
calculating the delta between 0% and 35% has slight differnce from that calc from 0 to 50%. This would not amount to a concern with our uses of it however.
This data is valuable as to ascertaining the degree of degradation in old HP.
If you have gram scales, and no hydrometer. weigh a 100 cc container empty, add 100 cc HP, and weigh it again. Subtract the weight of the container and the resulting weight
of your 100cc of HP will be 100 times the sp gr.
multiply the weight of HP by 10 to get the hydrometer reading.
divide the weight of HP by 100 to get the sp gr.
Example 100 cc beaker weighs (fictional) 100 grams

filled with 35% hp it will weigh 100 +113.2 or 213.2 grams
213.2 total - 100 glass weight = 113.2 grams liquid.
113.2 x 10 =1132 hydrometer reading
113.2 div by 100 = 1.132 sp gr of the HP
This weighing method is much more accurate than the battery hydrometer, but either are good enough to make AP, by ratio to known accurate formula ratios of acetone and
acid. As I understand it the concentration of the acid only relates to the speed of formation of product, within wide variations. highly conc acid (sulfuric) needs be cut to battery
acid strength. Most places that sell lead acid batteries (car batteries etc) sell very pure sulfuric acid used to fill dry charged batteries or to renew spilled acid. It's of the proper
strength to use for AP, which is around 30% concentration. HCL only comes in about 30% commercially.
HP would apparently have to be several years old to show significant degradation if it looses 1% per year as given by one mfgr of 35% and 50% HP.

a n d I m provised C hemistry > T a b l e s w e i g h t s a n d m e a s u r e s
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View Full Version : Tables weights and measures
zylion January 27th , 2 0 0 3 , 0 1 : 1 4 P M

W e i g h t s a n d M e a s u r e s T r o y W eight
24 grains = 1pwt
20 pwts. = 1 ounce
12 ounces = 1 pound
Apothecaries'Weight
20 grains = 1 scruple
3 scruples = 1 dram
8 dram s = 1 ounce
12 ounces = 1 pound
t h e o u n c e a n d p o u n d a r e t h e s a m e as in Troy W eight
Avoirdupois W eight
27 11/32 grains = 1 dram
16 dram s = 1 ounce
16 ounces = 1 pound
2000 lbs. = 1 short ton
2240 lbs. = 1 long ton
Dry Measure
2 pints = 1 q uart
8 quarts = 1 peck
4 pecks = 1 bushel
36 bushels = 1 chaldron
Liquid Measure
4 gills = 1 pint
2 pints = 1 q uart
4 quarts = 1 gallon
31 1/2 gals. = 1 barrel
2 barrels = 1 h o g s h e a d
1 teaspoonful = 1/6 oz.
1 tablespoonful = 1/2 oz.
16 fluid oz. = 1 pint
Circular Measure
6 0 s e c o n d s = 1 m inute
60 minutes = 1 degree
360 degrees = 1 circle
Long Measure
12 inches = 1 foot
3 feet = 1 yard
5 1/2 yards = 1 rod
5280 feet = 1 stat. m ile
320 rods = 1 stat. m ile
Square Measure
144 sq.in. = 1 sq.ft.
9 sq .ft. = 1 sq.yard
30 1/4 sq. yds = 1 sq. rod
43,560 sq.ft. = 1 acre
40 sq.rods = 1 rood
4 roods = 1 acre
640 acres = 1 sq. mile
Metric Equiva l e n t s L e n g t h
1 inch = 2.54 centim eters
1 foot = 0.305 m eter
1 ya rd = 0.914 meter
1 mile = 1.609 kilometers
1 centim eter = 0.394 in.
1 meter = 3.281 ft.
1 meter = 1.094 yd.
1 kilometer = 0.621 m ile
Capacity
1 U.S fluid oz. = 29.5 73 m illiliters
1 U.S. Liquid qt. = 0.946 liter
1 U.S. dry qt. = 1.101 liters
1 U.S. gallon = 3.785 liters
1 U.S. bushe l = 0.3524 hectoliter
1 cu.in = 16.4 cu. centimeters
1 milliliter = 0.034 U.S fluid ounce
1 liter = 1.057 U.S. liquid qt
1 liter = 0.908 U.S dry qt.
1 liter = 0.264 U.S. gallon
1 hectoliter = 2.838 U.S.bu.
1 cu.centimeter = .06 1 cu. in.
1 liter = 1000 millilite rs or 100 cu.c.
W eight
1 grain = 0.065 gram
1 apoth.scruple = 1.2 9 6 g r a m s
1 av. oz = 28.350 grams
1 troy oz. = 31.103 gram s
1 av.lb = 0.4 5 4 k i l o g r a m
1 troy lb. = 0.373 kilogram
1 gram = 15.432 grains
1 gram = 0.772 apoth.scruple
1 gram = 0.035 av. o z.
1 gram = 0.032 troy oz.
1 kilogram = 2.205 av. lbs.
1 kilogram = 2.679 troy lbs
did I forget something?????? :confused:
<sm all>[ January 27, 2003, 12:39 PM: Messag e edited by: zylion ]
Anthony January 27th , 2 0 0 3 , 0 1 : 5 3 P M

Yep:
1 furlong = 1/8 m ile = 201 m etres = 2 20 yards
1 fathom = 6 feet = 1.83 m etres
1 l e a g u e = 3 m iles (or 2.937, depending on which source you trust) = 52 80 yards = 24 furlongs = 4.827 kilometres
1 chain = 66 feet (surveying) = 22yds = 20.108m or 100 feet (e ngineering) = 33.3*yds = 30.46*m.
I love obscure imperial m e a s u r e m ents :D
EP January 27th , 2 0 0 3 , 0 4 : 5 6 P M
Useful site:
<a href="http://www.convert-m e.com /en/" target="_blank">http://www.convert-m e.com /en/</a>
Timpsick January 30th , 2 0 0 3 , 0 3 : 2 5 P M

Another one:
<a href="http://www.adm iralm etals.com /m etric_conv.htm " target="_blank">http://www.adm iralm etals.com/m etric_conv.htm</
a>
BrAiNFeVeR January 30th , 2 0 0 3 , 0 4 : 2 7 P M

I couldn't agree with you less anthony, altho they may hold som e historical value, I absolutely hate them .
Hardly any of those m e a s u r e s m a k e s s e n s e ! !
I t h i n k e v e r y o n e w h o u s e s t h o s e r e t a r d e d m e a s u r e s s h o u l d g e t o u t o f t h e d a r k a g e s a n d g e t n o r m alized!!!
I would be glad to get 100= |_ (instead of 90 for a straight angle)

Now, I got both at school, just for making thing s complicated :m ad:
Anthony January 31st, 2003, 11:11 AM

I was taught metric at school and im perial at hom e , I u s e a c o m bination of the two. I pick and cho ose units from each to suit
the task at h a n d .
The reason I love obscure im perial units is because they are no longer used and no one understands them , making them
nicely obtuse.
W hat's not to love ab o u t h a v i n g " l e a g u e s p e r k i l o s e c o n d " o n y o u r c a r ' s s p e e d o ? ? ?
Go metricise time! :p

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Sodium Sulfide
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View Full Version : Sodium Sulfide
Al Koholic January 27th, 2003, 11:57 PM

Over the course of the last few w eeks I have been pondering a better way to make picramic acid from TNP. As part of this process I have spent a decent amount of time in the
university library finding journal articles and w hatnot.
My main point here is that picramic acid synthesis seems to be a fairly easy process but I believe that the method of producing it utilizing a sodium sulfide solution prepared from
S and NaOH may be less than adequate...at least for my liking.
I found out that there are a few other methods for producing Na2S besides making the nonahydrate in solution from S and NaOH which I fear is very inefficient. For one,
reacting sulfur and sodium metal in liquid ammonia is a method which has been cited as being in the Handbook for Preparative Inorganic Chemistry. I have not view ed this
method and I'm not sure how viable it is to be conducting reactions in liquid ammonia.
The other method is the reduction of Na2SO4 with plain ole carbon.
Na2SO4 + 4C --> Na2S + 4CO
Some other examples:
3Na2SO4 + 4CH4 --> 3Na2S + 4CO + 8H2O

Na2SO4 + 4CO --> Na2S + 4CO2
Na2SO4 + 4H2 --> Na2S + 4H2O
These reactions take place at temperatures ranging from 700 to 1000 C. K salts can be substituted for the Na salts as well if K2S is desired.
The carbon method is the one which interests me the most. I am thinking of constructing a reaction vessel from some sort of high temp resistant material. Im thinking either a
glazed ceramic container or a metal (iron/steel) one. I will base that decision on w hether Na2S in its anhydrous crystal state is corrosive to metal or not.
I am thinking a metal tube about 1 or 2 inches in diameter w ith a cap at one end will be filled for 10% of its length w ith an intimate pow der of C prepared from sugar/h2so4
and Na2SO4. This will be heated w ith a propane flame and the evolution of gas w ill be monitored by simply holding a flame into the tube to determine if CO2 is being evolved.
I believe if I react 2Na2SO4 + 4C --> Na2S + 4CO, the unreacted Na2SO4 will react with the CO according to Na2SO4 + 4CO --> Na2S + 4CO2.
My questions are:
Will the procedure I have in mind work even if the mixture is exposed to the atmosphere?
Will the Na2S formed attack a steel/iron reaction vessel? Stainless steel?
Edit: I forgot to mention that the reason I'd like to attempt this method is so I can w eigh out exact quantities of Na2S and KNOW how much I'm getting in solution before I react
with sodium picrate solution. I feel like the other method results in poorer solution which may be the cause for a lot of peoples' ailments when it comes to DDNP synth.
[ January 27, 2003, 11:03 PM: Message edited by: Al Koholic ]
nbk2000 January 28th, 2003, 12:35 AM

Well, if you had sodium metal, then the liquid ammonia reaction w ould be the simplist.
Na2S is a primary ingredient in the manufacture of mustard gas from ethylene glycol (anti-freeze), since it's used to convert chlorohydrin into thiodiglycol.
While it's still readily available for purchasing, the ability to make it from sodium compounds, carbon, and sulfur, would greatly further the ability of a home experimenter to
make mustard without being detected or traced.
From w hat I've gathered, you don't w ant to expose the reaction mix to the air because the oxygen w ill react with the sulfur, forming something that isn't Na2S.
Al Koholic January 28th, 2003, 01:17 AM

Not exposing this reaction to air is kind of what I w as leaning towards as well. I suppose that since my setup could be a fairly long tube (say, 2 meters) with the bottom 1/4
filled w ith the mixture, CO2 could easily be used to purge the initial air. Once the reaction was going, the evolved CO2 w ould prevent any influx of air. The cooling dow n stage
could be protected with a CO2 feed the same as the heating up stage.
It's interesting to note that I downloaded a bunch of movies made by a guy w ho had a "sodium party" with 1 pound of Na bought on EBAY!
I can upload a couple of the better videos to the FTP if anyone w ants... But the other day I was on Ebay looking for a heating mantle for 1000 ml rb boiling flasks and I came
across someone who in addition to selling a mantle, w as offering 1 pb of Na metal! What the hell? So I also did another inquiry and found a miriad of exotic chems for sale on
ebay among w hich was a bottle containing 917 grams of iodine crystals. WOW.
Anyway back on topic here, I'm also under the impression now that Na2S will be highly reactive to a metal reaction vessel at the temps required for the reaction. Im at a loss as
to what else I could use as a reaction vessel considering that the mix has to be sealed from air most likely. Originally I thought maybe it could be heated in a ceramic bowl...
Al
THe_rEaL_dEaL January 28th, 2003, 04:18 AM

If the Na2S is reactive with the metal why not use a ceramic pipe having a coupling of teflon spray coated metal pipe connecting to a threaded teflon coated end
cap on each end.
I have a feeling that the teflon would be scratched off on the thread area, leaving the metal open to possible reaction. Put plumbers tape over the thread to inhibit reactant
contact.
Would this reaction work more efficiently w ith high or low pressure?
Can PTFE take 1000K temps? (I have a feeling yes because they use it on the space shuttles.)
I'd be interested to see how well your ideas/designs work. Keep us Posted

No, PTFE can't survive 1000 degrees Celsius. It breaks down somewhere in the 400 degree range, IIRC. I have obtained sodium sulfide by accident when making sodium
cyanide with charcoal that had been incompletely cooked; organic compounds in the wood provided the sulfur, and the high-temperature reduction ensured that it became
sulfide.
I would just try heating your sodium sulfate and carbon together in ordinary steel containers first. You w on't know how w ell steel resists until you try it. And I don't think you
need to take heroic measures to exclude air. Do like I've done for cyanide production: get two steel food cans, one larger in diameter than the other. Fill the smaller one w ith
your mixture and invert the larger one over it, like so (pardon lousy ASCII art):
xxxxxx
xo..ox
xo..ox
xo..ox
.oooo.
Purging w ith CO2 should be quite unnecessary if you use an excess of carbon. The atmosphere within the setup will soon become mostly CO2/CO/N2 of its own accord. For that
matter, using carbon prepared from H2SO4 and sugar is extremely inefficient and unnecessary. Powdered charcoal (not charcoal briquettes) will work w ell and cost a lot less.
In any case, you are right to suspect the production of Na2S from sulfur and NaOH in solution. It mostly produces sodium polysulfides and thiosulfate. It's a reducing mixture,
sure, but it's not a very clean or easy to standardize one.
Al Koholic January 29th, 2003, 04:19 PM

Polverone, thanks for the idea with the cans. I also am w ondering what the temperature was for your sodium cyanide experiment where you said you might have gotten some
Na2S.
Al
Polverone January 29th, 2003, 07:03 PM
The cans w ere heated in a wood fire and they were a bright orange at their highest heat. I'm not sure w hat temperature that corresponds to. It was hot enough that the sodium
cyanide was evaporating; when I took the cans off of the fire and let them cool, the top can was stuck to the bottom one by glassy deposits.
Al Koholic January 31st, 2003, 06:20 PM

I do have to ask before I make my ow n Na2SO4...
What, if any, are the common comercial sources for this substance?
Mr Cool February 1st, 2003, 10:46 AM

I don't know, but ammonium sulphate is a common fertilser, and sodium hydroxide is a common drain cleaner. Mix the two, and you'll get sodium sulphate and ammonia.
Al Nobel February 1st, 2003, 07:57 PM

If you dont want to produce by yourself you can order it from omikron online.de (but I dont know if they sell chemicals to the USA).
nbk2000 February 2nd, 2003, 12:20 AM

Here's a current source in the US.
<a href="http://www .photoformulary.com/BULK-PRC-S2-Send.htm" target= "_blank">http://w ww.photoformulary.com/BULK-PRC-S2-Send.htm< /a>
Al Koholic February 18th, 2003, 12:04 AM

Well, just a little status update here...
I have just finished making w hat should be (once its dry) 140g of Na2SO4. I reacted 2NaHCO3 + H2SO4 --> Na2SO4 + 2H2O + 2CO2.
Cheap and easy.
For a w hile there I was going to do the whole H2SO4 + NaCl heated to evolve the HCl gas and leave Na2SO4 but that just creates mulitple problems (ie: I have to go to the lab
to do it b/c I have no fume hood in my room).
Then I thought 2NaOH + H2SO4...realized that w ould get expensive quick.
I don't know w hy I didn't think of the bicarb till yesterday...just managed to stay out of the limelight.
In the coming days when I can find a spare moment I'll be producing charcoal by sealing a container of w ood chips and cooking it in my grill for a w hile.

Ok, a little break in school occured (spring break which for me is only today and tomorrow ). I came home but forgot to bring my scale w ith me so please understand that this
update is a *bit* less than quantitative.
Anyway, I found a nice tin that I filled with oak chunks, then filled the spaces with sawdust of unknown w ood type. I placed the tin in a fire with some holes in the lid and
obtained a good amount of charcoal.
I mixed what looked like and felt like around 3 grams of the charcoal (this stuff w as almost airfloat so it was quite a bit volume-wise). I then added about 8 grams of Na2SO4. I
mixed it all up and it appeared very much still like charcoal with some white specks. I placed this into a tin can and made a makeshift tripod out of a coat hanger. I placed a
mini bunsen burner under the can and turned on the propane! The can was also capped with another can like Polverone suggested. I heated it like crazy to red heat for a w hile.
When I looked in expecting to see a melt, it w as still just looking like the original mix. Anyway, I scraped some of the stuff from the bottom and placed it in some w ater. I
obtained a deeeeeeep black solution that when diluted is a steely blue color. This was not a result of the carbon being contaminated as I checked by placing some in w ater and
not getting this effect. The solution also had a fairly strong rotten egg odor and maybe some SOx. The solution w as filtered and I added about 10 ml of vinegar...nothing
happened. Ill try adding some conc. HCl tomorrow.
Next, I figured I'd try a diffrent ratio this time to try and obtain a melt. I added 3 heaping teaspoons (like 10 or 20 grams) of Na2SO4. I added a small amount of the carbon
dust...maybe 2 level teaspoons all together. I heated this one even more strongly with double propane torch blasting. Heating commenced for about 15 minutes with a cap,
then I heated it directly under and with a flame from one torch right on the mixture as it had become a hard solid mass at this point. I ceased heating and let it cool. I scraped
the inside of the can and broke up the melt into chunks. Upon removing the chunks it was found that they were red/brown and porous. There was also still a considerable
amount of white Na2SO4 solid. I dissolved the chunks in water and got an incredible solution...jet black. I filtered it and poured it out into a tray to dry overnight and it appears
deep green/blue when spread out in the tray. I also added some chunks to some denatured alcohol, filtered it and noted that it has a lightish green/blue color now but nothing
like the w ater. Next I added maybe 15ml of hot w ater to the can to swirl it around a bit and clean it. The bottom was eaten away in about 9 seconds. A hole just formed and
the solution ran out into the sink. I continued heavily dosing the can w ith very hot water from my tap and for about 2 minutes, deep black solution flowed out through the 3 cm
wide hole in the bottom. Anyw ay...thats w hat happened tonight. By tomorrow the stuff should be dry so it can be observed a little better.
I don't know w hat this is though. Na2S is supposed to be white and colorless in solution. The smell and corrosiveness are in line with Na2S though. As is the differential solubility
in water and alcohol. Ill have to add some conc HCl to it tomorrow to see how much, if any H2S is liberated. You'll also be interested to note an additional experiment I
performed with it.
I heated some Na2SO4 on a teaspoon over a propane torch. The spoon was stainless and was glowing bright red/orange at its peak temperature. The Na2SO4 melted kinda
strangely and bubbled a tiny bit, then seemed to just melt into a yellow mass. This mass when placed in water also produced the same solution I obtained from the other
experiments. Is it possible to make Na2S by simply heating Na2SO4?! Anyway, more experimentation is DEFINETLY in order for tomorrow.

You can also make sodium sulfate by heating a solution of sodium bicarbonate (baking soda) and magnesium sulfate (Epsom salts). This precipitates magnesium carbonate and
leaves sodium sulfate in solution. I have been making a lot of this as waste while preparing magnesium compounds and as of yet I have found no use for it.
I have a little note somewhere around here that says "find out if sodium sulfate decomposes into sulfur trioxide w hen heated" w hich I w rote a few weeks ago after reading
something that indicated this may happen. This is not valid conformation of course, I am still looking. My desire is to convert sodium sulfate into sulfur or sulfuric acid, but that is
for another thread.
Mr Cool March 12th, 2003, 06:02 AM

NaHSO4 will:
2 NaHSO4 --300*C--> Na 2S2 O 7 + H2O
Na2 S2O7 --350*C--> Na2SO 4 + SO3
Also
NaHSO4 decomposes into Na 2SO4 and H2 SO4 by extraction with 80% EtOH. The former is insoluble in
the liquid and the latter goes into solution.
(all originally posted by rikkitikkitavi)
The later method might be easier if you w ant H2SO 4, not SO 3.
So you need something to react your Na2SO4 with first to make NaHSO4 . I suspect HCl could be used, it is cheap and readily
available and it is a strong acid. But at the higher temperatures used you might also get some HCl coming off, even though HCl is much more acidic than HSO4- so normally the equilibrium is nearer to NaHSO4 and NaCl:
NaHSO4 + NaCl <=-> Na2 SO4 + HCl
Tosh March 12th, 2003, 03:14 PM

How about plain old 2NaOH + H2S -> Na2S + 2H2O, sure H2S is pretty lethal but you dont have to be anywhere near the reaction site.
Btw, nice forum.
[ March 12, 2003, 02:22 PM: Message edited by: Tosh ]

From w hat I know about this reaction using calcium sulfate as the starting material the reaction is not very efficient. I assume the same reaction holds true for sodium sulfate
with respect to the chemicals produced. The reaction products are:
CaSO4 + C --> CaS (55%) + CaSO4 + CaSO3 + CaCO3
With calcium only calcium sulfide is soluble to any degree, but with sodium all the compounds are soluble. You may want to use alcohol as the solvent because neither sodium
sulfite, sulfate, or carbonate is soluble, but sodium sulfide is.
The process of converting sodium sulfate to sulfide is described in considerable detail as the old soda ash method for making sodium carbonate. If your research, Al Koholic,
has not found this I suggest try searching for it.

Tosh, I know about that reaction, its just that I would rather not set up an H2S generator if I can avoid it.
Mega, I have not researched the "soda ash" method. I'll have a looksie tomorrow when I'm in the library. I read in a book called something like Preparative Industrial Inorganic
Chemistry or something like that about the Na2SO4 + C method. It states that there are 3 different types of furnaces used for the reaction but it is mostly a qualitative source,
no real detailed procedure. It was an attractive route to me because of the ease of obtaining the materials and w hat SHOULD be a fairly easy procedure. However, judging from
my experiences this w eekend, it w ill require some more investigation.
I'll see if I can locate a detailed procedure sometime tomorrow and give it a look.
Tosh March 13th, 2003, 02:29 PM

<blockquote>quote:< hr /> Tosh, I know about that
reaction, its just that I would rather not set up an H2S generator if I can avoid it. <hr /></blockquote>Yes, ofcourse i
didnt mean to imply that you didnt (basic chemistry know ledge seen seems to be quit high on this forum :cool: ) i just suggested it because seems to be one of the few w ays
of making Na2S that will yeild a reasoble pure and consistent product! imho the other synths though interesting, will yeild a lesser quality product and will be difficult to keep
consistent and or time consuming to purify.
Al Koholic March 13th, 2003, 03:41 PM

I agree with you on that point. While it is not hard to filter out the insoluble waste from the reaction I have been working on, it will prove more time consuming and expensive
to separate the soluble material from the Na2S. If and when this reaction gets figured out, I'll have to first do a water extraction, then an alcohol extraction to separate out the
Na2S only. All this while the product is likely decomposing...
Im wary about a first step alcohol extraction because I fear some organic residues contaminating the product without a w ater step first. More and more, this is sounding like an
H2S generator might not be such a terrible idea :) hehehe.
Tosh March 16th, 2003, 05:03 AM

BTW if you dont want to make it there's a easy of obtaining the stuff. People who make wine themselves use Na2S as a preservative, i just found one who will sell me 1kg for
5 euro's :D ! I assume prices in america w ill be similar (w ich means $5 for a kg) :cool: ! Do a search on google on w ine making and you should be able to find one.
EDIT: Dammit it w ould appear that the wine guy i was talking to over the phone meant NaS2O5, dont you hate it when you have to deal w ith people who know nothing about
chemistry <img border="0" title= "" alt="[Frown]" src="frown.gif" />
[ March 16, 2003, 05:55 AM: Message edited by: Tosh ]

a n d I m provised C hemistry > Isotopic Explosives
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View Full Version : Isotopic Explosives
Al Koholic January 29th , 2 0 0 3 , 0 4 : 3 8 P M

As m any of you know, isotope s of com m o n e l e m ents are not always radioactive. For exam ple, 99% of the Earth's C is Carbo n
12, 1% exists in the form of C 13. C 13 is not radioactive like th e well known C 14.
I wish to propose this idea in a highly hypothetical manner since I know basically nothing about an y specific isotopic
compounds.
Suppose one were to com e into a supply of C 13 or C 14, and convert this carbon into lets say, ben z e n e , a n d f r o m there say...
phenol.
U n l i k e p h e n o l f o r m ed from C12, this p henol, while being nearly chem ically identical, would be heavier by 6 g/m o l o f C 1 3 a n d
by 1 2 g/mole of the C 14 derivative.
Now lets subject som e C 13 phenol to nitration to form TNP. This trinitrop henol is identical in every way to regular TNP except
for having a slighly higher mass and a slightly higer stability (I'll get to this). So, the molecules should pack together the sam e
way in a com position/crystal and you would therefore have a higher density produ ct, and a m ore powerful one as we ll.
The stability should a lso be higher because of Hooke's law. If one views (correctly) that a chem ical bond is a lot like a spring, it
can be shown that oscillations of chemical bonds involving C12 as compa red to C13, are slightly faster. This is because of th e
high er mass of C13 and its co rrespondingly hig her inertia. The faster a chem ical bond is oscillating, the less stable the bond
and the "faster" the rate of reaction in any reaction that bond participates in. This is one of the prim e principles of isotopic
dating in the quest to find the earliest evidence of life on this planet. The C13 pa rticipating in photosynthetic reactions is
"processed" m ore slowly by the plant than is C12, leading to a d iscrepancy between biological carbon residues and the natural
concentration of oxidized carbon in the atmosphere. This is due to C13 being heavier and therefore m ore stable in bonding.
Anyway, could the sta bility increase be of sufficient size that one could potentially stabilize very sensitive nitro explosives in
which a C is bonded to an N? W ould the effect be applicable to nitro esters like m ethyl nitrate?
Maybe all this is not m a k i n g s e n s e , a n d m aybe the stability increase would be qu ite low, but at the very least, utilizing C13 or
C 1 4 i n a n e x p l o s i v e s c a r b o n b a c k b o n e would lead to a higher density and higher power explosive compoun d.
L e m me know what yo u think.

Al
Mr Cool January 29th , 2 0 0 3 , 0 5 : 4 7 P M

It would be hideously expensive, but your reasoning looks sound.
Al Koholic January 29th , 2 0 0 3 , 0 6 : 3 3 P M

W ell...yeah. Totally expensive. Expensive beyo nd the point of any resem blence of control over cost. However, it is an
interesting theoretical thing I just thought of today on m y way hom e from class. I wonder if there has been any research done
into the topic.
Anthony January 29th , 2 0 0 3 , 0 6 : 4 7 P M

I d o n ' t s e e w h y i t w o u l d b e u n i m a g i n a b l e e x p e n s i v e . I t s e e m s that C13 can be enriched from natural sources of carbon.
T h i s c o m p a n y s e e m s t o b e s e lling a lo t o f c o m p o u n d s o f C 1 3 :
<a href="http://www.iconisotopes.com /c13cm pd.htm l" target="_blank">http://www.iconisotopes.com/c13cmpd.htm l</a>
firebreether January 30th , 2003, 12:48 AM

I would think that it m ight slow down the exlposive, and m a y b e m ake it less powerful, since the bonds are stabler.
W hy stop at C 13? You could u s e D e u t e r i u m i n s t e a d o f o r d i n a r y H , a n d O 1 8 i n s t e a d o f O 1 6 , a n d N 1 5 i n s t e a d o f N 1 4 . H e a v y

water (D2O) is a metabolic poison because it does not get proce ssed as quickly in the body as regular water does, so i
s u p p o s e i t w o u l d b e t h e s a m e with C13 as well.
I do think its m ore trouble and cash then it could possibly be wo rth though.
Al Koholic January 30th , 2003, 01:30 AM

W ell yeah...from a theoretical standpoint, why not use those ato ms. Hell, and since this is a theoretical topic...good point.
The point to any of this type of research would be sim ply to com pare the performance cha racteristics of the analogo us
e x p l o s i v e s . I a m highly interested in seeing if any of my predictions would be correct or incorrect.
The increased bond stability a s it relates to explosive power...

T h a t i s a g o o d q u e s t i o n . . . I ' m not convinced totally one way or the other what would happe n. On one hand, I want to think th at
the increased bond stability m eans that the whole m olecule is of lower energy and thus will not liberate as m uch heat on
detonation. However, this depends highly on what types of isotopes are used and on the way the products form .
On the other hand, I want to believe that the explosive power will still be sim i l a r b e c a u s e t h e g e o m etry of the analo g o u s
m olecues will be identical and thus any bond tensions will be as well.
Additionally, I believe the PO WER itself may not be affected at all now th at I think about it. Perhaps it will meerly be exhibited
in a different form . So the VoD is a little lower...the heat produced a little lower, b ut the energy should still be there in the form
of the higher m o m e n t u m of the resultant particles after the detonation. Could be these particles will have the same
m o m e n t u m a s t h e r e g u l a r p r o d u c t s o n ly will be m oving slower...
Pretty fun to think about...I m a y h a v e t o s p e n d s o m e time in the library fairly soon. :)

Edit: Anthony, I didn't see any prices for those com p o u n d s l i s t e d a n d f r o m what I gathered, they were being sold in .5 or 1 g
quantities....som ething indicative of high prices. Perhap s they are not as expensive as I was thinking though and at the very
least, they sure do have an in credible variety available!
Obviously this has no practical application to someone who wants to mak e a h o l e i n t h e g r o u n d . T h e t h e o r e t i c a l a n d

e x p e r i m ental "fun" that something like this can offer may be wo rth a decent sum of m oney....however one that is m ost likely
out of m y m e a g e r b u d g e t !
<sm all>[ January 30, 2003, 12:35 AM: Messag e edited by: Al Koholic ]
Mr Cool January 30th , 2 0 0 3 , 0 2 : 3 5 P M

W hile we're kinda on the subject, does anyone have any links to pages describing isotopic enrichm ent, other than for UF6? I
haven't been able to find anything useful.
T h e o n e I ' m specifica lly intere sted in is potassium .
Edit: <a href="http://dwb.unl.edu/Teacher/NSF/C04/C04Links/www.fwkc.com /encyclopedia/low/articles/i/i012001292f.html"

target="_blank">Here's</a> some information...
<sm all>[ January 30, 2003, 02:30 PM: Messag e edited by: Mr C ool ]</sm all>
Marvin January 31st, 2003, 10:10 AM

The effect would be sm all, far too sma ll to m ake a difference in noticable stability of a com p o u n d . T h o u g h m a k i n g a n
explosive out of radioisotopes is on another level alltog ether. I'm not convinced by the hooks law argumen t, but I dont
remeber wha t the official explanation for the kinetic isotope effe ct is in varios circum s t a n c e s .
Interestingly before the enrichment of deuterium by ele ctrolysis was discovered, several well respected scientists showed it
shouldnt happen. Quite ironically this turned out to be, and still is the m ost efficiant m ethod we have (in te rm s of enrichm ent
ratio), but rather expensive.
Usin g heavy atom s in explosives gets you a 'higher density explosive', b ut the energy density isnt im prove d . Y o u d g e t t h e
s a m e effect by adding lead powder to the explosive, an d in these term s its m ore obviosly not useful.
Mr C ool, Your after K-40, I'm sure. I'm after that m yself, but that high up enrichm ent is tricky, and it has 2 stable isotopes,
one either side. That page gives a basic grounding in theoretical effects, but is ra ther wanting on practical methods, which
often bear no resem blence.
A good way for nitrogen for example, involves taking a large vertical tube (filled with N2 gas), and stretching a fine wire down
the m iddle. The wire is heated electrically and you get an enrichm ent from the top to the bottom o f the tub e by a com bination
of therm al diffusion away from the hot wire, and convection currents up a nd down the tube.
I v e o n l y f o u n d o n e m ethod th ats been used successfully for potassium enrichm ent and I dont have the actual paper, only a
m ention of it, its not electrolysis, but it involves electrolysing a solution of a gel (to prevent m ixing) in which a K salt is
dissolved, exploiting the different ionic m obilities.
A n o t h e r o d d m e t h o d c h e m ically is currently the most cost effective deuterium enrichm ent m ethod from natural water. H2S and
H 2 O in conta ct can exchange hydrogen atom s fairly quickly, and at equilibrium the deuterium is enriched in one or the other
(offhand I dont remeber which). This sounds quite odd at first and came as a surprise to m e, that there wo uld be a 'static'
difference in the concentration of D between the phases, but it m a k e s s e nse when you remeber that equilibrium isnt when it
stop s reacting, its when the ra tes of both reactions becomes the same, and thus its preferential kinetics that determ ine it.
It gets weirder. The p artition coeffetient, a m easure of the 'preference' for D/H in the relative phases actually chang es noticibly
with tem pera ture, and its the difference betwee n 2 tem peratures thats actually used industrially. By having alternate hot and
cold towers, with coun ter currents of H2S and water, overall enrichm ent of a small amount of water can be a chieved (at the
expense of the bulk, obviosly) that doesnt use up any H2S. This process is very cheap, but its actually not very goo d in term s
of deuterium retention, only a bout 1 D atom in 5 in the feed water make s it to the heavy water produced by the plant. (This is
the first stage in a typical plant, the economics change, so higher retention methods are used later on).
C o m pair this with electrolysis, in which the water rem aining can have 12 times the concentration of D of the hydrogen gas
produced in a well built cell (for natural water concentration). The drawback is you have to turn all the water into hydrogen and
oxygen gas, and this is very expensive.
I h a v e s o m e a l t e r n a t i v e i d e a s o n K - 4 0 enrichm ent, but its too early to know if they would work well enough to be useful and
m ore im p o r t a n t l y b e t h e c h e a p e s t / e a s i e s t t o d o a t h o m e. In the shorter term I'm planning on trying D enrichm ent at hom e for
several reasons. Its the easiest, I want som e, I want to do it m y s e l f , a n d I h a v e a D I Y m e t h o d o f m easuring D concentration
that doesnt require a mass spectrometer, or rely on hoplessly in s e n s i t i v e d e n s i t y m e a s u r e m e n t s .
Since I'm throwing in everything except the sink, I'll add the trivia that since 'hydrogen' refers to all of its isotopes, when
refering to H-1 specifically, its called protium. W h e n I r e m e b e r , I ' l l a d d s o m e of the intern et URLs I found on practical isotope
enrichment (of anything), there is very little out there that isnt too theoretical, or too shallow to be useful.
Mr Cool January 31st, 2003, 02:18 PM

That H2S m ethod is interesting! I might try getting som e D2O , just as an experim ent. I'd use successive fractional distillatio ns,
I've heard th is can be quite efficient. Sodium a n d p h o s p h o r o u s a r e m ore imm ediate goals though, it'd be nice to be able to
produce either of these so that's what m ost of m y experim enting time is used by at the m oment (results will be posted if I find
out anything new. I have high hopes for m y specially designed Na producing cell, and furn ace construction is due to start this
weekend...).
Y e s , I ' m after K-40, since enrichm ent could easily be measured by an increase in count ra t e , o n c e I p r o c e s s e n o u g h t o
m easure. I was thinking along the line s o f s o m ething like chrom atography or electrophoresis, that sort of thing. I don't care if
I get all the K-41 and a load of K-39 a s well. I've seen products for sale with K-40 enriched to 4%, no higher. Maybe C-14
would be easier due to the bigger % difference in mass. I suppose if you rotted down som e plants and collected the m e t h a n e
you could use the hot wire me thod, in theory. Natural gas would be too old and anything bigger than H on the C would reduce
the % m ass difference too m uch.
How are you thinking of measuring D enrichment? I can't think of anything easier than careful density measurement, this
should be accurate if you process a lot.
firebreether January 31st, 2003, 06:11 PM

I t h i n k t h e e a s i e s t m e t h o d f o r D e u t e r i u m s e p a r a t i o n f o r a n a m a teur would jsut be straight distillation. The enrichm ent factor
isnt large, and youd need a bunch of successive distillations, but it's quite sim ple. I think to get a decent p urity you would
need around 100 stages though. This was used before they used the H2S m ethod.
Al Koholic January 31st, 2003, 06:18 PM

" U s i n g h e a v y a t o m s i n e x p l o s i v e s g e t s y o u a ' h i g h e r d e nsity explosive', but the energy density isn t im proved. Youd get the
s a m e effect by adding lead powder to the explosive, an d in these term s its m ore obviosly not useful."
True...I hadn't thought of that.
BTW , for what reason are you seeking 40K?
Mr Cool February 1st, 2003, 1 1:08 AM

Personally, just to see if I can get it, as a challenge.
It'd also m a k e a n i c e h i g h - e n e r g y ( 1 . 3 M e V ) b e t a a n d g a m ma source. 25 kg of KC l contains 1.57g of K-40, producing around
400KBq. It decays by B-, B+, and electron capture, and also rele a s e s g a m ma rays, with a half-life of 1.28 billion years. So,
25kg of KCl produces a whopping 84nW! This is tiny, bu t in total it contains aroun d 4900000000 J, equivalent to a ton of TNT!
Isn't nuclear energy amazing?!
<sm all>[ February 01, 2003, 10:13 AM: Message edited by: Mr Cool ]</sm all>

a n d I m provised C hemistry > Ethyleneurea
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View Full Version : Ethyleneurea
simply RED February 9th, 2003, 07:57 AM

As you know ethyleneurea(cyclo -CH2-CH2-NH-CO -NH-) is the precursor for EDNA.
EDNA is made by nitrating ethyleneurea with H2SO4, HNO 3 or HNO3, acetic anhydride and then hydrolising of the fin al product.
Very m uch chemical suppliers sell ethyleneurea and it's very cheap, so m y question is:
W hat are the physical properties of ethyleneurea, is it toxic and carcinogenic. Som ewhere in the web was typed it is?
Do you know are EDNA and MEDINA toxic?
Mr Cool February 9th, 2003, 09:07 AM

T h a t r e m i n d s m e, I was m eant to be getting an EU s a m ple, but it never arrived :m ad: . And I was looking forward to playing
with EDNA :(.
EU: also called 2-Im idazolidone. I did a quick search and couldn't actually find any MSDS for it, only alkyl d erivatives etc. I did
find: "2-im i d a z o l i d o n e ( a l s o k nown as ethyleneurea) induces tum ors in com bination with nitrate and causes genetic damage ."
concrete feet February 13th, 2003, 02:29 PM

try <a href="http://www.fishersci.ca/m s d s . n s f / 9 6 c b 2 0 1 9 d a d 1 3 1 1 a 8 5 2 5 6 6 7 0 0 0 1 d 9 2 b 9 / 4 3 0 a 7 7 e 0 1 3 1 f 8 4 3 4 8 5 2 5 6 6 f 1 0 0 0 7 e 5 1 4 ?
O p e n D o c u m ent" target="_blank">here </a>.
and for a good MSDS/Material Toxicology database, go <a href="http://www.hazard.com / m s d s / i n d e x . p h p "

target="_blank">here</a>.
<sm all>[ February 13, 2003, 01:30 PM: Message edited by: con crete feet ]</sm all>
simply RED March 1st, 2003, 03:04 PM

thanks, just before i buy it :) !!!!

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Boric acid
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shooter3 February 9th, 2003, 03:21 PM

(I think this is the right section for this).
An artical on the Drudge report says a truck load of Boric acid was hijacked in California. It goes on to say that the authorities ar very worried because it is a component of high
explosives.
What are they talking about. Does anyone know how this stuff is used?
Is this just another bunch of crap?
vulture February 9th, 2003, 03:38 PM

Bullshit.
Boric acid is just poisonous, the only use I could see in explosives is to stabilize nitrate/Aluminium mixes.
Anthony February 10th, 2003, 11:21 AM

I concur...
Moving to Chemistry Related.
Trinitrotoluene April 26th, 2003, 04:44 PM

I don't really see boric acid as being that bad. It dosen't seem that toxic, and it only seem to be used for in pyrotechnics is a flame coloring agent. When I did a flame test on
it, it gave off a nice green flame.
NERV April 26th, 2003, 05:49 PM

Most likely the pigs are just trying to scare people. You see the more people that fear chemicals the easer it is for them to ban them.
megalomania April 26th, 2003, 06:21 PM

You have to see this from the perspective of the media sheeple: Chemistry = bad! Some monkey probably checked a chemical databse of possible uses for the compound and
as soon as his eyes saw "pyrotechnics" his brain said "bomb" and his mouth said "the sky is falling!"
You can buy this stuff in a drug store FFS! Hell, they could saw water is a bomb making component, but too many people know what water is. I am sure at one point or
another just about any chemical that has been around longer than 100 years has been used in explosives in one way or another.
Them saying this is some bomb making material is just a ratings booster, shock and awe applied to the mass media. This could also be a tactic to alert people to help find
these loathsum terrorists with weapons of mass destruction hijacked for the purpose of killing CHILDREN!!! Would anyone bother to help locate a stolen truck of inert chemical
of little value, what this really is?
Just break down the key action words: Hijacked instead of stolen implies people have been taken hostage and the driver is being forced to drive to some unknown destination.
Boric acid, uh oh, chemical buzzword, break out your duct tape and plastic sheeting. A "component of explosives" instead of common industrial substance; clearly designed to
incite panic and loathing for the person when caught. The thief will be tried as a terrorist instead of a car thief.
jfk April 26th, 2003, 07:40 PM

ok this might be a bit off topic, but its about borates, sodium borate, for stain removal and silly putty, ive got a whole lot of it, but i was wondering does it have any use in
explosive synthesis? ive searched all over and cant find anything except different brands of stain remover

Sodium borate is a componant of no explosive I know, its not reducing, and its a fairly crappy oxidiser. By adding HCl you can make boric acid, which you can usually buy at a
pharmacy anyway. Boric acid is used as a pH stabiliser for pyrotechnics with aluminium in. With a fair amount of effort you can make boron powder which is used in some high
energy pyrotechnics, and with a lot more high molecular weight boranes can be made which are high energy rocket fuels, though largly ignored nowerdays.
Picking up a random household chemical and asking what explosives can be made from it isnt a good way to get furthur. Learn about classes of real explosives and try to work
backwards chemically from what you have available, if this is the sort of chemitry you are interested in.
jfk April 27th, 2003, 06:10 AM

Ok, thanks for that Marvin, i really should have stated my question "is it a precursor of a precursor" but since i didnt really know I wouldnt have done that. In New Zealand you
cannot buy boric acid from any shop, i had a look when I was out today, so you've helped me out quite a bit there. Because now I know where to get boric acid from.
As for precipitating boron from boric acid, im going to do some research about that. as boron metal will be quite usefull to me also.
FadeToBlackened April 27th, 2003, 10:01 AM

I think it would be nice to isolate boron from boric acid
Magnesium Boride + HCl -> diborane
FadeToBlackened April 27th, 2003, 10:20 AM

Does anyone know if B2O3 + HCl -> BCl3? If so then..
2BCl3 + 3Zn 3ZnCl2 + 2B (900 oC)
One should be able to drive the water out of boric acid with heat, treat with HCl, and pass the BCl3 through a length of pipe containing Zn powder at said 900 degrees C. The
MSDS says 'Incompatible with metals', I wonder if the pipe would need replacing or if the pipe would mess something up..

Thats going to be just a little tricky, since zinc melts at 419C, and boils at 907C :D
mt1988 April 27th, 2003, 10:35 PM

a small amount of Boric acid mixed with meyths give a cool green flame and im going to try making green fireballs

Boric acid will dehydrate to boric oxide pretty easily, but you cant make the chloride that way. The standard method for technical production of boron last I looked was
reduction with stoichiomentric amounts of magnesium powder, basically another thermite type, like production of silicon from sand. Some magnesium borides will be formed
also, treatment with dilute acid should dissilve everything except the impure boron. Using enough magnesium should produce magnesium boride instead, but I gather lower
boranes are a tad toxic, and react with water...
Adding boric acid to methanol, with a drop or two of conc sulphuric as a catalyst will produce the ester methyl borate. It renders flames green due to the boron flame colour,
and being completely voltaile works a lot better than solutions of boron containing salts. If the boric acid used is made from sodium borate, the sodium ion residue will probably
reck the flame colour unless the borate is distilled. Methyl borate is rather toxic. You can make ethyl borate which is much less toxic, but the reaction needs to be driven
forward with a lot of conc sulphuric.
I've been wondering if the different readyness to form the borate esters could be used to remove methyl alcohol from methylated spirit, since they are very difficult to seperate
by distillation alone.

Originally posted by FadeToBlackened
Does anyone know if B2O3 + HCl -> BCl3? If so then..
2BCl3 + 3Zn 3ZnCl2 + 2B (900 oC)
One should be able to drive the water out of boric acid with heat, treat with HCl, and pass the BCl3 through a length of pipe containing Zn powder at said 900 degrees C. The
MSDS says 'Incompatible with metals', I wonder if the pipe would need replacing or if the pipe would mess something up..
Thats "2BCl3 + 3Zn -> 3ZnCl2 + 2B", right?
would it be worth trying to dehydrate boric acid with sulphuric acid?
FadeToBlackened April 28th, 2003, 05:58 PM

Yes, the site I copied that equation from must have had a graphic for -> and I didn't notice. It did list reduction with magnesium as one way of production. Magnesium Boride is
probably like the silicide, add HCl and get borane (or silane). Silane is pyrophoric, borane probably is too. I wondered about making BCl3 like that since I seem to remember a
post about BF3 made similarly (it was a post about RDX i think). I wonder if you could use something with a higher melting point than zinc, since even if it doesn't have a
volatile chloride that will be released, you could just dissolve and filter the salt out (unless boron would try to react with it?). Random thoughts...blah.
The document I got that from has lots of boron-related info. I found it searching on ask.com, once I get my computer moved I'll run httpd on it also.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > weird white
precipitate
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THErAPIST February 11th, 2003, 11:50 PM

Um hi.. I know I havent been of much help to anyone here quite yet but if anyone could help me with this I would be greatful.
I was going thrue and reading some of the files on my comp today since I stayed home from school and had nothing better to do, when I came across a synthesis for
nitrocellulose which I had gotten from brainfevers site. Seeing as how I was bored I figured I'd go attempt to make some. I went and got my H2SO4 and the 2g of papertowel I
would need, and then I went to get my KNO3 and realized I didn't have enough. Well i grabbed this bottle of stuff that I've had laying around for about 4 months now. I
produced the stuff that was in the bottle by mixing about 25 grams of road flare innard with about 15 grams of KNO3 in warm water. Then I filtered off the stuff that wouldn't
dissolve and I let the water evaporate. What I was left with was about 30 grams of a yellowish crystalline solid. I assumed this crystalline solid was about 50% KNO3 and about
50% calcium nitrate. (I may be wrong but i think Calcium nitrate makes things burn with a red flame...). I figured I'd either get nitrocellulose or nothing at all if I used this
bottled stuff so I said what the hell and decided to give it a try. ( I was thinking that CNO3 has near the same nitrating ability as KNO3)
Anyways, I went outside and measured out my 30 mL of H2SO4 and put it in a beaker. Then I added 25 grams of the supposed KNO3/CNO3 to the acid. nothing happened so I
started stirring it. At first the mixture got kinda cloudy and then to my suprise everything in the beaker turned extremely white. It was the same color as HMTD. so I quickly
touched the beaker to see if it was warming up and again I was suprised because the beaker was rather cold. I stirred it for a few more seconds and then let it set there for
about 10 minutes. When I came back I tried to stir it and found that it was about as thick as yogurt. As of now I have filtered and dried the white precipitate. I have about 10
grams of this stuff. It's about as fine as baking flour and it sticks together when you squeeze it with your fingers. I have tried to light some of it with a match and it did nothing
at all. Tomorrow I'll do an impact test to see if it does anything. I'm pretty sure it's still some kind of oxidiser since two oxidisers went into it (I think) but does anyone think it
will detonate? Maybe it's like AN, it's an oxidiser yet it detonates. I'm not all that great at chemistry yet so if anyone knows what this stuff is or if anyone can help me then
please do.
----------------------------------------
use correct chemical formula as it is misleading and makes you look stupid when you don't - kingspaz
[ February 16, 2003, 01:01 PM: Message edited by: kingspaz ]
Aaron-V2.0 February 12th, 2003, 12:18 AM

The nitrate in road flares is Strontium Nitrate, very nice for red coloring in fireworks. The nitrate actually has two NO3 groups on the Sr, so that would make it a dinitrate (I'd
imagine.)
So possibly one NO3 group went to the cellulose and the remain SrNo3 is leftover, although there is no known SrNO3 on chemfinder...
This is confusing. :(
EDIT: Also Strontium Nitrate is a white powder, so there may be another chemical in your flare that's causing the white precipitate.
My road flares are also a yellow powder with woodchips. Hmm.
EDIT 2: Upon further thought the yellow is probably Sulfur, and also Strontium Carbonate is a red coloring agent, so that'd clearly screw the reaction up.
----------------------------------
di, tri, tetra, etc are only applied to organic compounds so strontium nitrate, having two NO3- ions (not groups), is simply called strontium nitrate - Sr(NO3)2
also use correct chemical formulas, a simple seacrh on google will find it - kingspaz
THErAPIST February 12th, 2003, 12:30 AM

AH! YEA! THANKS! I was goin nuts over here tryin to think of SRNO3 because calcium nitrate just didn't sound right. :p
My road flares had a brownish colored stuff in em that also had wood shreds in em. Looked almost like really weird dirt...
[ February 11, 2003, 11:34 PM: Message edited by: THErAPIST ]
a_bab February 12th, 2003, 05:38 AM

What you got there is SrSO4, isoluble as BaSO4. You'll better read some more chemistry before mixing up things without knowing what will happend! And if you'll gonna
detonate the SrSO4 I'll kill myself.
Machiavelli February 12th, 2003, 05:48 AM

The effect when you mix any nitrate with concentrated sulfuric acid is that HNO3 which is the weaker acid is driven out and you get HNO3 and sulfates. So if you start with
Sr(NO3)2 you'll get SrSO4.
The Sr-ion is has a positive charge of 2 units, it's 2+ while the Nitrate-ion is 1- and Sulfate is 2-.
So the reason that you don't get SrNO3 is that this is a charged compound, it would actually be (SrNO3)-.
Your precipate is probably a mix of K2SO4 and SrSO4. Anybody knows what else is in these road flares?
THErAPIST February 14th, 2003, 12:35 AM

Update: The white powder i got is soluble in warm water so i decided I'd mess around with it a little. I decided I'd see if i could put this into a batch of HMTD to get some
different effects.
In a 250mL beaker I put 50mL of warm 6% H2O2. to this i added 3G of this white powder and I stirred untill it dissolved. Next I put in 5G KNO3 and stirred till it was all
dissolved. finally I added 40mL of H2SO4 about 10mL at a time(I think its at about a 90% conc.) and i stirred it for another minute or so. I left the mixture outside over night
under a plastic bowl (it was really cold out. something like 30 F. I got home from school today and checked it and found that I had some white precipitate. There were two
layers to the precip, one layer looked like a solid on the bottom of the jar and then there was a thicker much more fluffy layer ontop of that and then there was more fluffy
stuff floating ontop of the mixture. I filtered, washed, and dried the precip, and I was left with 4.75g of precip (the crystals are a little bigger than regular HMTD crystals). Then
I went to flame test some of it. Normally when I flame test HMTD it just gives a somewhat bright flash with a whoomph kinda noise. However, this stuff flashed extremely
brightly blinding me for a couple seconds and it didn't make much noise. I have 1g pressed into a drinking straw that I will detonate tomorrow. If anyone is interested, I'll post
results and I'll link to all of the pics I have collected over the last couple days of this stuff and what it does.
kingspaz February 16th, 2003, 02:08 PM

solubility is greater in warm water than cold. also the addition of H2SO4 will have made some HNO3 from the nitrates you added. a byproduct of this is sulphates - SrSO4 and
K2SO4. these are distinclty less soluble than their nitrate counterparts so will precipitate. this will be greatly increased by cooling the solution. so basically you have some
sulphates and HMTD most likely.
i'd also like to add that adding a bunch of anything that you don't know shit about into an HMTD reaction mixture is fucking stupid. if you want to find out more about it then
learn some fucking chemistry and do some research.
edit: i'd also like to add that machavelli has already told you what it is and if you'd bothered to do a little research then you'd have found out that sulphates are pretty inert
and generally useless.
:mad: :mad:
Machiavelli February 16th, 2003, 05:44 PM
Well Therapist, now the flashing part sounds like nitrocellulose but the crystals don't, anyway it's a bit hard to tell what it is exactly since you're happily mixing every shit
standing around the lab without really knowing what you're doing, kinda like the AP whores from lesser boards.
So please improve your chemical knowledge and in the meantime at least try to use only pure chemicals, don't modify established procedures and refrain from doing anything
on a large scale.
As an alternative, you could just go on like this while at the same time starting to practice eating, typing and similar manual activities using your feet.
PS: "brownish colored stuff" is about as useless as you can get with an answer
[ February 16, 2003, 04:50 PM: Message edited by: Machiavelli ]

Sorry... I can assure you that I wasn't just mixing everything around. I usually use H2SO4 and AN or KNO3 in my HMTD mix, so that wasn't anything new. I agree that I
probably shouldn't have thrown the other stuff in there and I also realize now that I should learn a good bit more about chemistry before I do anything else. thanks for tellin me
about the sulfates though. <img border="0" title="" alt="[Frown]" src="frown.gif" />
Machiavelli February 18th, 2003, 03:56 AM

The "mixing everything standing around" part refered to your handling of the precipitate, you had no idea what it was but you tried to turn it into an explosive. I can assure
you, that's not the best way to determine the identity of your substance.
[ February 18, 2003, 03:06 AM: Message edited by: Machiavelli ]
Anthony February 18th, 2003, 01:50 PM

This may be an odd question, but why do you add KNO3 or NH4NO3 to your HMTD reaction?
kingspaz February 18th, 2003, 04:31 PM

must be because they too can be explosive thus improving performance of the HMTD :rolleyes:
seriously, IMO that should be avoided because you will have sulphate contaminents in the HMTD which is not good. and also its a fucking waste of chemicals!

I usually add NH4NO3 because then I dont have to use ice or stick my HMTD reaction into the fridge. The KNO3 I don't add anymore. I used to add KNO3 because I read
somewhere that it reacted with the hex and made it stronger or some shit. I read this before I ever knew of this forum and I've realized over time that what I had read was
pretty much complete crap so I quit with that. I get my NH4NO3 for either free or extremely cheap (which is why most of the charges I set off are AN based). since I get AN so
easily I'm never very worried about wasting it. Reguarding the sulfate contamination, I assume this would make the HMTD less stable, and even though I've never had any
problems with it even with storage I'll stop using AN.

a n d I m provised C hemistry > R eduction of Styphnic acid
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blindreeper April 16th, 2003, 09:13 AM

As m ost of you know picirc acid is reduced to piram ic acid via sodium sulfide/te ( I am not too sure on this sorry)
This picramic acid is then reacted with a nitrite ion to m a k e d i a z d i n i t r o p h e n o l .
Could styphnic acid be reduced in a similar way and end up prod ucing diazodinitroresorcinol (DDNR)?
L e a d s t y p h n a t e i s m ore stable and powerful oposed to lead picrate so logic would suggest that diazodinitroresorcino l would also
be more stable?
Any thoughts on this or is it m e just mindlessly rambling about oblivion?
Picric acid
http://chem finder.cambridgesoft.com/structure.asp?MOL_REL_ID=951
Styp hnic acid
Picramic acid
I think the reduced "version" of styphnic acid would just be the same as the picram ic acid but with an extra OH attached.
I couldn't find any info on the reduced "version" of styphnic acid, sorry. Any help on this would be apprehsiated (sp?)
I f a n y o n e h a s any resorcinol or styphnic acid th ey m ay want to try it
:rolleyes: :rolleyes:
IPN April 29th, 2003, 01:00 PM

I have some styphnic acid rem a i n i n g f r o m m y tests, so what me thod should I use to the reduction?
In ALENGO SVIGs pdf is one method for the picram ic acid, should I use that or something else?
Oh, and do you have any further info about this?

a n d I m provised C hemistry > Trying to m a k e O TC trim ethylsilyl chloride
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megalomania April 18th, 2003, 01:40 AM

I have been researching as of late a way to m a k e s o m e trim ethylsilyl chloride from O TC ingredients to use as a pro tecting
group in other OTC needs. I have been having trouble finding any inform ation regarding the synth esis of trim ethylsilyl
chloride itself. It seems to ubiquitous to be fou nd in the available literature, but not enough to be in some industrial
literature. I praise the powers that b e f o r R h a d o n s r e c e n t u p l o a d o f t h e U l l m a n s En cyclopedia which m a y h e l p a bit.
I would just like to know if anyone has any references h andy about this chemical. I really hope I will be able to m ake it from
tetrachlorosilane. One can ma k e m a g n e s i u m silicide fro m m a g n e s i u m m etal and silicon dioxide (fine powder), and react that
with HCl to form silane gas. This gas can be directly com bined with chlorine gas to m ake tetrachlorosilane. Alternatively one
c a n p a s s c h l o r i n e g a s o v e r a m i x o f s i l i c o n d i o x i d e a n d c a r b o n h e a t e d t o a r e d h e a t t o m ake tetrachlorosilane.
Tetrachlorosilane will react with methyl zinc (itself made by reacting m eth yl iodide and zinc I believe) to form tetram ethylsilane.
I can only sp eculate at this point that one can form trim ethylsilyl chloride by incomplete reaction of m ethyl zinc, perhaps by
limiting the zinc com p o u n d .
Knowing how they do this indu strially m ay lead me to find a better route.

Horray, I think I have found a route to day. More specifics as i work them out, but it involves tetram ethylsilane and chlorine with
a catalyst at a m o d e s t p r e s s u r e a n d t e m p e r a t u r e , a l l s e e m i n g l y O T C ' a b l e .

I don't see the point in going to the trouble to prepare SiH4 whe n SiCl4 can be prepared by passing dry chlorine over heated
SiC l2.
How about preparing trim ethylsilyl chloride by a dding a stoichem itric quantity of CH3MgCl to anhydrous SiCl4 (with the
appropriate solvents, of course)?
megalomania May 4th, 2003, 05:15 PM

I really dislik e the high tem perature reactions m yself; this is just a personal prefeance as I find running them to be a bit
difficult and unreliable. I know one can run the reaction with silicon and chlorine gas, I did not know about SiC l2.
Of course, where does one get the SiCl2?
I would love to try the Grignard route, however I have found no references for it. I have re ad m any allusion s to the process,
and I have seen the general outline, but the specifics are missing. The gold is in the deta ils.
I have decided to go with a nifty circuitous route involving m ethyl alum inum dichloride (MAD) and silica gel (or any basic silicon
containing compound excepting sand). In this all OTC route I ca n m a k e t h e M A D f r o m a l u minum foil, m ethyl chloride, and
alum inum trichloride (see m y website, it is m a d e f r o m A l a n d C l). The MAD reacts with silica gel to form tetramethylsilane
(TMS) quite readily. The TMS is reacted with antim ony trichloride (hence m y recen t post asking about it) to form
trimethylchlorosilane in a nifty pressurized setu p along with chlorine gas. The goo d thing is this route is all O TC.
My goal is to use the stuff as a protecting group on ethylene bromohydrin or chlorohydrin in which to run a Grignard reaction
with ethylene oxide to extend the carbon chain and m ake, after deprotection, 1,4 -butanediol. From here it is all OTC GHB or
T H F d e p e n d i n g o n w h at you want to do. I am sure m y friends over at the Hive will enjoy this.
H a v i n g O T C trimethylchlorosilane will likely com e i n h a n d y i n m a ny ways. If someone would like to suggest other handy
p r o t e c t i n g g r o u p s p l e a s e d o s o . T h e a b o v e p r o c e s s o f m a k i n g M A D c a n b e e a s i l y a d a p t e d t o m a k e o t h e r a l k y l a l u m inum
chlorides, which in turn can m ake other alkyl silanes. TMCS is just easier to add a n d r e m o v e t h a n o t h e r a l k y l s i l a n e s .
About that, I could use som e help narrowing down a good acid scavenger for the silation reaction. W hen trim ethylchlorosilane
is added to an alcohol forming an ether it produces HCl as a byproduct. The silyl ether is quite reactive to acids (one of the
r e a s o n s i t m a k e s a g o o d p r o t e c t i n g g r o u p i s t h e e a s e o f rem oval, especially in an OTC se tting; ad d a little HCl and it breaks
off) which is not a good thing as it will form an equilbrium that does not favor the silyl ether. In fact I think acid converts the
silyl portion into a silyl alcohol (please correct me if I am wrong I would like to know). If true that means our
trimethylchlorosilane will end up as trimethylsilyl alcohol, a com plete waste :( A scavenger is needed to react with the acid as it
is fo rm ed instead of it deprotecting the target m olecule.
I h a v e h e a r d such things as pyridine or triethylam ine co uld be used. I would prefer som e t h i n g , e h h , O T C . It does not have
to be perfect at the O TC level, m a y b e s o m ething sim ple like sodium hydroxide or zinc oxide would work? W h a t I r e a l l y n e e d
to find is some old literature about using silanes as protecting groups; the new stuff all use fancy chemical reagents. If I
c a n t f i n d a g o o d O T C s c a v e n g e r t h i s w o u l d h a r d l y b e a u s e f ul OTC project.
John A shcroft May 4th, 2003, 06:09 PM

I t a k e b a c k m y suggestion to prepare SnCl4 from SnCl2. I'm worried that heating S n C l 2 * 2 H 2 O ( p r e p a r e d b y dissolving tin in
HCl) will not yield SnCl2. But, SnCl4 can still be prepared by passing dry chlorine over heated tin. Beware, the reaction can be
vigorous.
The silyl ether would probably react with acid to reform the silyl chloride and the a lcohol. Keep the reactants dry, and the
reaction equilibrium between the silyl chloride and the a lcohol should be far to the right.
Am i n e s a r e e a s y O T C com pounds if you can get ahold of nickel salts (for urishiba nickel - NiO and NiCO 3 c a n b e b o u g h t f r o m
ceram ics sup pliers) or of mercury (for Al/Hg am a l g a m - thermom eters, switches, etceteras). They're just a reductive am ination
away from your favorite aldehyde/keto ne! See this thread: http://www.sciencem adness.org/talk/viewthread.php?tid=534 for
discussion of preparing uber-OTC nickel.
Mr Cool May 5th, 2003, 09:59 AM

"SiCl4 can be prepared by passing dry chlorine over heated SiCl2."
"I take back my suggestion to prepare SnCl4 from SnCl2. I'm worried that heating SnCl2* 2H2O (prepared by dissolving tin in
HCl) will not yield SnCl2. But, SnCl4 can still be prepared by passing dry chlorine over heated tin."
D a m n that Si <=> Sn equilibrium reaction! The bane of all sem iconductor research... ;) :D
(But you are right, he ating SnCl2*2H2O --> Sn(OH)2 + 2 HCl, although I believe it can be dessicated over H2SO4 e tc.
Anhydrous chlorides need to be prepared by passing chlorine gas over th e solid e lem e n t s a n d c o n d e n s i n g / s u b l i m ing the
vapours.)
Edit: "From here it is all OTC GHB or THF depending on what you want to do."
THF is OTC, and Na-GHB can be made from it by oxidising it to -OCH2CH2CH2(CO)- (I have seen NaO Cl and HNO3 mentioned
for doing this), then breaking the ring with NaO H to form Na-GHB.

D a m n that Si <=> Sn equilibrium reaction! The bane of all sem iconductor research...
O h m y. I rea lly shouldn't be p osting anything when I'm as ill as I've been. Feel free to jettison me i n t o s p a c e . : e e k :

I h a v e s e e n t h e p o s t s a t t h e H i v e a b o u t c o n v e r t i n g T H F t o G H B a n d I d o n t think they w e r e c o n c l u s i v e . I g a t h e r e d t h e
r e a c t i o n w a s m o r e o f a p i p e d r e a m a s n o o n e w a s a b l e t o p r o d u c e t h e g o o d s . I a l s o k n o w o n e c a n g e t T H F f r o m p i p e c e m e n t,
b u t t h a t s e e m ed like such an expensive way to g o a b o u t i t . C h e a p b a s t a rd that I am I want som ething more plentiful.
I would think it may be a bit easier to m ake triethylam ine from ethylbromide and am monia in alcohol. Actually this would be a
three step process because th is produces ethylam ine hydrobrom ide, which m ust be reacted with a base to m a k e e t h y l a m ine.
In the second part the ethylamine is again reacted with amm o n i a i n a l c o h o l t o p r o d u c e d i e t h y l a m i n e h y d r o b r o m i d e , a g a i n a d d
base. In the third we react this yet again to get triethylamine.
I would gather ethylam ine or diethylam ine m a y b e j u s t a s g o o d a s t r i e t h y l a m i n e s i n c e b o t h a r e b a s e s a n d l i q u i d a t r e a s o n a b l e

t e m p e r a t u r e s ( O K m a y b e n o t s o m uch ethylam ine). These just need to dissolve the reactants.
I didn't realize it before, but I suppose the HCl can't react as there should be no water in the reaction. This could be why some
references recom m end using a nitroge n a t m o s p h e r e . F o r t h e l i f e o f m e I d i d n ' t s e e a n y c h e m ical that would react to air, so it
m ust be the moisture then.

If you're looking for an am ine sim ply for its basic prope rties, I suggest reductive am inatio n on ace tone (or MEK, if you're
wanting a higher-boiling am ine) using Al/Hg am a l g a m i n a m m onia/alcoh ol/water. I've found that it's a *lot* easier than the
a l k y l h a l i d e + a m m onia process - largely because alkyl halides (unless the substrate alcohol is tertiary) are a nuisance to
prepare OTC.

John, could you please post the reductive am in ation procedure for acetone?

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Making Anhydrous
Ethanol...
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kryfo April 24th, 2003, 06:10 AM

I assume this topic goes here... if it doesn't, I apologize.
I was looking through the net trying to find ways, other than distillation, of concentrating ethanol, and specifically to concentrate it above 95.6% (highest concentration
obtainable through distillation). I found the following two links that discuss that matter specifically:
http://journeytoforever.org/biofuel_library/eth_separate.html
http://journeytoforever.org/biofuel_library/ethanol_manual/manual12.html
The quicklime method from the second link, and the castor oil method from the first link seem the most promising to me, and I plan on testing them soon, but today I am
leaving for a week's vacation :D (Eastern Orthodox Easter this weekend, and in my part of the world that's what is celebrated), and I won't be able to test it till I get back.
Although I am not sure how I would be able to test the resulting ethanol for purity.
Anyway, I thought people would at least find the links interesting, and if anybody else tries any of those methods, a post of your results would be interesting...

The whole first page on journey to forever seems flawwed, particulalay about the sulphur. It also fails to express why at the critical point, you need a differential solubility to
seperate the supercritical ethanol from the liquid water. I suspect under these conditions what would be going on would be very complicated. I was also under the impression
that the solubility of sulphur in ethanol was miniscule so I cant see this working usefully in the lab. Fundamentally these methods are only intended to produce burnable ethanol
(possibly <15% water) directly from fermented material, not absolute or anhydrous ethanol.
Leaving the az ethanol in contact with quicklime for a day or two and then decanting or distilling should bring the water content down to below 0.5%, thats absolute ethanol,
but its not anhydrous. The quicklime retains considerable ethanol and excessive atempts to remove it liberate the water as well.
Entraining is the standard industrial method for absolute ehtanol, it can be done in any good still (reflux type, not pot), you add a slight excess of the calculated amount of
benzene, toluene or xylene (many others possible) as an entrainer, the trinary mixture comes off first, then the excess entrainer and ethanol as a binary mixture, then virtually
anhydrous ethanol. The trinary mixture when condensed seperates into more than one layer, so the entrainer can be recycled if you know the composisiton. I dont have any of
the numbers for these though, and a websearch will probably only produce the numbers for benzene.
The common lab method for anhydrous ethanol is to use magnesium ethoxide to remove water as insoluable magnesium hydroxide, and then distill from the resulting
ethoxide/ethamnol solution. The ethoxide is made simply by adding magnesium turnings to a small portion of absolute ethanol with a small amount of a starter like carbon tet,
or ethyl bromide and refl;uxing until the reaction starts. The success of this method usually depends on how well moisture is excluded from the aparatus, below 0.05% water
should be easily possible. This method should ideally be tailered to the amount of water in the ethanol but example numbers from a lab book are,
5g magnesium,
60ml absolute ethanol, which must be absolute or better, or the reaction wont start.
a few drops a carbon tet
Reflux until reaction starts, then decant from excess magnesium and add to 900ml of absolute ethanol (below 0.5% water) then distill.
Ultimatly it depends what you want it for, how far you need to go.
Mendeleev April 1st, 2004, 06:04 PM

Wow, this thread has been dead a long while. There is a very easy method of making absolute alcohol, which involves bubbling equimolar amounts of ethylene through sulfuric
acid. This forms an ethyl goup bonded to an oxygen of bisulfate. Adding an equimolar amount of water to this mix will yield an equimolar mix of ethanol and sulfuric acid. The
products can be separated through distillation, and the sulfuric acid is not wasted at all. Basically just add water. Now that I think of it, would it be possible to just mix
denatured ethanol, 95% with sufuric acid and distill it to get absolute ethanol? This would be more advantageous as I suspect ehtylene would be restricted due to its anasthetic
properties, does anybody know how to get it? It work much like nitric acid distillation. The question is does it? As for the benzene synthesis a solution of about 18% ethanol,
7% water, and 75% benzene is used. Does anybody know where to get ethylene?
Bert April 1st, 2004, 06:12 PM

Now that I think of it, would it be possible to just mix denatured ethanol, 95% with sufuric acid and distill it to get absolute ethanol?
No, but it's a great way to make yourself some diethyl ether. First organic chem lab I remember doing in HS chemistry...
Mumble April 4th, 2004, 05:14 AM

With higher heating you could just get the ethylene wanted. This is the main way I know how to prepare it. It'd just go around in a circle. Breaking down ethanol to make
more. Perhaps it would be one way to purify the Ethanol out of Denatured Spirits.

Kryfo, you're 2nd link describes the most practical method for dehydrating the
ethanol. I've used this method myself. To make sure you got all the water
out is easy. Use a hydrometer, or lacking that, put a drop of the ethanol on
your tongue and taste for salt. If you taste salt, it still has water in it.
Density of ethanol: 0.7893 @ 20 C(68 F) per CRC 52nd Edition 1971-1972.
For use as fuel supplement, mix it with gasoline before putting it in the fuel
tank. That way the water separates out as layer.
ordenblitz August 26th, 2004, 01:17 AM

Molecular sieves are the easiest way to make absolute ethanol.
I think 4 angstrom, potassium aluminum zeolite are the best.
Milamber August 27th, 2004, 10:47 PM

I think you'll find that 4A sieves will absorb ethanol just as happily as they do water... 3A are the only option for drying the lower alcohols, if memory serves
Dr_Pind September 4th, 2004, 11:10 AM

I stumbled over this when I was working on making bio-diesel in a school project. Rather interesting procedures:

(cut) Entraining is the standard industrial method for absolute ehtanol, it can be done in any good still (reflux type, not pot), you add a slight excess of the calculated amount
of benzene, toluene or xylene (many others possible) as an entrainer, the trinary mixture comes off first, then the excess entrainer and ethanol as a binary mixture, then
virtually anhydrous ethanol. The trinary mixture when condensed seperates into more than one layer, so the entrainer can be recycled if you know the composisiton. I dont
have any of the numbers for these though, and a websearch will probably only produce the numbers for benzene.(cut).
As with water, ethanol also forms a minimum-boiling-point binary azeotrope with benzene. See Perrys Chemical Engineers Handbook, part 13. It contains 44.8% ethanol and
boils at 68.24C at 1 standard atmosphere (760 mm Hg). The ethanol-water azeotrope has 10.57% water, and boils at 78.15C. This data is originally from the International
Critical Tables (which are hard to get hold of as they have not, AFAIK, been released in electronic form, or issued in a revised edition for many years). As for the ternary water-
ethanol-benzene system, Perry has only it boils at 64.48C, with 22.8% ethanol, 53.9% benzene, balance water. Unfortunately, the full data on the ternary water-ethanol-
benzene system, in the form of a ternary phase diagram (triangular), which would be needed to design the apparatus, seems to be only in the International Critical Tables.
Virtually anhydrous ethanol prepared this way, with recycling of the excess benzene (or toluene) used as an entrainer, is supposed to contain a trace of benzene (or toluene),
which is toxic. This would rule out its being used to make alcoholic liquors for consumption, e.g. ports or sherries, or liqueurs obtained by mixing with fruit juices etc. or
steeping/macerating fruit in it.
Bugger.
FrankRizzo September 4th, 2004, 10:27 PM

I stumbled over this when I was working on making bio-diesel in a school project. Rather interesting procedures:
Yeah...so I was, like, doing this school project on biodiesel, and just happened to run across this link. Seriously, WTF?!? This is the same damn link that Kyfo started this thread
with.

Thankyou John, those numbers differ somewhat from mine and after an hour of calculator bashing I think most of the difference is due to your numbers being in molar percent.
Everything else on this forum is in mass % unless otherwise indicated maybe chemical engineers have different assumptions. Going by the CRC values,
Ethanol water is 96% Ethanol boiling at 78.17C.
Benzene ethanol is 68.3% Benzene boiling at 67.9C
The trinary azeotrope is 7.4% Water, 18.5% Ethanol and 74.1% Benzene boiling at 64.86C.
You cant drink the alcohol produced by this process but then its not normal to demand more than 96% Ethanol content for drinks or making tinctures.
We dont need anymore information to actually use this process, but aside from benzene being carcinogenic and not widely available if we cant recycle the entrainer we may as
well just use a throw away dehydrating agent. The trinary azeotrope is positive 2 phase heterogenious. So when you condense the vapour it forms 2 layers. One layer is rich in
water, the other is rich is benzene. If we knew the composition of these layers, we'd be able to recycle the benzene (and probably most of the wasted ethanol) for furthur
dehydrations.
We can look up data for other useful azeotropes to use something safer than benzene but we'd still lack the information on the way the trinary splits. I'd have to agree with
later posters that if you can get 3A molecular sieves, this has to be the easiest way to absolute ethanol. Does anyone know how well (ie % water remaining) these work?

The percentages of components given in Perrys Chemical Engineers Handbook, part 13, are all in MOLE %.
Perry also has the mole % and boiling-point particulars (but not the full ternary phase diagrams) of the following further ternary azeotropes, which may constitute other
dehydration methods: Water-CCl4-ethanol, Water-trichloroethylene-ethanol, water-ethylacetate-ethanol.
Bugger.
FrankRizzo September 5th, 2004, 08:30 PM

Here's a few links that may be of use:
Liquid-Liquid extraction process for acetic acid/benzene azeotrope. A similar process could be adapted for ethanol.
http://www.ddpsinc.com/ProcessProfiles/pp50.html
Drying Agent Selection Guide

http://www.rhodium.ws/chemistry/equipment/dryingagent.html
Drying Agent Data

http://www.rhodium.ws/chemistry/equipment/dryingagent.data.html

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Sodium Party
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a_bab April 26th, 2003, 05:59 AM

I recently found a site concerning collecting of chemical elements. The autor bought three and half pounds of Na from e-bay (100 b dollars), and then he set up a Sodium
Party. Basically, he dropped into the water about 2 pounds of it, in chunks ranging from 50 grams to 175 grams, into various containers of water. The page is fully documented
with lots of pics and movies. The efect of a big chunk in water is a huge explosion instead of the fizzling blob running above the water surface. The link is here (http://
www.theodoregray.com/PeriodicTable/Stories/011.2/index.html) .
Any comments ?
irish April 26th, 2003, 07:54 AM

good clips on that site,
a mate of mine put a block of sodium about 3x3 Cm in a school swimming pool when he was a kid, the pool was full of kids one second later they were all out :D .
The result looked very much like the video in the lake, remarkably no one was hurt just had the shit scared out of them.
As I can think of much better things to do with it, it is an awful wast of sodium to one who can't get any tho.
The Crazed April 26th, 2003, 02:30 PM

the site is realy cool. I have been looking for a good place to buy some pure sodium or pure potassium but all I can find is realy small pieces that are like only 15g. I cant find
something bigger and I was hoping someone could help me here.
Trinitrotoluene April 26th, 2003, 04:39 PM

That site is really cool, nice explosions made by the sodium too. I can't really get my hands on sodium metal mainly becauses it seems a bit expensive, and I'm a pretty cheap
person. But I hope when I order a transformer I can make my own sodium through electrolysis of sodium hydroxide.
simply RED May 14th, 2003, 07:47 AM

Before 3 years, a friend of mine "get" some sodium (600-800 grams). The sodium was in form of cylinders, about 250 grams each, all 3 cylinders were in a big jar.
We get to the nearest water chanel, I leak the petrol on ground, and threw the jar in the water. About 5 seconds nothing and then, 3 huge blasts, with less than a second
interval between. Very much smoke and fire, smoke was mainly NaOH, Na2CO3. So my friend had very bad coughing and headache 2 days after this.
We also tried to use some Na for fishing- with no success.
vulture May 14th, 2003, 04:34 PM

Do not throw alkali metals into swimming pools or water in which people swim! Not only because of the explosion hazard, but also because of the formation of NaOH, which
will quickly achieve a high concentration in the water.
For example, 1M NaOH solution already has a pH of 14.
Leadazide May 15th, 2003, 03:36 AM

Sounds like the perfect reason to throw Na into a pool full of people! :)
Leviathan569 June 1st, 2003, 07:12 AM

When I was in college some moron almost blew up the entire lab with sodium. We were preparing sodium ethanolate. The sodium we used was in the form of small pellets,
submersed in hexane. The dude that caused the accident was working too slow and by the time he prepared his setup, it was too late to get started. He decided to dispose the
sodium and just prepare a new bathch the next week. What did he do? He just dumped it in the sink and then tried to flush it with water! Two liters of hexane and 50 grams of
sodium! A fireball blasted from each sink in the lab. Miraculously, nobody got hurt.
Xioa March 16th, 2004, 09:30 PM

A mix of sodium and calcium metal can be prepared relatively easy (easier than trying to make pure sodium) by dissolving 40% NaCl and 60% Ca2Cl in water and
recrystalizing it (to get an intimate mix). Once dry, heat up to it's melting point (~590 C) and electrolyze it. Beware because Cl gas is evolved. This method is easier because
the mixture melts at a much lower temperature than pure NaCl (~800 C for 100% NaCl). Of course, the drawback is that you get quite a bit calcium metal, but it can be
extracted out.
chemoleo March 16th, 2004, 10:35 PM

Well well, a swimming pool of i.e. 5 x 10 x 2 m would contain 100 tonnes of water (=100000 litres). a couple of pounds of sodium surely wont get the pH high enough to
hurt... unless you were so unlucky as to receive some spattering hot NaOH straight into your eyes! So yes, I wouldnt recommend dropping it into a pool full of people!
Be a lot more carefule with potassium, last winter I found it would spontaneously ignite on snow! with lots of spattering!
vulture March 17th, 2004, 10:13 AM

Let's say someone throws about 50g of sodium into a pool with pH = 7 (usually it isn't because of ClO-), at 23g/mole Na that is ~2,17 mole of Na.
2Na + 2H2O --> H2 + 2NaOH
So we have 2,17mole OH-/1x105L = 2,17x10-5 mol/L
pOH = - log [OH-] = - log 2,17x10-5 = 4,66
pH = 14 - pOH = 14 - 4,66 = 9,34
MightyQuinn March 17th, 2004, 11:08 AM

Let's say someone throws about 50g of sodium into a pool with pH = 7
This is assuming all 50g of Sodium stays in the pool. Any material (Sodium) ejected beyond the edge of the water from the initial reaction would alter the calculations.
atlas#11 March 17th, 2004, 12:55 PM

Thats theoretical, the point is it would do damage. Think what the pool guy's face would look like when he went to test the Ph( :eek: )! Though it would be entertaining to see
it would be fairly stupid as their is no reason to do so and it is wastefull of good sodium, I guess we all have our days though.
I have been wanting to prepare pure alkali metals for a while now but I cant find a good high temp crucible to use. Does anybody know a good place to find them other than
on the internet? I will just throw one in next time I go to order some glassware which will be a while, but those videos have sparked my intrest, I want to do it now.
Xioa March 18th, 2004, 12:20 AM

My chemistry teacher had us use Coors crucibles for one lab. He said that they make the best high temp porcelain for the money they cost. If there's a Coors factory nearby,
maybe you can buy some crucibles from there. Here's an internet shop link with some Coors crucibles: http://www.labsafety.com/store/dept.asp?dept_id=552
ikbendirk May 15th, 2004, 05:20 PM

Would the same thing be possible with solid Lithium bricks?
I know Lithium reacts way less violent than sodium does, but they are quite big (say, 3 x 3 x 15 cm) so do you think they would explode? I know I can try it out myself, which
I will, but if someone can assure me it will not explode, what's the point trying :P?
[EDIT:]
Ok, I couldn't wait, so I tried it and guess what; it didn't explode :(

I guess lithium just isn't reactive enough :(
K'Luuppo May 24th, 2004, 04:50 PM

If one melts the NaCl, it will be some ~900-1000 C no problem. But then you electrolyze it, resulting 900-1000 C sodium, which will be in gaseous form (boiling point 883 C).
Somehow I have a feeling that hot sodium gas will react with something. If not with water, then with oxygen.

Having had lots of arguements with people over the years, I can state that even small bits of Sodium will explode.
The best way to get it to work is to put a bit on the floor, and add a small drop of water. This will react quite fast, and give off lots of heat. This melts the Sodium, and so
when you throw a full bucket on it, it will explode very violently! Watch out for secondary explosions!
a_bab May 25th, 2004, 10:21 AM

Yeah, that happened to me aswell. I once throw a small piece on Na in the toiled for fun. It was really small (like a corn seed). I spit afterwards directly on it and it exploded
very violently. That was pretty shocking as I didn't expected.
In order to achieve Na explosions with small amounts of Na, the metal must be in the melted state and hit by water. That will divide it into small drops which will vaporise
hence explode in contact with the water.
The effect can be reproduced in a heavy rain with a small piece of Na: because of the water drops, it'll eventualy explode.
And now, this is what I would love to have: sodium bricks cutting (http://www.armory.com/~images/imgbrowse.cgi?s=sodiumCutting&presentation=thumball)
nbk2000 May 26th, 2004, 06:23 PM

Where did he get that much sodium?
a_bab May 27th, 2004, 06:45 AM

He probably ordered it. The guy is John DuBois' , apparently the author of the famous "Diary of a pyro". the guy's site (http://www.armory.com/~spcecdt/pyrotech/)
I'm still perplexed that one can get such an ammount of sodium in America, without licence or something.
Myrol May 27th, 2004, 11:24 AM

One Year ago I had also 500g of pure Sodium from "Phywe". I sold it to a Friend in Berlin because I had no real use for it :rolleyes: That was damn stupid :( Now I have only
50g left. Seems to be a nice amount for one Test in a lake :) ikbendirk: Yes Lithium can explode also forceful but you must ignite the Hydrogen with a Torch etc.! I extracted
some Lithium from old Lithiumbatterys (you can get old ones for free from your local Photoshop! Ask them and say you need it for a Schoolproject :cool: ) I rolled the Gray Foil
together and threwed it into Water....nothing happened.....but after I lit the Hydrogen.....it fizzes some seconds and PAAMM, it explodes!
nbk2000 May 28th, 2004, 06:00 PM

I've got dozens of used lithium batteries I get from my work. I'll eventually get around to stripping out the lithium via electrolysis in pyridine.
He probably ordered it.
No shit. I thought he might have made his own molten electrolysis cell to get it from salt. :rolleyes:
The question is where?

D'oh! I posted a link to the same place as the OP. Anyway, the guy there says he bought it off ebay. A quick search on ebay.co.uk shows none, so YMMV.
MightyQuinn May 30th, 2004, 01:29 AM

About 3 weeks ago there was a block of 260g for sale. I was the high bidder at $60.00 US but the auction was cancelled early for listing violations IIRC. I cannot find the email
now.
I have looked faithfully since then and have found none. I have found a place in india that sells it at a premium....I will check here and there.
Edit* After typing this, I found this (http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&category=413&item=6100074881&rd=1&ssPageName=WDVW) :D
K9 May 30th, 2004, 02:09 AM

He didn't get too bad a deal with it. Three and half pounds for 100 dollars is ok. Then again I wouldn't pay that much to do that, but if you were going to then 100 isn't so bad.
I've never seen that much on eBay at one time, but I have seen fairly large amounts of it for auction.
Jacks Complete May 30th, 2004, 09:41 AM

1 and a half kilos for ~65? Top bargain! I paid comparatively more for 100 grams from a proper chemical supply place, and that was a long time ago...
Searching on Google found me this, which I found rather funny:

<hr>
 <a id=aw5 href=/url?q=http://service.netmeans.com/bfast/click%3Fbfmid%3D37920209%26siteid%3D40694226%26bfp age%3Dredir%26loc%3Dhttp%253A//
search.ebay.com/search/search.dll%253FMfcISAPICommand%253DGetResult%2526q uery%253Dchemical%2Bsupply%2526cgiurl%253Dhttp%252
53A%25252F%25252Fcgi.ebay.com%25252Fws%25252F%2526 ht%253D1%2526from%253DR10%2526currdisp%253D2%2526i
temtimedisp%253D1%2526st%253D2%2526SortProperty%25 3DMetaEndSort%2526BasicSearch%253D%26bfinfo%3D8015
831&sa=l&ai=AudC4oSduAhswoEp3IZd5Zu4Bwa_4FAf5D-YA5X6pJkTBQ6EAQb4ABUQBKaBAAAAAAEAA&num=5 onMouseOver="return ss('go to www.ebay.com')"
onMouseOut="cs()">Discount Chemical Supply</a> Large selection of new & used. aff Check out the deals now! www.ebay.com<hr>
"used" chemicals? :confused: wtf?
Myrol October 2nd, 2004, 12:29 PM

Hmm, well. Im working as a Laboratory Chemist and very soon
my Lab wants to waste around 1kg orginal sealed
Potassium made in the UDSSR :eek: It's 20 Years old but absolutely
pure because the Container is very tight sealed (I saw him twice,
it's a grey Metalbox 25cm diameter and 20cm high, 2kg heavy).
If my Master is so nice and give me that kilo Potassium......I can

celebtrate a POTASSIUM-Party :D So my Questions:
Has someone expirience with Pot. and HOW STRONG is it compared
to Sodium? I believe both are as same strong, but who knows?
Around one Year ago, I used all my left Sodium and even this was
very good! Chunks bigger then 5g always explode in Water (I had 500g).
Lithium is also good, but if you dont lite the Hydrogen with a Torch etc.
it just bubbles off relatively boring :rolleyes: Any expiriences are very welcome!
Pb1 October 10th, 2004, 01:16 AM

Years ago, I saw a video in school where they dropped various alkali metals in water. Potassium, as can be expected by its position on the periodic table, was a good deal
more vigorous than sodium. For the curious, this is what I can remember: Lithium bubbled slowly, sodium floated and gave of hydrogen, potassium did the same but more
virorously, and cesium and rubidium have blurred in my memory into one big explosion:D.
Centimeter October 21st, 2004, 09:12 PM

Potassium produces a much more entertaining explosion. It becomes hot enough to ignite the hydrogen every time and it creates a rather significant amount of fire. In my
chemistry class, we watched this video in which they showed some guys neutralising a pond with sodium. They had a five gallon bucket full and just for fun they threw a
gigantic chunk in. It must have been about half of what they brought. The explsion was tremendous and further explosions lasted for several minutes. If I can get the video
from my teacher, I might post it. I was working at a university in an organic chem lab and I noticed that they had quite a large amount of both sodium metal and potassium
metal. I asked why they had it and they said that they used it to create metal (such as iron) compounds capable of being distilled. Surprisingly the potassium metal was a
distinct purple. I was tempted to take a little but my damn conscience wouldn't let me. In any event, they made it sound like it was a common thing to find in organic chem
labs. I have been considering electrolysing my own sodium and potassium for a while. I live right next to the primary coors plant in golden colorado and I can get crucibles for
free from the university. I tried melting some gold that I recovered from computer circuits in them but every single one of them shattered. Of course I WAS trying to bring them
up to 2200*F with a torch. I guess this will be my next project!
Pb1 October 23rd, 2004, 12:24 PM

I, too, have had the shattering crucible problem. The problem is that you need an even heat source. A torch from one side will produce high heat stress due to the other being
much cooler, but a Bunsen burner's flame that engulfs the whole thing evenly should have no problems.

a n d I m provised C hemistry > W ould this work? (sodium chloroace tate)
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After reading the fluoroacetate thread in battlefield chem istry, i began wondering if one co uld electrolyse sodium acetate in HCl
solution to produce sodium ch loroacetate (for nitrom eth a n e ) ?
Einsteinium April 27th, 2003, 12:57 AM

Sodium acetate will first react with HCl producing acetic acid and sodium chloride. W hat you get if you electrolyse this solution is
chlorine gas, water and sodium chloride. If all HCl is consumed NaOH will also be produced. Chlorine gas m ay react with acetic
acid through a radical reaction (heat or better, light-catalyzed) and this is the reaction that would p roduce chloroacetate. The
reaction proceeds very well (som etimes too well) in the vapour p hase. I think there are easier ways to produce chlorine than
electrolysis for this reaction, for exam ple HCl and bleach (NaO C l o r C a ( O C l)2) reacts together and ultim atly produce chlorine
gas. Dichloro and trichloro ace tic acid may well be produ ced in larger am ount than chloroacetic acid if you don't control the
reaction thoroughly.

Dry HC l in glacial acetic acid will certain ly work, and directly as the electrolysis produces chlorine radicals, not chlorine as the
first step product. The chlorine radicals are the lim iting step in light stim ulated reactions, and here light and heat arnt required.
Additional water, and salts are to be avoided, dry HCl is easy to make with conc sulphuric and salt. Unfortunatly, with any
preparative electrochem istry you are lim ited by the very high value of the faraday, so high currents and long tim e periods are
needed. In this situation you m ay as well generate just the chlorine electrochemically, and use this in the standard synth with
potentially higher yeilds and avoiding cell problem s like kolbe electrolysis of the organic acid...

from what ive read the chlorine radicals bond togethor to form Cl2 at the annode (positive term inal), please tell me if im right/
wrong
or were you m eaning that the first step is form ation of chlorine radicals, and the second step was the form ation of chloreine
gass at the annode ?

Chlorine radicals does bond together forming chlorine gas but they m ay also react with acetic acid instead as Marvin states,
m uch chlorine gas will be lost though. Dry HCl in acetic acid without addin g salt or water dosen't conduct electricity very much as
the ionic m obility of protonate d acetic acid is quite sm all. Also, if you don't separate your cells you will have the reduction of
chloroacetic acid to acetic acid at the cathode, which make the overall process quite useless.

If one were to allow the acid to fully chlorinate (to CCl3COO H), would reaction with NaNO 2 give trinitromethane?

a n d I m provised C hemistry > M a n g a n e s e H e p t o x i d e ' s h a logen cousin :)
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FadeToBlackened May 6th, 2003, 09:47 PM

from http://www.bartleby.com /65/ch/chlorate.html:
Form ation of Perchlorates

Perchloric anhydride, or chlorine heptoxide, Cl2O 7, is a colorless, oily liquid that boils at 82C without explo ding but that may
be detonated by shock; it can be prepared by adding phosphorus pentoxide to cold perchloric acid. The perchlorate free radical
(chlorine tetroxide, ClO4) can be prepared by adding brom ine to silver perchlorate; it is extrem ely reactive and unstable
S o u n d s l i k e C l 2 O 7 i s m o r e s t a b l e t h a n Mn2O 7, though I im agine H2SO4 is a bit m ore com m on than P2O5. Also, any idea how
ClO4 com pares to ClO2? ;)

a n d I m provised C hemistry > electrolosis of organic salts
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zeocrash May 7th, 2003, 02:19 PM

ok its 3 weeks before m y chem istry As level and we were doing some revision, an d covering organic salts e.g. sodium
ethanoate, sodium benzoate etc.
t h e s e c o m p o unds are ionic, which got m e wondering, what do you get if you electrolyse these. m y chem istry teacher didn't
know, i was wondering if there was a general rule,
e . g . s o d i u m benzoate ==> Na+ and C6H5O -
w h i c h t h e n g o e s t o p h e n o l a n d s o d i u m hydroxide.
any ideas

Electrolysis of carboxylic acid salts induces decarboxylation. For exam ple, electrolysis of sodium be nzoate solution should yield
biph enyl and s o m e p h e n o l .
kingspaz May 7th, 2003, 06:02 PM

thanks john, thats pretty interesting.
jfk May 8th, 2003, 05:01 AM

y e s b u t t h e n y o u n h a v e t o s e p e r a t e t h e b i p h e n yl and the phenol, right?
any ideas?

isn't there any way to either break down biphenyl to phenol or to turn phenols into biphenyl.

Nothing realistic.

look ing at the m erck index it looks like it should be easy to separate the 2. biphenyl is insoluable in water, whereas phenol is
not.

Its called Kolbe electrolysis. You form radicals at the electrode which decarboxylate, and then typically dim e r i s e a s J o h n h a s
said. Acetic acid would form CH3CO O * , l o s i n g C O 2 t o p r o d u c e m ethyl radicals, CH3*, which would become ethane gas.
B e n z o a t e s s h o u l d f o r m phenyl radicals C6H5* which should mostly react with themselves to form b i p h e n y l b a s i c a l l y 2 b e n z e n e
rings linked together. Butanoic acid would produce C H 3 C H 2 C H 2 * r a d i c a l s r e a c t i n g t o h e x a n e . I t s b e e n u s e d a l o t t o m a k e l o n g
chain alkanes.
Phenol is a weak acid , it will dissolve in aq sodium hydroxide, and be ppt by HCl. Sodium carbonate wont work.
Edited for apalling gram m e r a n d c o n t e n t .
inFinie June 9th, 2003, 10:02 AM

I think that's wrong.
If you electrolyse C6H5ONa solution you will get H2 and O2 because electronegativity(positivity for positive valences) of them
are greater than C6H5O - and Na+ .
Kolb e electro lytic reaction(it says like that):

a process for preparing alkanes by electrolysis of Na salts of carboxylic acids. The carboxylic group must be at the e nd of a
carbon chain. A cold concentra ted solution of a salt is electrolyze d using Pt electrodes.
Marvin June 10th, 2003, 05:22 AM

Good point.
W e arnt electrolysing sodium phenate however as sodiu m b e n z o a t e . B o t h t h e s e c o m p o u n d s h a v e h i g h l y s t a b i l i s e d a n i o n s , i t s

possible they m ight object rather m ore to being oxidised than alkyl carboxylic acids. Its also possible the ring structure
reso n a n c e m ight stabilise the radical a nd provide a lower yeild of decarboylated p roducts. Lowest redox potential reactions arnt
the only reactions that happen in a normal electrolysis, it only m eans there is a cell voltage below which they are the only ones
happening. In order to get a decent current, the cell voltage is u sually lot higher and the lowest po tential reaction doesnt even
have to be the dominant reaction. If you electrolyse a solution of sodium chloride you dont just ge t oxygen or chlorine, you get
both. Cell voltage, concentrations, and electrod e overpotentials for each reaction m a k e b i g d i f f e r e n c e s .
Its quite possible these effects would vastly reduce the am o u n t o f b i p h e n y l a n d p henol produced in the rea ction current wise, it
m ight also introduce a lot of unwanted side pro ducts. Biphenyl is usually thought of as the wurtz side produ ct in phe nyl
grignard reactions, and got rid of as it has no real value. I cant see this as being a useful method for phen ol production either,
even if production was quantative as there are easier ways.
inFinie June 12th, 2003, 05:16 PM

In the first post it says C6H5O - and i tricked :m a d :
yt2095 August 4th, 2003, 08:33 AM

Has anyone tried to electrolyse Hexam ine?
I`m about to start som etim e today, and wondered if an yone else had tried this and m ayb e we cou ld com pare results?
also, does any have any predictions as to what may or m aynot be produced as a result?
m y Organic chemistry isn`t pa rticularly brilliant, but m y GU ESS would be the libera tion of Am m o n i a g a s p r o b a b l y l e a v i n g
Form alin.
any input?
Additional: it`s been running now for a bout an hour, I started at 4.5v, hardly a fizz, I`ve now stepped it up to m a x o f 3 6 V , a
little m ore fizz but no thing noteworthy, Cathode is Stain less steel, Anode a Carbo n rod.
here`s a rough pic as it is at the m o m e n t ;
http://www.yt2095.net/tests/hm taelec.jpg
t h e P S U i s h o m e m a d e f r o m an old CB powerpack, hence the voltage control in the middle, you ma y a l s o b e a b l e t o m a k e o u t
t h e H e x a m in e b o x .

and Improvised Chemistry > preperation of formaledhyde
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jfk May 8th, 2003, 04:59 AM

Formaldehyde, or methanal can be produced by the first oxidation of a primary alcohol. Namely methanol, or methalyted
spyrits.
This can happen just by leaving the bottle open to air for some time, or by chemical oxidation by a dichromate ion (Cr2O7 2-)
or a permanganate ion (MnO4 1-).
Have you ever had sour white wine? this is the result of the second oxidation of a primary alcohol, namely ethanol.
first the alcohol is oxidised to its aldehyde (eth goes to ethanal, meth to methanal) then oxidised to its carboxylic acid.
Now, methanol is an odourless liquid, however if youve ever smelled formaldehyde, well it smells like rotting fish or something
close...in New Zealand its rather hard to find formaldehyde due to its toxicity, and companies wont sell it unless you are a
school or have a hazardous goods storage area.......so im going to embarke on making some out of methanol.
I know this can be done because i have the result of it in my cupboard, which i found today. I fould 1 litre of methanol in my
cupboard which has been there for 5 years. (cap on) it smells like formaldehyde and also tests acidic so there is carboxylic
acid there also.
So if you left it with the cap off, it would obviously oxidise faster. However, i was wondering what you guys think about this,
would you be able to extract the formaldehyde from the mixture, if not would the small ammounts of carboxylic acids + left
over methanol be a problem in reactions with it? I was thinking RDX but i cant figure out what the fuck paraformaldehyde is
since para is telling you on which carbon the aldehyde is but formaldehyde (methanal) only has one carbon so it shouldnt
matter........
and so its RDX, HMX actuayl those are the only ones i can find ATM
Flake2m May 8th, 2003, 07:21 AM

I was going to post a topic on this... you beat me to it.
I am currently doing basic organic chemistry ATM. While I was reading my chemistry text book on this module. A section on
converting alcohols to aldehydes was brought up.
The textbook explained, that if you added a suitable oxidiser to a primary alcohol you can convert it to an aldehyde. The
reaction would be something like this:
Alcohol + Oxidiser --H2SO4--> aldehyde + salt.

Or
CH3CH2OH + Cr2O72- --H2SO4--> CH3CH2O + Cr2-
The equation isn't balanced, but I think you get the idea. If you use KMnO4 it will oxidise again it into a caroboxylic acid.
This process does have advantages, the first one being that you have a cheap raw material; Methylated spirits (yes I do know
its mainly ethanol, but it should not matter). The only problom would either
1. getting hold of some DiChromate
2. controlling the permangenate reaction so it only produces the aldehyde

Check suppliers of photographic chemicals for potassium dichromate.
IIRC, potasssium permanganate in alkaline solution is less vigorous than in acidic solution, and since you're distilling the
aldehyde out as it is formed (or in the case of formaldehyde, just allowing it to escape), it may be possible to use it. Even
permanganate in acidic solution will yield some formaldehyde I would have thought, which will escape and be collected, and
the formic acid can be processed as below.
If you end up with methanoic/formic acid, just neutralise it with calcium carbonate, collect it as crystals, dry, then thermally
decompose it to produce formaldehyde gas. You lose half your methanol as calcium carbonate, but the formaldehyde
produced should be pure and in high yield.
Also, it might be worth investigating other oxidisers, like manganese dioxide, hydrogen peroxide + catalyst, or even doing it
electrochemically..?

You really can t use something like potassium dichromate or permang anate to oxidize a primary alcohol to an aldehyde. The
aldehyde is readily oxidized further to a carboxylic acid. You have to use a special selective oxidizing agent like pyrindium
chlorochromate (PCC) or pyrindium dichromate (PDC). You can make PCC by adding pyridine to chromium(VI) oxide with HCl.
The PCC is added to the alcohol mixed with a solvent like dichloromethane. The PCC is insoluble in pyridine from which it can
be isolated, and it is insoluble in dichloromethane in which it has to be stirred, and can later be removed by filtration.
You may also wish to consider a method similar to the industrial method, run methanol vapors through a heated pipe stuffed
with copper. I have a lab method of making formaldehyde that involves heating a loop of copper wire in a burner to red heat
and plunging the wire into methanol. The odor of formaldehyde is quite apparent after a few heats and dips. This method is
not exactly conducive to production, but it serves to illustrate how theoretically easy it should be to use the catalytic system of
alcohol vapors and a heated pipe. I wrote a post some months ago describing the process.
If anyone wants to know how to mak e PCC I think I have a lab procedure here somewhere
Please do post that procedure if it's not too much of a hassle.
On a further note, I noticed that www.sciencemadness.org claims heating moist calcium formate will yield formaldehyde, but
I've read that heating formates decomposes them to oxalates (?)

If the aldehyde is removed as it is formed from oxidation of the primary alcohol, realizable yields can be achieved.
VX May 8th, 2003, 08:53 PM

Formaldehyde, or methanal can be produced by the first oxidation of a primary alcohol. Namely methanol, or methalyted
spyrits
Methylated spirits is not methanol... in fact, hardly contains any methanol at all. Typically it is around 95% ethanol (although
this varies) with only the remaining 5% consisting of methanol, Bitrex, dye and other denaturants.
Two years ago, whilst I was at college we actually made aldehydes from primary alcohols by using the above method of
heating with potassium dichromate, the reaction vessel was attached to a condenser to collect the aldehyde as it was formed,
and delivered it to a flask. Yields were high (cant remember how high) and because the boiling temperature of aldehydes is
much lower than both their corresponding alcohols and acids, they hardly vaporise at all, hence the product is high purity.
Come to think of it, I thing that the reaction was self sustaining as it was so exothermic, and no external heat was required.
Einsteinium May 8th, 2003, 09:15 PM

Indeed formaldehyde can be removed from the reaction mixture as soon as it's formed but it's often difficult to achieve when
water starts to be present in noticeable amount in the alcohol; a large amount of anhydrous alcohol must be used to produce
quite small amount of aldehyde (as water is produced in the oxidation steps). Water interferes with the reaction because it
reacts with formaldehyde producing formaldehyde hydrate, which is very easily oxidized to formic acid (and two molecules of
water). Formic acid is too easily oxidized, to carbon dixodide and water. Formaldehyde itself isn't very reactive toward
oxidation; in PCC oxidations, which stops at the aldehyde, the solvent used is methylene chloride, where PCC is soluble and
where water isn't, thus the hydrate cannot form. It you have some oxalyl dichloride, DMSO, methylene chloride and CaCO3 (or
better Et3N), you may want to try Swern's oxidation as it gives excellent yield but that would be rather costly for
formaldehyde...
Swern's Oxidation http://www.orgsyn.org/orgsyn/prep.asp?prep=v77p0064

diPyrimidium Chromate (similar to PCC) http://www.orgsyn.org/orgsyn/prep.asp?prep=cv6p0644
jfk May 9th, 2003, 03:53 AM

Well, i knew that using a catalyst like permanagmate or dichromeate would be far to vigourous, converting the aldehyde into a
carboxylic acid once it had formed, but i hadn't thought of those catalyists Meglo. Also the fact that methylates spyrits isnt
methanol, well pure methanol is easily obtainable anyways from a local Reidel de Haen supplier(for me anywayS). Also thanks
for that interesting copper pipe proceedure there Meglo, ill search for that and post it here also.
Plus, i waswondering if you were planning any updates to your chemical weapons pages ?
xyz May 9th, 2003, 06:33 AM

I have seen formaldehyde solution (About 20-30% IIRC) for sale in camping shops. I think it is used to stop mould growing
on damp tents. It was reasonably expensive though, $10AUD for 1 litre. Perhaps you could try camping stores if you are
looking for a source of formaldehyde.

Preparation of pyridinium chlorochromate (PCC)
Place 18.4 mL (0.11 mol) of 6M HCl in a 100-mL Erlenmeyer flask, add a magnetic stir bar, and stir the acid rapidly. Add
10.00 g (0.10 mol) of chromium (VI) oxide to the acid, and stir the mixture for 5 min at room temperature. Cool the solution
to 0°C in an ice bath, and add 7.7 mL (0.1 mol) of pyridine dropwise over 10 minutes with the cooling bath in place. Re-
cool the solution to 0°C and collect the orange-yellow solid by suction filtration. Dry the solid under vacuum over
phosphorus pentoxide for at least 1 hour.
I do plan on adding some chemical weapons info to my website eventually. I am working on a sarin prep right now, but to be
thorough I am also figuring how to make all the precursors. Incidentially the info applies to soman, cyclosarin, cyclosoman,
and pretty much every alkyl derivitative of sarin. I have decided to do my chemical weapons part all in XHTML, which is causing
me trouble as I learn it. Eventually my entire site will be XHTML.
I know I can get paraformaldehyde solid and formaldehyde solutions at Wal-Mart. I hear it is not a simple matter of heating
paraformaldehyde to decompose it to formaldehyde, although I may be wrong on this. I have never tried it myself, so I can
not say. Does simply heating paraformaldehyde make formaldehyde? If so the Wal-Mart stuff would be a good choice.

Pyrolysis of zinc or calcium formates are supposed to be a good source of formaldehyde.
Manganese dioxide does ok for production of acetaldehyde, but I'm not sure how well it would work with methanol. As pointed
out formic acid isnt the end product of this reaction, so there might not be much to reclaim for pyrolysis. Permanganate in
alkaline medium is less agressive, but aldehydes in alkali are just going to get destroyed.
Anyhydrous methods, and exotic oxidisers are all very well for complex molecules where yeild is everything. hardly worth it for
formaldehyde and acetaldehyde where cost and availability of the reagents is rather more important.
For Acetaldehyde, one book recommends,
6 parts sulphuric acid.
4 parts az Ethanol
4 parts water,
Mixed and poured onto,

6 parts powdered manganese dioxide in a large container, with a reciver cooled by ice water.
Distill until 6 parts of liquid have passed over. The distillate is redistilled twice from calcium chloride, mixed with twice its
volume of ether and saturated with ammonia gas, the adduct which ppts is then decomposed by distilling from 50% sulphuric
acid, careful recification from calcium chloride, not exceeding 30.5C provides acetaldehyde pure and anhydrous.
I suspect simply knowing how much acetaldehyde is in the 6 parts distillate would suffice for most uses, the impurities being
mainly water and alcohol.
Edit, Meg snuck in while I was typing.
Heating metaformaldehyde or paraformadehyde should be fine, possibly with a small amount of dilute sulphuric acid? Using
them as is in most reactions is usually fine anyway.
On the subject of PCC, does anyone know an OTC source for pyridine? Currently the only OTC route I can think of, wouldnt be
cost effective as I cant find niacin cheeply enough.
btw Meg, if you still need a synth for DDT, I have one.
jfk May 10th, 2003, 10:05 PM

Mega i was under the impression that you heated formaldehyde so it decomposed into paraformaldehyde..im sure i read that
somewhere. I would be able to figure it out myself but all my links have been deleted (i wont go into it.....but boy it makes
me mad).
Thanks for that camping store siggestion, would have never found it out my self. ill have to go check it out soon, as for $10
AUD / litre i think thats cheap !

T h a n ks, Marvin, but I alread y have a s ynth for DDT. I do need to get around to writing th at up
I too have mulled on getting OTC pyridine the last few days. I wonder if it would be possible to make it from piperidine
extracted from black pepper through some sort of dehydrogenation reaction? This would probably have to be some sort of
ind ustrial type reaction with high tempera tures and a catalys t to work Le ts see, British patent 745,400 titled Catalytic
D e h y d r o g e n a tion of Piperidine us es platinum or palladium metal supported on silica g el. The piperidine is pass ed over the
catalyst heated to 300-400 degrees with an excess of hydrogen. A similar US patent, 4,523,016, uses a copper/nickel/
chromium catalyst under similar conditions. I wonder if either of these patents could be improvised on the lab scale. Neither
patent mentioned industrial equipment, and indeed the second uses lab equipment, albeit of a more sophisticated nature.
nbk2000 May 11th, 2003, 09:52 PM

Piperine is extracted from black (or white) pepper, then converted into piperidine, then finally pyridine.
I believe there's an electrolytic process for conversion mentioned in either Merck, or the C.A. index. That'd be the first place to
start.
I (personally) think any process that relies on catalytic reactions is too hard, because there's so many variables involved,
especially if it's a pyrolytic process.
Better to get results at low yeilds in wet chemistry, than to dink around wasting time and money aiming for perfect yeilds.
Also, if I remember correctly, if you continue the chlorination of DDT, you eventually get Dioxin. :)

I agree that industrial caliber reactions tend to be a bit difficult to replicate on a lab scale, but I feel these types of reactions
are just waiting to be explored by improvisational chemists. I think with the proper equipment one could feasibly do these
kinds of reactions. It is just getting the equipment that is the hard part. I have noticed that the vast majority of these
industrial reactions follow a common theme, pass chemical X through heated tube with catalyst Y and out pops chemical Z.
Once someone works out a way to do this with one, all the others should work very much the same. I wish I had taken some
chemical engineering classes, of course they probably only tell you about equations. I would prefer good old wet chemistry
though. The unfortunate fact is most of your very basic common ubiquitous lab chemicals are best made through industrial
type reactions.
The extraction of piperine from pepper is des cribed in detail over at the Hive, or rathe r Rhodiu m s website:
http://www.rhodium.ws/chemistry/3base/piperonal.pepper/piperine.pepper/index.html
The site also describes the conversion of piperine to piperidine here:
http://www.rhodium.ws/chemistry/3base/piperonal.pepper/degradation.piperine/index.html
I did see in the Merck that pyridine can be electrochemicially converted to piperidine. Perhaps that is what you saw nbk.
Otherwise I think the only way to get pyridine would be from coal :(
knowledgehungry May 12th, 2003, 07:21 PM

I think that using potassium dichromate and sulfuric acid along with methyl alcohol will give formaldehyde. formaldehyde's BP
is very low, as soon as it is formed it will boil off, or so i believe. Perhaps some of it will be further oxidized to formic acid but
this synth is cheap enough that a slight loss in yeilds should not be a problem, you can reuse the dichromate over and over.

An even cheaper method, discovered by accident by polverone IIRC, is adding peroxodisulfate (persulfate) to methanol. The
reaction did not need to be carried out in acidic environment IIRC.

Looked at the black pepper stuff, primary extracting a 3,4 methylene dioxy phenyl compound. Gee what could they be
planning to do with that :D
Unfortunatly I dont own a black pepper plantation, or it might be worth extracting the few percent of piperadine to convert to
pyridine. Compaired to what should be a very easy synthasis from niacin, and with the current bulk price (for 25Kg ish) of black
peppercorns, theres not a lot in it.
A few hundred grams of pyridine is fairly easily obtainable, but I need about a litre of pyridine to convert to the hydrochloride
to use as reactant and solvent. >100US is
prohibitive for this amount for me. The cheepest Niacin I can find is about $15US for 100g.
jfk June 9th, 2003, 05:43 AM

ok i know that this thread is slightly old, but i have been inactive of late and i just read the recent post.
i wanted to recap on the posts about formaldehyde here.
if you use a slightly basic solution of potassium permangamate with sulphuric acid (reas high % ?) and methyl alcohol,
formaldehyde will be produced, and because of its low boiling point (and using high conc chems) it will boil off hopefully before
it becomes oxidised to formic acid.
and you can collect it in your condensor. now what i was hacing trouble with is getting high concentrations of sulphuric acid to
do this (i could look around for battery acid and boil it, but i think there would be to many impurities? am i right?) that aside i
have a bottle thats got mrthyl alcohol, formaldehyde and formic acid in it - does any one know if the boiling points of methyl
alcohol and formic acid are higher / lower than formaldehyde?
or what they are exactly. ? because i might consider distilling this if i can get the right temperatures going. which would be
good, then i would be back in RDX business.
Tuatara June 9th, 2003, 07:24 AM

jfk, you said you couldn't get formaldehyde here in NZ. Wrong!:D Try your nearest farm store, eg Wrightsons, or RDI.
Formaldehyde is sold in 10l packs for disinfecting milking sheds. Theres lots of yummy things to be had in farm stores - go
check it out
vulture June 9th, 2003, 07:32 AM

if you use a slightly basic solution of potassium permangamate with sulphuric acid (reas high % ?)
You cannot have a basic solution with free sulfuric acid in it. I think you got something wrong there.
There's a simple trick to avoid production of the carboxylic acid. Add it to the reaction mixture!
Carry out the oxidation in a solution of formic acid. Why? If one of the products is already available, this will shift the
equilibrium to the left, to the aldehyde also.
Only possible problem would be an acid catalyzed condensation between formaldehyde and formic acid, but I'm not really sure
of that.
rikkitikkitavi June 9th, 2003, 02:24 PM

vulture, about your last question, I wouldnt worry to much. At work we do have formaldehyde and formic acid together -no
problem.
Beware that formaldehyde undergoes selfcondensation in alkaline solutions, and happily with other aldehydes. I am not 100
% certain about kinetics though, but I believe that it is quite a fast reaction.
Caustic + acetaldehyde is much faster and exothermic, which one of our storage tanks at work disovered when it found itself
600 m away .with its bottom valve blown out, beacause there was a backflow of caustic into the acetaldehyde. Strangely there
was no fire. (this was in the 70s)
/rickard
jfk June 9th, 2003, 09:33 PM

ok thanks for that vulture. :) wasn't my mistake :P that post was like a summary of the posts in this thread.
ok living in rural NZ like i do, farm shops are close and plentiful :) thanx for that tuatara. i had been looking in the wrong
place. supliers wouldnt sell to me because i dont got no dangerous goods liscence (bs you need one for it) and the only
camping stores that sell it are in AUS

Do the oxidation in formic acid and discover a great new way to make carbon dioxide. Formic acid isnt really an 'end product'
as its a very good reducing agent itself, unlike the higher carboxylic acids. I'm also not convinced that simple product
concentrations will have much of an effect on redox reactions, it doesnt seem to fit what we know about canizzaro reactions for
example. In order to have any real bearing the reaction that produces the carboxylic acid, this would have to be usefully
reversable under the same conditions, which it isnt.
If anyone can get hold of the large amounts of formic acid anyway, they would be better making zinc or calcium formate and
making formaldhyde from these by pyrolysis.
blindreeper June 10th, 2003, 04:51 AM

Why would you want the stuff in camping stores? It comes in brown (what appears to be brown HDPE) 1L bottles for $9 and is
of 23% concentration and is dyed blue. Honestly it has no uses. Is there any way to maybe boil off the formaldehyde and lead
it into some ethanol to make a stronger solution?
jfk June 13th, 2003, 03:19 AM

uhm apparently those crazy australians use it to stop mould growing on tents.
i think static_firefly or someone else told me.

Aussies are not crazy, we took an airfield in the Iraq war and helped the USA out heaps. Well anyway thats OT. We don't use it
to keep mould off tents it's for portable toilets.
Can anyone answer my question about making the formaldehyde more "useful"?
0EZ0 June 17th, 2003, 01:12 AM

blindreeper, don't assume that because a chemical is dilute or it's appearance is startling, that it has no use. Formaldehyde
solutions are actually rather useful for the production of hexamine.
Since Formaldehyde is a gas I assume that a solution of it can be heated to give off the gas. Or possibly the heat may
evapourate some of the water giving a stronger solution, but I would think the formaldehyde would evapourate first. Be aware
that without stabilisers the solution may form crystalline paraformaldehyde with prolonged storage. Commercially a few percent
methyl alcohol is added to the solution to prevent such crystals from forming. Formaldehyde solutions are used widely in
industry and can be found in most laboratories usually labelled under 'Formalin'. Solubility of formaldehyde in water can reach
approximately 55grams per 100ml of water.
Maybe another avenue to explore is to produce a solution of formaldehyde from solid paraformaldehyde in an alkaline
solution. Place powdered paraformaldehyde in distilled water and add a drop or two of NaOH/KOH solution to dissolve it. Heat
the solution to de-polymerise paraformaldehyde back into formaldehyde?...

I thought that the formaldehyde had to be dissolved ion methanol so it wouldn't polymerise. So if I led the formaldehyde into
water I'd be left with some nice paraformaldehyde crystals, which I would use for RDX.
0EZ0 June 17th, 2003, 11:00 PM

I think you misunderstood my previous post blindreeper. Only prolonged storage of formaldehyde solutions will it polymerise,
not all the formaldehyde polymerises into paraformaldehyde at once. I think it's only a gradual process.
Leading formaldehyde into water to get paraformaldehyde is not going to be as productive as you might think. In any case,
paraformaldehyde is already available as a cheap OTC item that has wide use. Use 'Trioxane' as the keyword in a search
should you want to explore that path.
I would advice you that to answer any more questions, first do a bit of searching on the topic, as it's most likely already been
discussed. Bringing up the same thing over and over again is not productive for the forum and only serves to waste time and
bandwidth.
On another note about the RDX, as a wise man once said, "You must first learn to learn to walk before you can run;) ......", as
is the case in this hobby, trying to run without first learning to walk can very easily get you killed:( .

Not meaning to be disrespectful to you 0EZ0, but I think I am quite capible of walking. I have made several things like AP,
HTMD, HDN, TNP and heaps of LE stuff. I know it's a slow process. And I don't intend to start making RDX in the next 6
months but it would be good to have the precursors on hand. I mean if you see a special on drain cleaner you don't just say
to yourself "I'm not making any nitric acid today, nope I'm not buying it"
Chade September 12th, 2003, 12:47 AM

Has anyone looked into possible alternative methods of oxidising the methanol in this 'home-brew' formaldehyde method? If
things like permanganates are too vigourous, there are loads of other oxidising compounds. Heck, we seem to spend most of
our time discussing them. Would something like a chlorate work?
Given that Methanol oxidises if just left for a long time, the problem would appear (to me, a non-chemist) to be increasing the
oxidation rate a bit, but not so much that you oxidise the formaldehyde in excess. Perhaps bubbling air, or even oxygen
through the methanol would increase the rate of oxidation to a useful amount. I'd imagine that such a setup can be left
running for days without too much trouble.
For example: Maybe set the meths in a bottle with a two-holed cork. A glass tube runs from one hole to the bottom of the
meths, allowing air to bubble through when a low pressure is applied to the second hole. A tube runs from the second hole to
a second bottle full of water, so any gaseous formaldehyde bubble into the water, where it dissolves. (Just like HCL, water can
hold large quantities of dissolved formaldehyde) The second bottle also has a double cork, with the second hole in this case
simply connected to a low pressure source. If you want it as simple as possible, just attach it to a T-junction of a tube
connected to a tap. The tap water flows slightly faster at the t-junction and creates suction. (I'd be suprised if this method of
suction hasn't been mentioned somewhere on the forum before)
I'll try this myself when I have time, but not before I've figured out a method of analytically testing formaldehyde that doesn't
involve how strong it smells.
Just to clarify, formaldehyde bubbled through water dissolves and is often known as Formalin, or simply as formaldehyde. It
seems quite possible to get 37-40% solutions without too much trouble. At such concentrations it won't form paraformaldehyde
in the short term (e.g. weeks)
It's recommended you store Formaldehyde solutions in the dark and above 4 degrees C to inhibit paraformaldehye formation.
You can always reverse this if you actually want paraformaldehyde, I suppose, but it's still not a quick process, and it's tricky to
store something in a cold, light place. (Leave the fridge light on?)
Vogel's 'textbook of practical organic chemistry' includes a method for producing dry gaseous formaldehyde as heating
paraformaldehyde at 180-200 degrees C. Or, if reaction temperatures top this, it says to just add paraformaldehyde and let it
be produced in situ. I include this, as some people seem to be more easily able to access paraformaldehyde.
kingspaz September 12th, 2003, 05:21 AM

chade, the problem is, if i remember correctly, that aldehydes oxidise easier than alcohols.
Chade September 15th, 2003, 02:36 PM

Right, I had a good look into this. I've asked three professional chemists and three biochemists. It comes in handy to have
scientist mates.
You can add certain oxidising agents to methanol to make methanal. potassium and sodium dichromate in acidified solution,
and potassium permanganate (otc at the chemist) in acidic solution. Heat the solution to assist the oxidation. If there is any
excess oxidiser than that required to make the formaldehyde, it then starts to oxidise the aldehyde to formic acid then carbon
dioxide and water. So if you measure out the molarities correctly, you should be able to convert most of your methanol to
methanal. Bubble this liberated gas through water to make a saturated solution and that's it.
My idea of bubbling air through methanol was not as far fetched as it seems, as it turns out that's the industrial method of
making methanal. They use methanol at 400 degrees C, with a catalyst. As before, you stop when you run out of methanol.
The catalysts used include silver (let's not, shall we?) or the more reasonable copper (yay!) at just 300 degrees C in the
vapour phase with air. A method could be worked out with simple copper piping.
I'd also imagine H2O2 might work as an oxidising agent as well as it shouldn't give any nasty byproducts, other than adding
oxygen to the equation.
I did say i was waiting for a titrimetric test, and I think I've found one. Just titrate potassium permanganate solution against
the sample until it turns purple. That'll mean you've oxidised all the remaining methanol to methanal, then all that to formic
acid. It won't take any more oxygen in the compounds in the solution.
Most of the essential info is here.

http://www.wikipedia.org/wiki/Methanal
frogfot November 23rd, 2003, 03:42 PM

I found a very promicing method of formaldehyde preparation in one Russian book (Preparation of chemo-pharmaceptical
substances M.M.Kacnelson 2:nd ed)
Method gives 160 ml of 40% formaldehyde from 200 g methanole, with very simple copper catalyst. Got some time to
translate it, maby there are some members that want to try it out (I'll try it out hopefully in newyear holidays..).
Ok, here we go..

..my comments goes after //
"
Process:
CH3OH + O ==> H2CO + H2O
Following equipement is used to prepare formaldehyde:

http://www.geocities.com/frogfot/stuff/methanalapp.png (copy&past)
It consists of:
1. Washer with conc. H2SO4
//washer is probably optional, some air humidity shouldn't be a problem, else NaOH filter would be sufficient IMO
2. 500 ml round-bottomed flask with side output.

Flask is loaded with 200 ml pure methanole and closed with cork with dropping funnel (for additional methanole) and a pipe
connected to washer. Flask is placed into 45-48*C water-bath.
//we don't need dropping funnel cause it would be easier to reload methanole "manually"
3. 30 cm heat resistant pipe, 1 cm in diameter. Copper coil, 3 cm in length, is located in lower part of pipe.
//any metal would do as a pipe, however I'm eager to test out my quarz pipe.
4. Two long necked 200 ml flasks. Both are immerced into ice-bath and connected in series as shown on picture.
When apparatus is set up, first, whole heat-resistent pipe is heated by a gas burner and then it's heated only where copper
coil lies. Apparatus is connected to a good pump through flask (5), and strong air flow is sucked through.
//don't know what is a "good pump", but I would test 10 torr water jet pump
Air from H2SO4 washer will enter heated flask and mix with methanole fumes, produced gas mixture will pass hot copper
catalyst where methanole will be majorly oxidised producing formaldehyde and water.
Reaction will produce great ammount of heat, if burner is removed, copper coil will continiue to glow for a long time.
Ubtained formaldehyde thogether with water and unreacted methanole collects in flask (4).
Described procidure usually yields 160 ml 40% formaldehyde, dissolved in mixture of water and methanole.
Formaldehyde that did not condence in flask (4), will condence in flask (5).
Yield depends on heating of copper catalyst. To strong heating may convert methanole partially to formic acid.
Paraformaldehyde (CH2O)n is ubtained by evaporating aqueous solution of formaldehyde in exicator above H2SO4.
"
Also, as a note they mentioned to use copper oxide, ubtained by following method:
Usual asbest is soaked in concentrated solution of copper acetate and then heated. Copper oxide will form on asbestoes
fibers as very fine particles.
Comments/suggestions are more than welcome.
megalomania November 26th, 2003, 03:30 PM

As a matter of fact I have the exact same thing, but in English. I was writing it up a couple of weeks ago but I forgot about it.
I will finish it off and post it in the next few days (with pictures).
EDIT: I guess I already had most of it written, so here it is...
Ahh sweet vindication, I have found a published procedure just like my proposed copper oxidation of methanol. Indeed this
procedure passes copper vapors through a heated copper catalyst, and the best thing the reaction is a lab scale one! Without
further ado I will reproduce this gem in its entirety.
The side tube (length about 10 cm) of a distilling flask (capacity 250-mL) is bent upwards at the junction with the neck of the
flask. The end of the side tube, drawn out into a capillary (internal diameter 1.0-1.5 mm), is then inserted through a cork into
a piece of combustion tubing about 30 cm long (fig 53). Within the tubing and about 6 cm from the point of the capillary is a
copper spiral 4 cm long. The tubing slopes upwards at a small angle and its upper end is connected with a vertical condenser,
preferably of the coil type. To the lower end of the condenser there are attached two communicating receivers which, during the
experiment, are almost completely immersed in a freezing mixture. The short side tube of the second receiver is connected to
the pump. Into the distilling flask, which is lowered as deeply as possible into a water bath kept exactly at 46-47 degrees C,
100 mL of methyl alcohol are poured. The flask is then closed with a rubber stopper, through which is inserted a glass tube
reaching nearly to the bottom. Through this tube air is drawn in, and when the air is passing, the copper spiral is warmed in
the flame, cautiously at first, until, when red heat is reached, the reaction sets in. The air current must now be so regulated
that the spiral continues to glow quite feebly without further application of heat. If the experiment is carried out in this way
there will be complete freedom from explosions. The region within which methyl alcohol-air mixtures explode is indeed
reached when the temperature of the bath is too low (42-44 degrees C), but the flame strikes back no further than the
capillary tube, since the rapid current in the latter prevents further striking back.
The two receivers contain 110-115 mL of a 30-32% formaldehyde solution after all the methyl alcohol has been evaporated. A
further small quantity of formaldehyde may still be collected in a third receiver containing a little water.
The following paragraph contains some points which should be considered in carrying out gaseous reactions.
In order to dehydrogenate one mole of methyl alcohol 0.5 mole of oxygen is required, and hence for one volume of the
alcohol half as much oxygen or two and a half times as much air. The stoicheiometrical must therefore contain methyl alcohol
and air in the proportions (by volume) 1 : 2.5, ie. 28.5% of methyl alcohol. Since the volumes vary as the partial pressures
the temp of evaporation (of the alcohol) must be so chosen that its vapor pressure shall be 28.5% of the atmospheric
pressure, ie. About 210 mm of mercury. With the simple type of apparatus here described complete saturation of the air with
methyl alcohol vapor is not reached, and hence a temperature somewhat higher than the theoretical is used.
frogfot November 28th, 2003, 11:28 AM

Never thoat about choosed temperature that way :) So, concentration of methanole can be estimated from its partial pressure,
if air flow is not too high.
Autoignition made me worry.. for some reason my book doesn't mention this! But what if we pass large excess of air into
apparatus, to lower methanole concentrations below danger? or, if we doesn't dip air inlet tube into methanole..
Wonder if 200 ml thick-walled filtering flask will hold explosion of air/methanole, else it wouldn't affect yields much, but it
would be a scary synthesis..

If you alter the air/methanol mix you screw up what you are trying to make. The problem isnt really autoignition as this
happens in the combustion tube, the problem is striking back into the methanol flask, and this is prevented by the capillary.
Provided the actual amount that can ignite is small, explosion shouldnt be a problem. It is always a risk with these sorts of
catalyctic oxidations though. In any case this oxidation operates with a level of methanol above the explosive limit, so adding
more air or forcing less to evaporate would make the system more likley to explode, not less.
Edit, I'm fairly sure the 1:25 needs changing to 1:2.5 btw.
frogfot November 29th, 2003, 10:58 AM

Well, it would probably ignite occasionaly, that still wouldn't affect yields much. Though there could maby settle a continious
flame in methanole flask :eek:
How could chanses of explosion increase if we decrease methanole concentration (say, decrease it 10 times less than
stochiometric). Reason I don't wanna use capillary is because I'm afraid to implode my recieving flasks (by water jet pump). I
have only thin walled (measuring flasks), and capillary wouldn't be enough to eaven up vacuum, or?
In any case this oxidation operates with a level of methanol above the explosive limit
You mean, that stochiometric mix of methanole/air is unable to ignite in described conditions? I really hope that's true.

Yes, the concentration of methanol is indeed supposed to be above the upper explosive limit in this reaction. That's why it is
important to keep the water bath heating the methyl alcohol at exactly 46-47 degrees C, this keeps the evaporation rate of
methyl alcohol just right.
That ratio of methyl alcohol to air was supposed to be 1 : 2.5 not 1 : 25, I edited it above to reflect that fact.
frogfot December 30th, 2003, 02:51 PM
Finally tested that synthesis, couple of minutes ago, luckily no autoignitions. I used setup nearly as on pic posted before
(without H2SO4 washer). As combustion pipe I used 28 cm quartz pipe 8 mm (inner diameter). Copper coil was clutched
together by plyers to fit inside pipe, total lengh of coil was 4 cm.
I had totally 100 ml MeOH and temperature in water-bath was always between 46,3 and 46,7 *C (temp control was provided by
my experimental termostat circuit). After I heated coil, air was sucked through apparatus by water jet pump (suktion was
regulated by a homemade clamp).
It was actually really easy to keep the coil glowing by its own. 2 cm was glowing steady. Closer to the end, glowing increased to
3 cm of coil, this was noticed when MeOH level was below air inlet pipe (air wasn't bubbling through MeOH). I think this
increased oxygene concentration and reaction become more vigorous (autoignition was expected.. but there was none).
Here, IMO, one would have a clear indication that autoignition is coming: whole coil starts to glow. This overheating can be the
only cause of autoignition. Basically, non-glowing part of coil will be as a safety heat-sink. Or?
Results:
Synthesis proceeded about 2 hours. In the end I had 64 ml liquid in first recieving flask and about 4 ml in second, no strong
smell was detected. Both liquids was mixed and excess of 25% ammonia was added. I'll report how that will go after couple of
hours in an edit...
Additionally, coil was examined after the experiment. It became much softer, and, 0,5 cm from one end was fused together!
(end closest to MeOH fumes inlet) It was probably above 1000*C...
EDIT
Well, excess ammonia was destilled away and HMTA was dryed at 100*C. 16 g (+/-1 g) dry solid was ubtained.
Assuming HMTA formation is 100% (is it??), formaldehyde yield is 26-29%. Thats crappier than book claims primarily because
there was some difficulties since this is first attempt, (had some troubles with crappy pipe connections) :P Next experiment will
give better yield.
I also forgot to mention that pipes leading from second recieving flask to pump had small ammounts of white crystalline solid
substance on walls. I dunno if that can be paraformaldehyde.. it didn't melt from lighter (though it gave a sharp smell)
Hang-Man December 30th, 2003, 10:09 PM

I admit, I didn't read the whole thread, but platinum is only mentioned once so I think I can post this without worry of overlap.
I was doing some research on catalysts and discovered that platinum, a well known catalyst, has the wonderful property of
converting methanol to formaldehyde. A thin wire suspended in methanol vapor will quickly glow red hot and oxidize the
methyl alcohol to formaldehyde. (It is also used to convert ammonia to nitric acid)
frogfot January 4th, 2004, 05:54 PM

If I understood correctly, platina begins to glow without external heat provided in beginning?
Had a very nice idea for those who don`t have access to heat-resistent pipes. Using a thin walled iron pipe, one can indicate
temperature with a homemade thermocouple (copper/iron) to see if catalyst is glowing. The copper wire is fused directly on
iron pipe near catalyst, with help of a car battery (i found that copper wire must be thick enough to make a good fuse spot).
On heating of fuse-spot with lighter, voltage across it got from 0,0mV to 1,5 mV
And ofcaurse I drawed a pic of what I mean:
http://www.geocities.com/frogfot/stuff/ironpipecat.png
As you can see iron pipe is slightly clutched to keep the catalyst coil in place, since in first experiment with quartz pipe it
moved (cause coil become very soft)
Temperature that`ll affect thermocouple can be regulated by distance between fuse-spot and catalyst coil, this way one will
avoid overheating of thermocouple.
If one worries about heat loss from catalyst, heat dissipation of iron is not that high. However, it would be adviseable to use
long iron pipe (>50 cm) to avoid overheating of connection pipes.
I would test this thing if there was more time.. any idea if this will work?

Do you happen to know of any calibrated voltage tables for iron-copper thermocouples available on the net? It would not do
much good if people can't measure the temperature of the improvised thermocouple to begin with as the voltages would be
meaningless.

Nope, I don't have it. But, one don't have to know exact temperature. The important thing is to know that copper coil inside is
"hot".
One can determine this value by experimenting. After heating/removing the gas burner from pipe without methanole/air flow,
and, heating/removing burner from pipe with methanole/air flow. By comparing voltage changes, this way one can probably
indicate when heat of pipe is maintained by catalyst..
Though that table would be sure very useful, I learned about what thermocouples was from Tuataras post in "Setting up a lab"
thread. He mentioned several different compositions. (never thoat that temperature probes was so simple to make)
Dave Angel January 6th, 2004, 12:02 PM

I came across a product called Cool Glass in the garden centre the other day. It's a white powder that is moistened and
painted onto greenhouses to... keep them cool. Turns out that it is titanium dioxide.
Apparantly this can be used as a photocatalyst in the oxidation of methanol to formaldehyde. I happen to have some pretty
pure methanol lying around doing nothing so if I get a sunny day or some kind of decent light source I will do a few qualitative
experiments. And maybe ethanol to acetaldehyde?
Also, the Japanese have tiles along the sides of some of their roads which contain or are coated with TiO2. This
photocatalytically converts NOx pollution from exhausts and water vapour into nitric acid, which is then washed safely away
when it rains. If I get round to doing some experiments in that area, I'll make sure to post them in the nitric acid section.
Imagine replacing the catalytic converter in your car with a TiO2 cat and UV bulbs, making nitric acid whilst you drive!
As for calibrating thermocouples, I think that fairly cheap (30) IR thermometers can be bought these days and they go up to
something like 500 degrees C.

a n d I m provised C hemistry > Simple qu estions about dichloroben z e n e s . .
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Okay first qu estion: If one were to reflux NaOH with some 1,4-dichlorobe n z e n e , a v a i l a b l e a s n o n - n a p t h a l e n e m o t h b a l l s , w o u l d
it becom e 1,4-benzenediol? Second question, any way to change that 1,4- to 1,3-?

It won't work.

O k a y . C are to explain why not? I think I've seen similar things referenced before..

i cant see wh y the dichloroben zene to benzinediol wont work, but converting it from 1, 4 to 1, 3 will be highly im practical /
im p o s s i b l e
a s i t w o u l d i n v o l v e b r e a k i n g a n d r e f o r m i n g 2 b o n d s , t h a t h a v e n o g o o d r e a s o n t o b r e a k , y o u ' d b e m uch better off trying to find
s o m e 1, 3 dichlorobenzene.

Y e a h I h a d f i g u r e d t h at about going to the 1,3-, doesn't hurt to ask though
Ok, found this:
D i c h l o r o b e n z e n e s b e l o n g t o t h e g r o u p o f o r g a n ic halogen com pounds replacing two hydrogen atom s i n b e n z e n e b y c h l o r i n e

a t o m s . T h e r e a r e t h r e e i s o m e rs; ortho -dichloro b e n z e n e , colorless liquid boiling at 180 C, used as a solvent and chemical
intermediate for dyes, pigm ent, agrochem icals and wide range of organic synthesis ; meta- , colorless liquid boiling at 172 C,
u s e d a s a s o lvent and chem ical interm ediate; para- , white solid with a with a characteristic penetrating odo r. It is used mainly
a s a n insecticidal fum i g a n t a g a i n s t m o ths, as a space d eodorize r, as a general in secticide and fungicide on crops, a n d a s a
chemical interm ediate for plastics, dyes, pharm aceuticals and other organic compounds. All they are insoluble in water and
denser than water. They are p repared by the chlorination reaction of benzene in the prese nce of iron(III) chloride. (the
chlorination under strong illum ination and without iron(III) chloride leads to benzene hexachloride instead of m o n o o r
polychlorobenzenes). The chlorination reaction leads to sim ilar ratio of ortho- and para-dichlorobenzene, but sm all am o u n t o f
the m eta isom er is performed . The ortho and para isom ers are separated by fractional freezing. W hile the para isom er
crystallizes, the ortho isom er remains liquid. The m e t a - d i c h l o r o b e n z e n e i s p r e p a r e d b y h e ating and pressure with aluminum
chloride.
Does anyone know where I can find specifics about the heat+pressure+AlCl3 method, or k now if theres a nam e for it?
Mega, wheres that O T C b e n z e ne you were talking about awhile back? :P
Polverone May 9th, 2003, 03:38 PM

The reaction won't work because the two chlorin es strongly deactivate the m olecule. Believe m e, I've tried this before. Doesn't
work. If you can achieve higher pressure and temperature (i.e. in an autoclave) it quite likely could work, but I don't have an
autoclave.

Any idea of what kind o f p r e s s u r e / t e m p m i g h t b e n e e d e d ?
Or would NaNO2 react with it at all?

I b e l i e v e C u C l c a n b e u s e d t o m a k e c h l o r o b e n z e n e ( a n d p a r a - d i c h l o r o b e nzene, I assume) reactive enough for nucleophilic
substitution to be performed with relative ease. It probably makes the Cl bonded to the benzene ring into a superior leaving
group. The increased reactivity of iodobenzenes and brom obenzenes, relative to chlorobenzene and fluorobenzene, is largely
d u e t o i o d i n e a n d b r o m i n e b e i n g s u p e r i o r l e a v i n g g r o u p s t o c h l o rine and fluorine. Nucleophilic substitution of halogens on
benzene rings will proceed m uch m ore easily when there's a nitro group bonded to the benzene ring - and assum ing you're
after a nitrated produ ct, you m ight want to try initially m ononitrating the para-dichlorobenzene (it definitely won't be easy,
though, because of the deactivating chlorines).
FlaA lchemist June 18th, 2003, 01:26 AM

This is a hard chem ical to utilize, after all its tough getting rid of halogenated hydrocarbons in the environm e n t . F o r e x a m ple
DDT Not m any ways to get rid of the chlorine, b ut it can be done under the right conditions.
THe_rEaL_dEaL S e p t e m b e r 2 5th, 2003, 05:16 AM

W ell today I went snooping in some cleaning storeroom in som e public toilet. I found this stuff called De-odo-air. Its quoted
o n t h e l a b e l t o b e 9 9 % d i c l o r o b e n z e n e a n d f r o m the po st above I now know its para-dcb.
Anyway it was in som e 20kg tub and was made by : (either of th ese two nam e s d u e t o m y d o d g e m e m o r y ) ; M o d e r n C h e m ical
C o m p a n y , o r , M o d e r n C l e a n i n g C o m pany and it cam e from Aust.
Hope thats h elpfull as a potential source if anyone finds a decent use for it. As yet I have made no enquires about possible
uses or prices but ill keep you all posted when I find som e.
Al Koholic S e p t e m b e r 2 6th, 2003, 06:44 PM

W ell, if you can deal with the 1,4-dichlorobenzene then by all m eans disregard this...
However, I just spent a good deal of tim e researching som e pathways and cam e up with a fairly sim ple route to 1,3-
diam inobenzene. Now, I know for a fact that refluxing this with HCl at 180C leads you to resorcinol (1,3-dihydroxybenzene),
a n d I a m almost 100% sure that I saw a quick reaction leading to 1,3-dichlorobenzene as well. I will have to go back and take
a look at the database to find out what conditions and such. If you are still interested I'll check it out next tim e I ca n...
Although I suppose I would also have to explain the entire route to 1,3 diam i n o b e n z e n e ( f r o m n a p t h a l e n e ) a s w e l l a n d y o u
m ay not be able to follow it all the way through....
Anyway, let me know.
frogfot S e p t e m b e r 2 6th, 2003, 07:32 PM

Couldn't find m uch on nucleophilic substitution on benzene halides in m y chem book, but IMO those two chlorines in 1,4-
dichlorobenzene should help together to withdraw electrons from b e n z e n e a n d m ake it m ore positive. So that at lea s t o n e C l
should be replaced with OH (a t relatively norm al conditions, no high pressure etc..)
Only similar reaction I could find in basic chem book was substitution of Cl in chlo robenzene by NH2-
The reaction won't work because the two chlorin es strongly deactivate the m olecule.
Deactivate toward electrophilic substitution, yes.. but opposite, toward nucleophilic..

It is not difficult to replace a halogen with O H b y refluxing in a strong base. However, once you append the OH you will never
get the O off again, at least I haven't seen any lab m e t h o d s o f d o i n g s o .
That bit about substituting a halogen for an am ine is nasty stuff, the rea ction pro ceeds with a m etal am ide in liquid am m o n i a .
Liquid am m onia is not the kin d of thing m o s t h o m e e x p e r i m enters should be playing around with if they value their health.
Al Koholic S e p t e m b e r 2 6th, 2003, 11:56 PM

T h e r e i s a l a b m e t h o d o f g o i n g f r o m phenol to aniline but it uses some exotic catalysts and I do n ot believe thre is a very
good yeild. Perhaps it was something like a zeolite cata lyst? I m ight be wrong...it was a couple weeks ago that I found out
a b o u t t h e m ethod. Difficult an d m ost likely im p o s s i b l e f o r t h e h o m e - e x p e r i m enter but possible...p erhaps it was silicon dioxide
with something else in the catalyst.
The only other way is to do it at som e ridiculously high pressure for a loo ooong tim e.

a n d I m provised C hemistry > W eird nitration pro cess - Archive File
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megalomania May 10th, 2003, 12:05 AM

HMT D Factory
Freq uent Poster
Posts: 220
From :
posted March 06, 2001 04:17 AM
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W ithout using HNO3 and H2SO4? This process is m o r e l i k e a n e x t r a m e t h o d f o r k nowledge since HNO3 and H2SO 4 m u s t h a v e
flooded in you people's room .
C a m e across this patent that use NO2 and Fe(NO3)3.H2O--"wet" ferric nitrate, to nitrate aromatic compound, like to l u e n e .
T h e p r o c e s s t a k e s p l a c e a t r o o m t e m p erature and under norm al pressure. Produces no waste

acid and m ild tem perature. By product is washed away with water. Funny huh?
nbk2000
Moderator
Posts: 1135
From : G u e s s
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Rather than teasing us, why not give u s the patent num ber?
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HMT D Factory
Freq uent Poster
Posts: 220
From :
posted March 06, 2001 03:54 PM
--------------------------------------------------------------------------------
Not listed, I think it is a JP patent num ber,
not US.
nbk2000
Moderator
Posts: 1135
From : G u e s s
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Than type the details or scan it in. Hell, even a screen shot would be OK.
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HMT D Factory
Freq uent Poster
Posts: 220
From :
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Details are just like that. Things are all done in room condition, solid liquid mixing, gas blowing.... No liquid is involved except
the benzene derivatives.
I think both ferric nitrate hydrate and NO2 involves in the nitration, neither of them is
a catalyst.
ezekiel
Freq uent Poster
Posts: 110
From :
--------------------------------------------------------------------------------
Shall I let you in on the secret?
Here we go:
The NO2 gas dissolves into the hydrated iron oxide,

Now you have a curious little particle that essetially contains HNO 3.
The iron oxide will not nitrate itself, pa rtly because is is unreactive, and partly becasue of the local charge configuration in th e
particle.
Now, the NO 2 (kinda part of a HNO3) is being ionised and pushed into an electrostaic filed created by the iron oxide. This
m a k e s i t e v e n m ore of a nucleophile than norm al.
W hen a tluen (or wha tever) atom com es along the NO2 can't wait to jum p o f f a n d react with it.
Thus you are still left with your iron oxide; which acts as a catalyst.
------------------
Ezekiel
' T h i n g s b a d b e g u n m a k e s t r o n g t h e m selves by ill'
HMT D Factory
Freq uent Poster
Posts: 220
From :
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It's not even iron oxide.
It's Fe(NO3)3 . H2O
Just because you have a general idea of catalyst m e c h e n i s m d o e s n ' t m e an you have to let out a lot of "educated guess".
Plus, hydrated iron oxide will react with NO2 in the instant they com e in contact. "partially because it is not reactive"?
W achatalkinbout?
ezekiel
Freq uent Poster
Posts: 110
From :
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Sorry Im u s t h a v e m i s r e d t h e q u e s t i o n .
I said "partly" beacsu e it is a com plex electrostatic mechanism that is no t easy to explain to anybody witho ut alot of time and
a basic knowlege of chem istry.
The reason i assumed it was iron oxide is that a sim ilar reaction occurs b e t w e e n s o m e g a s e s i n t h e p r e s e n c e o f i r o n o x i d e .
I'm really ever so sorry for assum ing something like that, really I am .
A "BASIC KNOW LEGE O F C A T A Y L T I C P R O C E S S " e h ?

W hy do you have to try and imply that I do not fully understand it?
I accept that I am not an expert, and catalytic chem istry is a subject in itself that is im possibly com plex in nature.
W ell, having been so rightiously corrected by the m an who m a k e t h h e x a m ethylenetriperoxidediam ide...

I will conlcude that in fact the reaction is still catalytic (it m u s t b e a s N O 2 a n d t o l u e n e d o n o t r e a c t n o m ally).
It could be basically what I said before but wiht the NO2 anion form ed differntly. In the en d there m ust be a NO2 nucleophile
ion to bond into the benzene ring.
Sorry guys for misreading that...
I m ean I was sjut so out of place!
------------------
Ezekiel
HMT D Factory
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From :
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Now our venerable gu e s t s p e a ker who jumped in, didn't read careful enough, acted like an know-it-all, condescende d , a n d t h e n
backfired, apologized !
If it is a reaction catalyzed by ferric nitrate hydrate.
Then try explain this : (HA!)
R-H + NO 2 ---> R-NO 2
without any byproduct or involvem ent of ferric nitrate hydrate...
Now where'd "thine" H atom go? Shake-a-spear?
Mr C ool
Freq uent Poster
Posts: 991
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Ezekiel: just checking , but you didn't really m e a n t o s a y a t o l u e n e a t o m , did you? An ATOM of tolu e n e ?
N o ? O h g o o d , that's OK then.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
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If you knew m ore about organic chem istry, you would know the chlorination process of arom atics to involve a Cl(+) ion m a d e
from C l2 with a catalyst; this one is AlCl3 (dry) or Fe(Cl3)....They act as Lewis acid by complexing the Cl(-) anion...
FeCl3 + Cl-Cl--> (FeCl4)(-) + Cl(+)
W hitout this C l2 is inert or attacks but outside the arom atic ring.
C6H6 +Cl(+) ---> (C6H6Cl)(+)---> C6H5Cl +H(+)
Then
H(+) + FeCl4(-) gives HC l (dry gas) and FeCl3.
As a conclusion when all term s in com m o n h a v e b e e n t a k e n a w a y (catalyst):
C6H6 + Cl2--> C6H5Cl + HCl
W hy to tell this? Think a bit....
Fe(NO3)3 + O2N-NO2 ---> NO2(+) + O 2N-Fe(NO3)3(-)
NO2(+) + C6 H6 --> (C6H6NO2)(+)--> C6H5NO2 +H(+)
H(+) +O2N-Fe(NO 3)3(-)---> HNO2 + Fe(NO3)3
2HNO 2--> H2O + N2O3--> H2O + NO + NO2
2NO + O2 -->2NO 2
Thus after sim plification:
C6H6 + N2O4 --> C6H5NO 2 + 1/2H2O + 1/2NO +1/2NO 2
ASAT: As sim p l e a s t h a t
------------------
" C h e m istry is all what stinks a nd explode; Physic is all what never works! ;-p :-) :o)"

a n d I m provised C hemistry > Hydogen Iodine - Archive File
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C h e m Boy
A new voice
Posts: 7
From : s d f a s
R e g i s t e r e d : M A R 2001
--------------------------------------------------------------------------------
Has anyone m ake Hydrogen Iodine? If you havnt heard of it its hydrogen gas and iodine gas combined to make a explosive.
Or h ydrogen gas driped into iodine (liquid) to making a gas. If you have heard it or m a d e i t p o s t a m e s s a g e .
m egalom ania
Adm inistrator
Posts: 653
From : U SA
--------------------------------------------------------------------------------
Do you m ean hydrogen iodide gas? If so, it is not explosive, nor flam m able. It is just anhydrous hydroiodic acid, like HC l. The
only way a m i x t u r e o f i o d i n e a n d h y d r o g e n i s e x p l o s i v e i s b e c a u s e h y d r o g e n i s e x p l o s i v e .
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For the m o s t c o m p r e h e n s i v e a n d i n f o r m a t i v e w e b s i t e o n e x p l o s i v e s a n d r e l a t e d t o p i c s , g o t o M e g a l o m a n i a ' s E x p l o s i v e s a n d
Stuff at http://surf.to/m e g a l o m a n i a
nbk2000
Moderator
Posts: 1135
From : G u e s s
--------------------------------------------------------------------------------
Hydriodic acid (HI gas in water) is used in clandestine chem istry for m a k i n g m e t h a m pheta mine by reduction of ephedrine.
It has no explosive use.
T o m a k e i t , p l a c e a q uantity of iodine crystals in distilled water. Bubble a stream of hydrogen sulfide gas through th e solutio n
till n o crystals are visible at the bottom of the flask.
Then filter th rough glass wool to rem o v e t h e e l e m ental sulfur that precipitates out. Concentration is determ ined by specific
gravity.
Distillation yields the 1.54 needed for reduction.
Hydrogen sulfide is easily m a d e b y m ixing sulfur and paraffin wax (or ke r o s e n e ) a n d h e a t i n g t o j u s t h i g h e n o u g h t o m e l t t h e

sulfur. Pass the gas through a long, wide tube loosely filled with cotton wool to filter out sulfur particles.
I f n o n e o f t h e a b o v e i n f o r m ation has any m eaning to you, you obviously didn't need to ask the question in the first place.
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Jhonbus
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From :
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Be careful... Hydrogen sulphid e is a *mite* tox ic
PYRO 500
Moderator
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From : s o m ewhere in florida
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Hydrogen Sulfide is VERY TOXIC!
HMT D Factory
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From :
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H y d r o g e n s u l f i d e s m ells like fart
hodehum
A new voice
Posts: 21
From : New Zealand
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Hydrogen Iodine is used as an inhibitor in liquid rocket fuel that contains red fum ing nitric acid/kerosene m ixtures to stop it
e a t i n g t h e m etal fuel tanks.
see for yourself
http://www.gulflink.osd.m il/irfna/irfna_sec01.htm
PHILOU Zrea lone

Freq uent Poster
Posts: 479
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2HI<==>H2 + I2
The reaction is easily reversible reason why HI is a good mild reducer...

a n d I m provised C hemistry > m a k i n g K 2 C O 3 - Archive File
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the_wingm a n
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From :
--------------------------------------------------------------------------------
I read in a form er topic that it's possib l e t o m a k e p o t a s s i u m c a r b o n a t e f r o m K N O 3 a n d C .
Should 1 part KNO3 to 2 parts C work?
I tried it but I wasn't successful.
blackadder
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Posts: 313
From : L o n d o n
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Just wondering why you want potassium carbonate, when you can have kno3?
hehe
[ T h i s m e s s a g e h a s b e e n e d i t e d b y b l a ckadder (edited February 14, 2001).]
firebreether
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From :
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Probably wants to ma ke fulm inating powder.
right?
jin
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Posts: 111
From : u k
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its b een a few years since i have done it,but i think its the same as norm al gunpowder without the sulphur
2kno3+3c=k2co3+3co
try 3 parts kno3 and 1c if that will not work try 2 parts c.
[This message has been edited by jin (edited February 14, 2001).]
M a m m ut
A new voice
Posts: 39
From : E s s e n , N R W , G e r m a n y
--------------------------------------------------------------------------------
quote:
--------------------------------------------------------------------------------
Originally posted by the_wingman:
I read in a form er topic that it's possib l e t o m a k e p o t a s s i u m c a r b o n a t e f r o m K N O 3 a n d C .
--------------------------------------------------------------------------------
U have KNO 3 and u will m a k e K 2 C O 3 o h o h o h

I can tell u a easier way to m a k e K 2 C O3, if u give m e the KNO3
J
Moderator
Posts: 605
--------------------------------------------------------------------------------
W hy not tell us all?
J
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"If the aquarium water has to be drunk don't waste the fish. In fact they'll probab ly be the easiest to eat even if you don't
need the water. The cat is next in the pot." - John 'Lofty' Wiseman
SMAG 12B/E5
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Posts: 61
From :
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Y o u c a n o b t a i n p o t a s s i u m c a r b o n a t e f r o m s o m e p o o l s u p p l i e r s f o r a k a l i n e Ph adjustment of water or leach it from w o o d a s h e s .
[This message has been edited by SMAG 12B/E5 (edited March 16, 2001).]
Agent Blak
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--------------------------------------------------------------------------------
Can't you also get K2 CO3 as Baking Powder? I will check the Pool thing today.
------------------
"...I Am Not Much of a Dancer But,
Just Wait Till The Fucking Begins"
Anthony
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From : England
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B a k i n g s o d a i s s o d i u m bicarbonate
washing crystals are sodium carbonate

and Improvised Chemistry > No nitric acid - Archive File
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radar
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Posts: 73
From: Redding California
posted 01-09-2001 01:42 AM
--------------------------------------------------------------------------------
Hey, any of you guys know some of the more common nitration recipes that are done without nitric acid but instead involve
adding some nitrate to the bath to make nitric acid? Thanks.
sadsakjoel
Frequent Poster
Posts: 170
From:
posted 01-13-2001 01:50 AM
--------------------------------------------------------------------------------
do you mean like picric acid with aspirin? where you mix the acid from aspirin with sulfuric and potassium or sodium nitrate
instead of nitric acid? If this is what your talking about I'll post the rest later.
radar
Frequent Poster
Posts: 73
posted 01-13-2001 02:12 AM
--------------------------------------------------------------------------------
No, I already know about that one, something like maybe NG or RDX, or TNT, or EGDN.
Stone
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Posts: 140
From:
posted 01-13-2001 04:20 AM
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Yes, recipes LIKE the picric acid one. Does that idea work for any other nitrations that usually require HNO3?
Anthony
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Posts: 2306
From: England
posted 01-13-2001 09:56 AM
--------------------------------------------------------------------------------
Apparently it will only work for simple nitrations like NG/NC etc. I'd say RDX without HNO3 is asking for a bit much! (i.e no
chance!)
Mr Cool
Frequent Poster
Posts: 991
posted 01-13-2001 11:47 AM
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Yeah, I've heard that impurities of sulphur compounds can cause very low yields when making RDX by decomposing one of the
intermediate reactants I think.
I know for a fact that it works when making NC, because that's the method I use.
radar
Frequent Poster
Posts: 73
posted 01-13-2001 07:48 PM
--------------------------------------------------------------------------------
Well, Mr. Cool, can you give me your exact method for making NC, I bet this would work for EGDN as well due to the acids
being the same.
Mr Cool
Frequent Poster
Posts: 991
posted 01-14-2001 07:22 AM
--------------------------------------------------------------------------------
Sure. I use 1 gram of sodium nitrate, added to 4ml of cold 98% H2SO4 and stir it to dissolve the NaNO3. Let it cool to around
5 C by placing the reaction beaker in a bowl of iced water. When this temperature has been reached, put in 2 grams of cotton
wool (the absorbent stuff from pharmacies etc.), and hold it under the acid with a glass rod, while stirring continuously for 20
to 30 minutes at 5 to 15 C. Then get the NC out with the glass rod and plunge it into 100ml of 10% NaHCO3 solution, then
rinse it with water, then again with sodium bicarbonate solution and so on until the wash with water is neutral, pH7. Then
dissolve the NC in acetone to form a runny liquid (not very concentrated NC solution), and filter it through a fine mesh to
remove any unreacted cotton. Evapourate the acetone, and you'll be left with pure NC. I then CAREFULLY file it into a powder,
slowly with a hand file and store it under 2% NaHCO3 solution. Obviously this can be scaled up to produce any amount.
I suppose the same basic method would work for EGDN.
Anthony
Moderator
Posts: 2306
From: England
posted 01-14-2001 09:02 AM
--------------------------------------------------------------------------------
Sounds good! Two questions, can you use KNO3 instead of NaNO3? Will 91% H2SO4 work or will I need to go out and buy a
hotplate to concentrate it?
Mr Cool
Frequent Poster
Posts: 991
posted 01-14-2001 09:27 AM
--------------------------------------------------------------------------------
KNO3 will work, but remember: K (39 atomic mass units) atoms are heavier than Na (23 a.m.u.) atoms, so each gram of KNO3
will contain less NO3- ions than a gram of NaNO3, so adjust the amount accordingly.
91%? Hmmm.... I think that'd work, but it might be worth getting a hot plate because it won't work for many other explosives.
Where did you get the H2SO4 from? I'm having to boil battery acid, which is dangerous, boring, time consuming and very
expensive.
Anthony
Moderator
Posts: 2306
From: England
posted 01-14-2001 12:08 PM
--------------------------------------------------------------------------------
Ok, I'll get the calculator our later and work that out. The H2SO4 is "one-shot drain cleaner" available from B&Q Wharehouse
stores, 4.99 for 1L.
radar
Frequent Poster
Posts: 73
posted 01-14-2001 03:51 PM
--------------------------------------------------------------------------------
Will this work with ammonium nitrate? THanks
Anthony
Moderator
Posts: 2306
From: England
posted 01-14-2001 07:20 PM
--------------------------------------------------------------------------------
Isn't NC hard to detonate? Or do you just use this stuff as a low explosive?
SATANIC
Frequent Poster
Posts: 237
From: australia
posted 01-15-2001 01:21 AM
--------------------------------------------------------------------------------
what is the process by which you purify the H2SO4? straight boiling? I thought you couldn't boil it over a certain % before it will
not purify any more. How do you test the conc. when finished? thanks in advance.
Mr Cool
Frequent Poster
Posts: 991
posted 01-15-2001 01:30 PM
--------------------------------------------------------------------------------
It will work with AN if you: a) dry it in a low oven first, and b) adjust the amount used so that you have the same amount of
nitrate ions.
NC isn't very hard to detonate, as long as it's got a high enough N percentage. It's much easier than TNT, ANFO or ammonium
picrate for example, and about the same as RDX I think. Also, since it's a very energetic deflagrant, it can make the transition
from deflagration to detonation if fairly large quantities are ignited in a strong container. I normally use it as a low explosive
or a plasticiser for AN or RDX with things like NM, but I do sometimes use it as a base charge in detonators.
Boiling can get H2SO4 to about 95-98%. The boiling point will rise to something like 140 C, but I don't know the exact figure.
You can test the specific gravity with a hydrometer which you can buy at places that sell wine making kits. 98% H2SO4 has a
specific gravity of 1.84 (H2O = 1).
Anthony
Moderator
Posts: 2306
From: England
posted 01-15-2001 06:00 PM
--------------------------------------------------------------------------------
Ah, I was thinking of smokeless powder NC, I didn't think it would be easier to nirate further than that.
I worked out 1.7gm of kno3 should give the same number of nitrate ions as 1gm NaNO3.
I tried it today, I used five timmes your figures, 20ml 91% H2SO4, 8.5gm KNO3, 10gm cotton wool. Having added all the kno3
(in an ice bath) and after a while of stirring, there were crutsy white lumps left, I figured either these were impurities in the
kno3 (the only thing I could think would be in there would be chalk which should have dissolved) or the solution was saturated.
I ran the solution through a fine sieve that got rid the crap, the solution was yellow at this point.
While I was weighing out the cotton wool I relaised that there was no way in hell I was going to get all that cottn wool into such
a small volume so I shredded and added enough so that ther remained enough liquid to cover the soaked wool (I reckon
about 1/2gm). I stirred it for 20mins then left it for another 20 to have a cup of tea. I washed it in 10% sodium bicarbonate
solution (lots of foaming!) 3 times with and equal number of plain water washes in between. I fished out the lump of wool and
put it in cheap, clear, no additive nail varnish remover, I'm going to leave it till tommorrow to give it fair chance to dissolve
(had a white soup after a few mins so I guess at least some of it has dissolved).
I kept a check on the temperature of the solution when stirring the wool and it stayed at 7*C throughout.
How on earth do you get 2gm cotton wool into 4ml of liquid?! Does it sound like I've seriously messed up? If this works it
would be good because it's really thrifty with the acid and cotton wool costs nothing.
Thanks for the procedure!
Mr Cool
Frequent Poster
Posts: 991
posted 01-16-2001 01:13 PM
--------------------------------------------------------------------------------
Sorry! I made a mistake in the method. I meant to say 0.2 grams of cotton wool per 4ml of H2SO4, not 2 grams! I can see
why you might have been a bit confused!
Also, I really think it would be better to use 98% H2SO4, because during the nitration, water is produced. When the acid conc.
gets below a certain point, the nitration practically stops. It would obviously reach this point a lot sooner if you're using 91%
acid, so the cellulose might not be as fully nitrated.
Don't worry, the nitration mixture should be yellow, due to the formation of nitric acid and nitrogen oxides in it.
Potassium nitrate is considerably less soluable than sodium nitrate (in g/100g H2O), and also more of it is needed so maybe
this is why it didn't all dissolve.
If the nail varnish remover is an acetone/water mixture, the NC might not dissolve fully, but it shouldn't really matter.
Also I forgot to mention (sorry!) that it's good to soak the NC in a weak, 1% or 2% sodium bicarbonate solution for 10
minutes or so at about 60 or 70 C to make it contain less acid, although the method I gave you should have done a pretty
good job of that already.
So it should have worked the way you did it, but if it's not fully nitrated then try concentrating your acid further. The fact that
it's dissolving in the acetone is obviously a good sign.
Let me know how you get on!
Hope this cleared things up a bit.
Anthony
Moderator
Posts: 2306
From: England
posted 01-16-2001 02:11 PM
--------------------------------------------------------------------------------
Ah, 0.2gm, certainly clears that problem up! I ran the NC/acetone through a fine sieve, the cotton wool recovered iso only
about half of what went in so at least some of it hould have dissolved. It's evaporating now.
As I was doing the procedure I glanced at some of my stuff and realised I already have a box of NaNO3, doh.
I'll concentrate the acid for next time. I'm moving house at the end of the month and this one's got a nice shed I can
permanetly setup as a lab, sort out a still and start doing things properly.
Mr Cool
Frequent Poster
Posts: 991
posted 01-16-2001 02:19 PM
--------------------------------------------------------------------------------
Yeah, a nitric acid still is essential for most high explosives if you're serious. And try to get an extractor fan in the shed, to get
some nice clean air in while you're using it!
Does anyone know how much a couple of acres of land is?! I really want a pyrotechnics liscence!
Smartguy
New Member
Posts: 11
From:
posted 01-16-2001 02:45 PM
--------------------------------------------------------------------------------
quote:
--------------------------------------------------------------------------------
Originally posted by Anthony:
Apparently it will only work for simple nitrations like NG/NC etc. I'd say RDX without HNO3 is asking for a bit much! (i.e no
chance!)
--------------------------------------------------------------------------------
Well, Anthony, you're wrong. One of the better recipes for making RDX doesn't use HNO3. It uses ammonium nitrate and
acetic anhydride. The latter will be a problem, though: you probably will have a difficult time obtaining it.
I'll try if I can retrieve this recipe for you...
[This message has been edited by Smartguy (edited January 16, 2001).]
Anthony
Moderator
Posts: 2306
From: England
posted 01-16-2001 02:50 PM
--------------------------------------------------------------------------------
Shall do. I suppose it depends what kind of land! Land suitable for beuilding on is about 12 a square yard (or metre)IIRC
but a field that's is useless for growing stuff or grazing should cost very much at all. Have you got something that lists the
requiremnts for a pyro license? COuld be an interesting read.
Mr Cool
Frequent Poster
Posts: 991
posted 01-17-2001 10:55 AM
--------------------------------------------------------------------------------
As far as I'm aware, the NH4NO3/acetic anhydride method for making RDX uses a different reaction than nitrate/H2SO4
reactions, which use the H2SO4 and a nitrate to form nitric acid in solution.
I've got the requirements for a liscence that enables you to make small amounts of low explosives written down somewhere.
I'll try and find it for you if you like. Basically, the place where you make them has to be at least a certain distance from roads
or anyone else's property, you need a well made place to make them in with all the safety stuff, and you need to convince
them that you're not mad.
How's the NC?!
Anthony
Moderator
Posts: 2306
From: England
posted 01-17-2001 02:02 PM
--------------------------------------------------------------------------------
The NC worked, it wasn't very well nitrated so it didn't burn very fast but I will try again soon with higher conc H2SO4. Once
again, thanks for the synthesis!
"you need to convince them that you're not mad" - Damn.
Can acetic anhydride not be synthesised from glacial acetic acid? If do manage to synthesise RDX using H2SO4/NH4NO3 and
post your results I'll gladly eat my words.
Mr Cool
Frequent Poster
Posts: 991
posted 01-17-2001 02:38 PM
--------------------------------------------------------------------------------
Try a more concentrated H2SO4, and if you like I bet you could take the reaction temperature higher, to about 25 C without
any danger of runaway nitration. And I think NaNO3 would be better than KNO3 due to it's higher soluability, but make sure
you dry it first.
The sanity problem has always been the main obstacle for me as well! Quack quack.
Where exactly did you buy your H2SO4 drain opener? I've just looked in the Nottingham B&Q Warehouse, but they didn't have
it! What section is it in? Would you consider selling me some if I can't find it?! If so, how much would you ask for 3L, including
postage etc? I really need some!
Acetic anhydride can be made from glacial acetic acid by bubbling the thermal decomposition products of acetone through it. I
forget what the gas is called. It shouldn't be very hard to do, but might take a bit of adjustment to make it work well (temp.
etc.)
Anthony
Moderator
Posts: 2306
From: England
posted 01-17-2001 03:41 PM
--------------------------------------------------------------------------------
I think it's ketane, it'd be a lot of effort to set up, but once yoy have it working then it'd be easy to run off batches.
I got my H2SO4 from Northampton B&Q Warehouse, it's in the plumbing section (same isle as the copper plumbing IIRC) with
a bunch of other drain cleaners. There's also a small diy shop a few miles from me that sells it, it's 4.99 for a 1L bottle, I can
send you some if you can't find it. It's need packing well because parcels get chucked about "a bit".
I'll try the NC without the ice bath next time (maybe have one on standby) if 25*C is OK. What are the dangers of run away
nitration aside from the solution boiling and billowing toxic fumes? Is there a detonation risk?
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 01-17-2001 04:44 PM
--------------------------------------------------------------------------------
What about for PETN?
does anybody know if you could use this method for that? and if so how much would you need to replace the HNO3?
Your help it greatly appreciated.
------------------
A wise man once said:
"... As He Waits For The Time When The Last Become First And,
The First Shall Become last"
--RATM
sadsakjoel
Frequent Poster
Posts: 170
From:
posted 01-18-2001 04:10 AM
--------------------------------------------------------------------------------
If your problem is that you cant find nitric acid i know of an explosive (primary) that doesnt use any, TACC it involves copper
sulfate which is what your looknig for and wither the copper sulfate you make TACC tell me if this is of any use and i will post
the entire pocess later.
------------------
All there is to fear is your own co-ordination
Mr Cool
Frequent Poster
Posts: 991
posted 01-18-2001 02:12 PM
--------------------------------------------------------------------------------
That's what I thought: Lots of effort to set up, but simple to run.
I've heard, although I didn't really want to try it, that there's absolutely no risk of a detonation or rapid decomposition from
runaway nitration until you get to about 80 or 90*C for NC. At 25*C it would nitrate substantially quicker than at 5*C or so.
I've never seen a method like this for PETN, but I can't think of a reason why it wouldn't work. I'll try and find out for you.
Where can you get PE? Or do you make it? I know how to make it, but it seems quite hard because I'd also have to make the
reactants.
I know of TACC, but have never tried it. I'd like to see the methid you use.
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 01-18-2001 02:53 PM
--------------------------------------------------------------------------------
I am going to find out if I can do it via this method before I start looking for it.
------------------
"... As He Waits For The Time When The Last Become First And,
The First Shall Become last"
--RATM

SofaKing
Frequent Poster
Posts: 399
From: YEAH RIGHT !!
posted 01-19-2001 01:57 AM
--------------------------------------------------------------------------------
Accoording to KID (kitchen imprvised detanators) M.M.A.N. (monomethylamine nitrate)can be made with nitic acid in
concentrations of 20%. I would think the sulfuric/nitrate method would work. The only problem would be procurring the
methylamine.
------------------
"ARE YOUR PAPERS IN ORDER" -- Jack Booted Thug
[This message has been edited by SofaKing (edited January 19, 2001).]
Mr Cool
Frequent Poster
Posts: 991
posted 01-20-2001 08:03 AM
--------------------------------------------------------------------------------
MMAN should work for absolutely any concentration of NA, because it's an ionic compound. Any concentration of NA will have
NO3- ions in it, so any concentration should make MMAN with methylamine solution.
Look under the "NM sensitising?" topic to find out how to make methylamine. it might help.
sadsakjoel
Frequent Poster
Posts: 170
From:
posted 01-23-2001 09:13 PM
--------------------------------------------------------------------------------
Heres the copper sulfate part: (from FEMFEP)1.5 Preparation of Copper Sulfate (Pentahydrate)
Copper sulfate is a required material for the preparation of TAC.
MATERIAL REQUIRED:
Copper wire or pieces

Sulfuric acid (battery)
Potassium nitrate or nitric acid (field grades)
Alcohol
Water
Two heat resistant glasses or jars, one pint
Paper towels
Metal pan (for hot water bath)
Wooden rod
Cup
PROCEDURE:
1. Place 10 grams of copper into one of the jars and add one
cup (240 milliliters) of sulfuric (battery) acid. To this
mixture add 12 grams of potassium nitrate, or 1.5
teaspoons of nitric acid. NOTE: Nitric acid gives a
product of greater purity.
2. Heat the mixture on a hot water bath (near boiling) until
the bubbling has ceased (requires about two hours).
* CAUTION: This reaction evolves strong toxic fumes, and

therefore must be performed in an open, well
ventilated area.
3. Pour the hot blue liquid into a second vessel (keeping

the unreacted copper in the first jar) and allow to cool
at room temperature.
4. After the crystals have formed, carefully pour away the
liquid and crush the crystals. Then add 1/2 cup (120
milliliters) of alcohol to the powder and stir.
5. Pour the solution through the towel filter and wash the
solid left on the paper three times, using 1/2 cup (120
milliliters) portions of the alcohol each time.
6. Allow the product to air dry for two hours.
And the TACC (KIBC)

TACC (Tetraminecopper (II) Chlorate)
DETONATION VELOCITY - Not given
FRICTION SENSITIVITY - This primary explosive is as sensitive as is lead

azide
BEHAVIOR TO FLAME - Deflagrates with a green flame. Requires confinement to

detonate.
Tetramine copper chlorate is a very interesting primary explosive.

While it has these good properties it is also easily made. It's drawbacks
are the tendency to "deadpress" or become so packed that it will not
detonate the base charge in the cap and water contamination problems. For
this primary explosive to detonate it must be loose in the detonator shell.
It would be best used in caps where the base charge is pressed in first.
Rifle shell improvised blasting caps would not work well with this
explosive due to this property. In this reaction the sodium chlorate and
the copper sulfate are heated together with methanol. This reaction
produced copper chlorate. This copper chlorate dissolved in methanol. It
then has ammonia gas bubbled thru the solution. The tetramine group is
added in this step. So the main actors in this chemical play are copper
sulfate other wise known as "blue vitriol". Copper sulfate is available
from feed stores or electroplating chemical supplier. Sodium chlorate is
also a chemical required and would be available from matches, dyes,
textiles manufacture and as a weed killer. "Kitchen Improvised Plastic
Explosives" has a section on chlorate manufacture in chapters four five and
six. Ammonia is the last building block. This can be generated in one of
two ways which will be explained in the manufacture section. The methanol
used is just a reaction liquid and a carrier, as it does not actually enter
into the reaction. One problem with this process is the contamination of
the methanol with water. This allows the sodium sulfate to become soluble
in the first reaction and will remove the ability to separate the products
of the reaction. The process is longer than others but is simple and
produced a good purity, stable product. This primary explosive should be
kept dry, as it could begin to decompose in the presence of moisture.
MANUFACTURE-
Measure 15 grams of sodium chlorate into a large mouth pint bottle.

Sodium chlorate is the oxidizer in matches. It is also available as a weed
killer. Add 360 ml of methanol or ethanol to the sodium chlorate in the
pint jar. To this add 24 grams of copper sulfate. Place this liquid in a
hot water bath. Heat at the boiling point for 30 minutes with occasionally
stirring the liquid during the reaction.
CAUTION: Remember methanol is very flammable and great care should be taken
to ensure the lack of open flame in it s proximity. Avoid
breathing the vapors of methanol.
Keep the volume constant by continually adding alcohol to replace what is

being boiled away. After 30 minutes remove the jar from the water bath. The
color of the solution should change from blue to light green. Filter the
solution into a jar through a paper towel or drip coffee filter. The
filtrate (liquid) should be caught in a jar similar to the one used in the
first step. Label this liquid #1. In a narrow necked gallonjar or flask
and a stopper (one hole) place 1500 ml clear ammonia water in the solution.
This is available from the grocery store in a clear non-soapy form. In the
mouth of this is placed a stopper with one hole and a plastic or rubber
hose. This is placed into a hot water bath. Ammonia will begin to generate
out of the gallon jug. A better ammonia generator could be made by filling
a long necked bottle or flask with 250 grams lye (sodium hydroxide). 500
grams of dry ammonium nitrate fertilizer or ammonium sulfate fertilizer is
added. Addition of small quantities of water and closing with a stopper
hose set up could generate greater quantities of ammonia and it would be
drier ammonia due to the nature of its generation. Generation would be
maintained by the addition of more water. But with either method the hose
should be placed in the liquid in the liquid #1. The ammonia gas should be
bubbled through the liquid. It will begin to absorb ammonia turn light
blue. Continue bubbling for 10 minutes.
CAUTION: The ammonia gas generated will kill or cause grave damage if
exposure is severe. Use with good ventilation.
The solution will turn dark blue. Bubble the ammonia gas through solution
#1 for ten more minutes and remove the hose from the solution. Reduce the
volume of the liquid by pouring into a shallow pyrex dish. Set this dish
under a fan and allow 1/2 the alcohol to evaporate. Filter (paper towel
or drip coffee filters) the crystals that remain in the liquid and wash
them with 50 ml very cold methanol. Set these aside to dry for 16-24 hours.
CAUTION: Explosive is shock and flame sensitive and great care should be
exercised during handling.
There is another method from FEMFEP that is similar to this one, say so if you want it.
Mr Cool
Frequent Poster
Posts: 991
posted 01-24-2001 02:25 PM
--------------------------------------------------------------------------------
Thanks
Field Expedient Methods for Explosives Production, or something like that? I think I've got that somewhere... Does it tell you
how to make lead azide from hydrazine and isopropyl nitrite and a few other things? If so, I already have it. I must have over-
looked the TACC section.
sadsakjoel
Frequent Poster
Posts: 170
From:
posted 01-24-2001 08:12 PM
--------------------------------------------------------------------------------
yeah thats the one, The production of TACC might not be in there, but from memory I thought it was.
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-09-2001 08:29 PM
--------------------------------------------------------------------------------
Hello.... i found this old post and tried to make nitrocotton like Mr Cool described. The interesting thing is that this 'cotton
wool' (that is used to clean wounds... um... this white stuff... ) disolved in H2SO4/KNO3 solution.... and mr Cool said "Then get
the NC out with the glass rod" how can i get it out if it is disolved ? ...i mean there was only liquid left... like syrup, yellow,
almost transparent.
[This message has been edited by Chainsaw (edited April 09, 2001).]
Rhadon
Frequent Poster
Posts: 95
From: Germany
posted 04-09-2001 09:31 PM
--------------------------------------------------------------------------------
Something went wrong with your reaction. The cellulose was probably dissolved in the sulfuric acid because of a condensation
reaction (just a theory of mine). This also explains the yellow color of your liquid. Perhaps the nitric acid you used wasn't
concentrated enough or you used too little. It might help if you tell us the ratio and the concentrations you used.
Microtek
Frequent Poster
Posts: 205
From:
posted 04-10-2001 04:12 AM
--------------------------------------------------------------------------------
Chainsaw: Did you cool your acid solution before adding the cotton? I seem to remember having my cotton dissolve, and I
think it was because I didn't cool the acids down after mixing them. I can't really remember; this was about 15 years ago and
I wasn't that old.
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-10-2001 11:24 AM
--------------------------------------------------------------------------------
i tried it again... now i cooled it somewhere 5 celsius. this time cotton wool went very sticky mess... like homemade napalm
(from gasoline and styrofoam).
Nitro
Frequent Poster
Posts: 51
From:
posted 04-10-2001 01:06 PM
--------------------------------------------------------------------------------
You can make lead azid with HN3
HN3 can made bye the reaction of HNO2 and Hydrazine.
c0deblue
Frequent Poster
Posts: 229
From:
posted 04-10-2001 03:14 PM
--------------------------------------------------------------------------------
Are you sure the "cotton" you're using is real cotton? Some of the cotton-like products used in pillbottles and sold for wiping
and cosmetic purposes are actually synthetic materials, which might account for the difficulties you describe. I don't think
*real* cotton should dissolve (even partially) during the reaction stage of the process.
Anthony
Moderator
Posts: 2306
From: England
posted 04-10-2001 03:17 PM
--------------------------------------------------------------------------------
The cotton wool shouldn't dissolve in the H2SO4/KNO3 solution... It should just be a wet mass, like when you put cotton wool
in water. At least mine did.
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-12-2001 09:19 PM
--------------------------------------------------------------------------------
YEEEEEHAAAWWWW!!!!!!
My first nitration completed ... successfully... (i have tried to nitrate evrery kinda stuff for 30+ times i could say... and every
time something went wrong...) Last time this "cotton wool" fucked up... i dont know... the package said 100% cotton wool...
but this time i got it from friend... and got it right
nbk2000
Moderator
Posts: 1096
From: Guess
posted 04-13-2001 12:17 PM
--------------------------------------------------------------------------------
So did it flash like it's supposed to? And I assume you're talking about the nitrocotton, right?
------------------
"The knowledge that they fear is a weapon to be used against them"
Go here to download the NBK2000 videos.
Anthony
Moderator
Posts: 2306
From: England
posted 04-13-2001 02:26 PM
--------------------------------------------------------------------------------
What a day...
I decided to have another go at NC today so I concentrated my H2SO4 and used NaNO3 this time.
The NaNO3 would dissolve fully so I warmed the a acid up on the hotplate and stirred it (I say "warmed" but it went upto
100*C before it dissolved). So I let it cool down, decided it was taking too long and put the dish in a water bath. Miss-judged
the depth of the water and some ended up in the reaction dish.
So, start again...
Again the NaNO3 wouldn't dissolve properly so I warmed teh acid to 40*C and with a lot of stirring decided to sod the small
amount that wouldn't dissolve and just leave it. Got fed up waiting for it to cool and decided that 35*C wasn't to high so put a
little cotton wool in and kept a close eye on the temperature. No rise so gradually added the lot, the temperature actually
dropped another 5*C by the I'd finnished the addition. Trouble was the cotton wool comletely dissolved... I've put the solution
in the fridge/freezer just incase it helps, but I doubt it.
So will try *again* at 10*C another day.
Anthony
Moderator
Posts: 2306
From: England
posted 04-13-2001 03:17 PM
--------------------------------------------------------------------------------
Nope, just checked it and it's very cold but still very much in solution. Seeing as it was nice and cold I put in another load of
cotton. The mass soaked up all the liquid so I poured in some more H2SO4 to maintain a "bath". The mass was a sticky mess
at this point and the goo had to be scraped off of the stiring rod. I put in some more NaNO3 for good measure and stirred
some more and the cotton wool go started to thin and eventually dissolved. I'm not sure whether the addition of the NaNO3
caused the cotton wool to dissolve or whether it was just a gradual dissolvtion that had started when the cotton wool was
added. The mixture didn't warm at all at any point. Something wierd is going on. I take it that boiling the solution presents an
explosion hazard or could it be done as a last ditch attempt?
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-13-2001 07:28 PM
--------------------------------------------------------------------------------
.
[This message has been edited by Chainsaw (edited April 13, 2001).]
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-13-2001 07:36 PM
--------------------------------------------------------------------------------
Your "cotton wool" dissolves because it is not real... it is probably synhetic (don't beleive what package said that you bought it
in) ... (that was where i failed first time)... try to get real cotton wool
I thik when you add cotton wool it shouldn't generate heat... (much) at least mine didn't.
Anthony
Moderator
Posts: 2306
From: England
posted 04-13-2001 07:42 PM
--------------------------------------------------------------------------------
The strange thing is, this is the same brand of cotton wool that I used last time (which worked)... I'll try with another brand.
frostfire
Frequent Poster
Posts: 266
From:
posted 04-14-2001 10:57 AM
--------------------------------------------------------------------------------
d
[This message has been edited by frostfire (edited August 17, 2001).]
Chainsaw
New Member
Posts: 34
From: Estonia
posted 04-15-2001 10:33 PM
--------------------------------------------------------------------------------
umm... what's this fuss about nitrating at low temperatures. It isn't because of danger of detonating is it? for exammple this
text from megalomania's site "If the temperature ever rises above 20 C it is ruined as no more nitro will be made" ...this was
description of making nitro clycerin. I thought that rising teperatures makes nitrating better.
Microtek
Frequent Poster
Posts: 205
From:
posted 04-16-2001 06:55 AM
--------------------------------------------------------------------------------
frostfire: NC is actually more brisant than AP if it is sufficiently nitrated, but it should be initiated with a cap rather than just
ignited. Batches that are nitrated close to the theoretical limit will probably make the DDT on its own, but to avoid burning a lot
of power in this process you should use a cap.
frostfire
Frequent Poster
Posts: 266
From:
posted 04-16-2001 06:17 PM
--------------------------------------------------------------------------------
d
[This message has been edited by frostfire (edited August 17, 2001).]
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
Registered: MAR 2001
posted 04-16-2001 06:22 PM
--------------------------------------------------------------------------------
Im pretty sure he means DDT as the transformation deflagration-detonation (burning to exploding). Not
dichlorodiphenyltrichloroethane (the insecticide)
frostfire
Frequent Poster
Posts: 266
From:
posted 04-16-2001 06:51 PM
--------------------------------------------------------------------------------
understood
shooter2
Frequent Poster
Posts: 56
From:
posted 04-16-2001 07:29 PM
--------------------------------------------------------------------------------
Frostfire. I read in an old tech. manual that guncotton ,in freshly nitrated form, is very friction and shock sensitive! Please
don't try to pack it hard into anything. It is also very unstable because of 1. residue acid 2. cotton is an insulator and doesn't
quickly dump the heat caused by decomposition. It can easily detonate all by itself.
Microtek
Frequent Poster
Posts: 205
From:
posted 04-17-2001 10:18 AM
--------------------------------------------------------------------------------
Yes, DDT is deflagration-detonation transition it's just a bit long. DDT is a common abbrevation for the phenomenon.
I know of only one test that is simple to make, and that is to light it with a match.
If it is highly nitrated it will go off with a slight thump and very intensive light much like unconfined acetone peroxide.
It is probably better to use the NC in its cotton form and pack it in a pipe like you suggested rather than colloidinizing it with
acetone:
- The cotton form will be less dense and thus easier to initiate.
- It is very difficult to get colloidinized NC without additives such as AP, to harden in a uniform fashion.
Regarding sensitivity, well-washed NC is quite stable; it is very flammable, but is totally impervious to shock. I don't know
about friction. It is not that hard to purify it sufficiently, but it does take some time. Just put the cotton in a jar with lid, add
lots of clean water then shake vigourously, replace the water and add sodium bicarbonate. Shake again ( and release the
pressure ). Repeat until no bubbles are formed.

JB
New Member
Posts: 27
From: UK
posted 04-17-2001 10:30 AM
--------------------------------------------------------------------------------
I've had a search through some of the topics and not found an answer so I'll ask here:
Is it possible to manufacture small amounts of AN by the addition of potassium nitrate in ammonia in an ice-salt bath? I know
it would be far wiser to buy the stuff but I was curious whether this method of nitration would work.
Also - I was told that a good source of aluminium powder is from costume & theatre shops to give a silver/grey colour to hair.
frostfire
Frequent Poster
Posts: 266
From:
posted 04-17-2001 08:29 PM
--------------------------------------------------------------------------------
hi, thanks alot for the info Microtek & Shooter2
I usually wash it over 'n over again in excessive number but that bubling indication will save a lot of time, thanks again.
PS: collodinized NC has unregular form, but what I do is to stuff a hollow pipe into the paste while it's still wet, (maybe insert
the detonator) then dry it, so when it dry it will take the pipe shape and is quite hard
frostfire
Frequent Poster
Posts: 266
From:
posted 04-17-2001 08:44 PM
--------------------------------------------------------------------------------
I'll just add one more question of my failed nitroglycerine
I use boiled H2SO4 until it lets out white fumes, 72 % HNO3 (test gravity), and lab grade glycerine
I take just about 30 ml of each acid, mix them, gets hot, then I wait and cool it.
Once it's cold, I began adding glycerine with a pipet drop by drop
There's about 30 seconds period between each dropping and I stirred gently and continuously
After 3 minutes, I saw that the glycerine looks like just floating around & no particular reaction or temp increase happen..
I think that the HNO3 conc is too low so I believe it's over and squirt the rest of the nitro into the solution.
Suddenly it's red NO2 gas all around.
Now, should I have succeded only I need more patience or is the HNO3 conc is too low that it's only sufficient to decompose
the mixture?( I think someone say NG & NC can be made using not so high HNO3 conc)Could it be the glycerine or H2SO4?
Anyway , thanks for any thoughts..
Microtek
Frequent Poster
Posts: 205
From:
posted 04-18-2001 09:16 AM
frostfire: When using 70% nitric acid to make NG, I think you should use more H2SO4; maybe about 2 SA to 1 NA.
Nevertheless, I think you should consider this method that I use:
4 grams of NH4NO3 is dissolved in 6 mL H2SO4, the solution is cooled and 1 mL glycerine is added slowly. I reccomend stirring
gently with a thermometer and keeping the temp between 10 and 15 degrees C. Note that if using these small amounts, the
H2SO4/NH4NO3 solution will be quite thick especially at low temperatures, but this does not affect the process.
Once the addition of the glycerine is complete, pour the solution into crushed ice bit by bit and keeping an eye on the temp.
I guarantee this process will work, and give a good yield. I use store-bought glycerine, which means 85% glycerine 15% water,
lab-grade will probably give a better yield.
Regarding the hardening of colloidinized NC in the pipe: Have you tried cutting the end product open? My guess is that you will
see a lot of cavities in the mass, which will lead to lower performance.
Oops I forgot to give credit to gcic who first ( to my knowledge ) suggested this
method on the forum.
[This message has been edited by Microtek (edited April 18, 2001).]
frostfire
Frequent Poster
Posts: 266
From:
posted 04-18-2001 11:01 AM
eheh, I believe that NC cavities appear to be true....nice observation

I'll try that method and how about the promising one that glycerine is added into H2SO4 first then nitric acid is added into the
cooled solution
Have you ever tried this and any good yield?
(wonder how the nitration process can be flipped-flopped?!?!?)
Microtek
Frequent Poster
Posts: 205
From:
posted 04-19-2001 04:27 AM
No I haven't tried that other method, as the one I have works so well; I get 1 mL NG for every mL glycerol ( when you take the
water content into account, so 0.85 mL NG per mL glycerine 85% ).
YTS
Frequent Poster
Posts: 61
From:
posted 04-19-2001 05:35 PM
Does any one know a non nitric acid formula for mercury fulminate .and microtec or anyone do you reckon you could substitute
the NH4NO3 for NANO3 by upping the H2SO4 & the NANO3 ?
YTS
Frequent Poster
Posts: 61
From:
posted 04-19-2001 05:46 PM
Sorry i meant microtek . mr cool the only hydrometer i have found in a wine making shop or have used for that purpose goes
from 0.990 to 1.150 sg at 20c know where near 1.82 even battery hydrometers only go to amax of 1.4 id like to know where to
get one that goes up to 1.82 if any knows cheers
nbk2000
Moderator
Posts: 1096
From: Guess
posted 04-19-2001 08:15 PM
I whipped up a MS works spreadsheet for calculating the amount of chemicals needed and the cost for making nitro according
to microteks method. Adjust the cost according to your local prices.
It's in my video link. 1KB in size.
It would cost me about $130 for 3000mL (3 quarts) of nitro.
Microtek, what amount of sodium nitrate would you use instead of the ammonium salt?
------------------
frostfire
Frequent Poster
Posts: 266
From:
posted 04-19-2001 09:20 PM
3 L for $130,
is that lab grade chemicals or improvised?
Man, then it should be made in 3rd world country
BTW, NBK2K, what is *.wks? I can't open the file with ordinary excel 97.....is that the same of MS Works Spreadsheet?
nbk2000
Moderator
Posts: 1096
From: Guess
posted 04-20-2001 03:37 AM
The $130 price is at "improvised" prices. That's drain opener, fertilizer, and ag. glycerine.
But 3 liters of nitro is a lot of explosive. Almost 9 pounds of HIGH explosive. And it can be mixed with a lot of other things to
make other high power explosives, like with nitromethane or AN. So you'll get at least double the nitros weight.
The biggest expense is the sulfuric acid. If you can recycle it than that would dramatically cut down the price.
Mind you, as quantities are increased, ratios change. So it may require more or less of each chemical, so prices may go up or
down, depending on what's what.
I also reposted an excel version of the spread sheet. The first version is for MS works 4.5 which comes with windows I believe.
------------------
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-20-2001 07:37 AM
Make your own liquid densimeter!

Use a straight Polyethylen or a glass pipe long and with a little diameter with one end enclosed! Add lead in it to allow a free
floatation of the densimeter (immersion far over the gravity center in distillated water- near the open end of the tube).
Now put a mark where it floats...it is density 1.00 in distillated water at 20C.
Now use another fluid like CCl4 carbon tetrachloride at 20C mark the level on it; it is density 1.594 (approx 1.60). Now you
have two lines at 1.00 and 1.60 divide this lenght in 6 equal segment with lines to get 1.10;1.20;1.30;1.4;1.5....you thus
have a scale; report this length under the 1.60 line and you get 1.60 to 2.20; divide and you have a full scale between 1.00
and 2.20 density ....Simple is it? Wel maybe that you will have to do it several times to be stil in equilibrium (floatation line
over the center of gravity!).
It should look like this:

top
d=1 line pure H2O
d=1.1
d=1.2
d=1.3
d=1.4
d=1.5
d=1.6 line of CCl4 (carbon tetra chloride)
d=1.7
d=1.8
d=1.9
d=2.0
d=2.1
d=2.2
/
/
center of gravity
/
.
.
.
lead weight
bottom
Let's hope it helped! ASAT (As Simple As That). Never problems, only solutions!
------------------
"Chemistry is all what stinks and explode; Physic is all what never works! ;-p :-) :o)"
Microtek
Frequent Poster
Posts: 205
From:
posted 04-21-2001 05:56 AM
You just need to have the same amount of nitrate ions to form the nitric, so the number of moles needs to be the same.
Since NH4NO3 has a MW of 80 grams and NaNO3
has one of 85 grams, you'd need 4*85/80=4.25
grams of sodium nitrate per mL glycerine.
The amount of H2SO4 remains the same.
Alchemist
Frequent Poster
Posts: 211
From: Woodland hills,Ca.,L.A.
posted 04-21-2001 06:31 PM
Hello all,
Here are two froms of Mercury Fulminate that do not need Nitric Acid.
1.Mix red oxide of mercury in ammonia water for 8 to 10 days. The material becomes white and then finally crystallizes. Rince
the product several times with distilled water, then dry on filter paper.The dried product explodes loudly from fire,or a heavy
hammer blow! I do not think this is really a Fulminate but the Nitride of Mercury ,Hg3N2.
2.For real Mercury Fulminate the Sodium salt of Nitromethane gives with an aqueos solution of Mercuric Chloride Hg(CLO3)2 at
zero degrees a white precipitate of the Mercuric salt of Nitromethane which gradually becomes yellow. Then when treated with
warm dilute Hydrochloric Acid HCL, gives true Mercury Fulminate Hg(ONC)2.
P.S., I think YTS asked!
------------------
Mr Cool
Frequent Poster
Posts: 991
posted 04-23-2001 01:18 PM
You mean chlorate, not chloride I assume.

Regarding the cavities in NC: surely these would make it more sensitive if they are quite small, which in my opinion is a good
thing. Does anyone know whether this is true?
Microtek
Frequent Poster
Posts: 205
From:
posted 04-23-2001 01:40 PM
I agree that it would, but the cavities are

rather large and, perhaps more importantly, very irregular.
This would give a rather unpredictable performance. To get an idea of the extent of the cavities, consider how much of the
volume of the colloidinized NC is actually acetone. Then consider that all of this acetone evaporates, leaving cavities.
I'm not sure how they prepared the NC blocks that the patent in nbk's pdf mentions.
Anthony
Moderator
Posts: 2306
From: England
posted 04-23-2001 06:37 PM
Maybe they pressed the wet NC?
frostfire
Frequent Poster
Posts: 266
From:
posted 04-24-2001 03:35 PM
if nitric/sulfuric acid solution is strong enough to decompose glycerine, is that mean that it's strong enough to nitrate it?
Mr Cool
Frequent Poster
Posts: 991
posted 04-24-2001 04:06 PM
I think they probably pressed NC, maybe with a little bit of acetone just to make it bind a bit better.
I don't think that just because it'll decompose it it will nitrate it effectively, but I could be wrong. It certainly isn't true for
everything.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-25-2001 04:22 AM
No frostfire! That doesn't mean this...HNO3/H2SO4 when slightly diluted loses its nitrating power and becomes only an
oxydising mix decomposing the glycerin into, aldehyds,cetons,acids and CO2!

Anthony
Moderator
Posts: 2306
From: England
posted 04-26-2001 06:09 PM
For the NC, I tried again using the ratios Microtek uses for HG (4gm NH4NO3 6ml H2SO4) and the same brand cotton wool that
I used before in NaNO3/H2so4 (1gm/4ml) and it didn't dissolve this time! I also put in some bits of NC ping pong ball to see
what happened. I'll wash and test it tomorrow to see if it's worked. Conclusion - there's something fucked up with my NaNO3!
Also, I tried a small test batch of Microtek's NG procedure, if NG burns with a yellow flame then it worked, anyone know what
coloured flame NG burns with?
simply RED
Frequent Poster
Posts: 240
From: HELL
posted 04-27-2001 04:57 AM
Yesterday I made some very high nitrated nitrocellulose. I used about 80-90% nitric acid made with lead nitrate and
98%sulphuric acid. This recipe for nitrocellulose is the best I've used since I haven't access to 90% pure nitric acid! (I posted
the recipe before 1-2 months). The nitric acid is mixed 1:1 with sulphuric acid (in volume) and then the cotton is put
(temperature in first 7 minutes about 8 degress in the next 7 minutes 15 degrees. The nitrocellulose burns really fast with no
ash. I will convert this nitrocellulose to acetone peroxide putty.
As I have read the nitroglycerine burns with blue flame, actually i've never made it...
ALENGOSVIG1
Moderator
Posts: 766
posted 04-27-2001 11:20 AM
Anthony: Well nitrated NC burns with a green-blue flame. Although your product must be slightly nitrated. None of the chems
needed in NC are flammible. Except for glycerine, which is not that flammible anyways. If you can place a match on it and it
light its nitrated something. Just soak i tiny piece of paper in NG and hit it wil a hammer.
------------------
Explosives Archive
frostfire
Frequent Poster
Posts: 266
From:
posted 04-27-2001 02:58 PM
nitroglycerine burn test? =green-blue flame means right product ?!?!??!

how did you lit it and see the burning flame?
I thought NG is heat sensitive as well as shock???
Anthony
Moderator
Posts: 2306
From: England
posted 04-27-2001 03:34 PM
I messed up last time and only had a few bubbles of "nitro" I sucked some of them out of the water with a pipette and
squirting onto a hotplate. There was water in pipette with the NG but it still went pop with a flash of organge flame. I've made
another batch now and I appear to have a nice thick layer of NG settling out.
The NC with KNO3 is only slightly nitrated. Methinks it's time to sort out some HNO3...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > propylene glycol? -
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rjche
Frequent Poster
Posts: 52
From:
posted 02-20-2001 02:05 PM
--------------------------------------------------------------------------------
members have tried to make ethylene glycol di nitrate but have a problem getting the ethylene glycol. Getting it from antifreeze is not easy.
It would appear that propylene glycol di nitrate ought be as easily nitrated, and that is obtainable rather pure from camper outlets where it is used to fill the camper's pipes
during freezing weather. To do that it must be non-toxic, hence fairly pure.
Anyone have data on nitrating propylene glycol, or its characteristics as an expl?
Also saw a post on a survival forum about maiing bio diesel fuel from vegtable oil. It said this:
"Vegetable oil (either virgin oil from sunflowers or other vegies OR waste oil from fast food fryers) is reacted with a catalyst composed of sodium hydroxide disolved into
methanol. The methhydroxide is stirred vigorously into the vegi oil and chemical reaction called transesterfication breaks the long hydrocarbon bonds resulting in high purity
diesel and glycerin. The glycerin is heavier and settles to the bottom of the mizxing tank."
Anyone familiar with this process for making glycerine?
ezekiel
Frequent Poster
Posts: 110
From:
posted 03-08-2001 03:54 PM
--------------------------------------------------------------------------------
I'm not big on the soap industry but I think your recipe is for maknig glycerine salts - precursors for soap.
You could extract them out, but then again you could buy a vat of the shit for tuppence.
I assume you don't realise that propylene glycol is glycerin. I may be underestimating you. Sorry.
So basically you are asknig, in different words, the most asked chemistry question in the world:
"How do I make nitro glycerin?"
ever heard of propylene 1,2,3 nitrate? That is nitro glycerin.
------------------
Ezekiel
'Things bad begun make strong themselves by ill'
ALENGOSVIG1
Moderator
Posts: 766
posted 03-08-2001 08:23 PM
--------------------------------------------------------------------------------
ethelyne glycol can be found as a chemical used to test gas lines. I have many bottles of this. It was dirt cheap. If you email me a address or P.O Box i could mail you 100 ml
or so. You just gotta pay the postage.
------------------
Explosives Archive
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 03-15-2001 07:39 AM
--------------------------------------------------------------------------------
Propane diol exist in two form:
1,2-propandiol and 1,3-propanediol
CH3-CHOH-CH2OH and CH2OH-CH2-CH2OH.
Use the same process and same care as for nitroglycerin or nitroglycol.
The nitrated product are about the same strenght and VOD as Nitrolycerin and nitroglycol.They are more fluid (less viscous), more volatile and more hydrophobic than
nitroglycerine.
The only difference is that the 1,2 compound is as impact sensitive as NG but the 1,3 is less sensitive....
------------------
rjche
Frequent Poster
Posts: 52
From:
posted 04-15-2001 02:07 PM
--------------------------------------------------------------------------------
Well thought you had made my day there but when I went to check Hndbk of physics it lists glycerine as c3 h8 o3 or
1,2,3 propanetriol.
propylene Glycol is listed as listed as
1,2, propanediol. or c3 h8 02
However that's close enough to probably nitrate ok, same say as glycerine.
The lack of on oxygen might not matter for NG is O rich, and balance would probably be achieved for the o2 glycol.
Glycerine costs about $25 per gallon in agriculture stores as a rub for horses.
Propylene glycol is a non poisonous antifreeze for use in cars (has additives) and in camper water pipes in winter (probably pure to keep it non toxic to the drinking water
systems. I think it comes at about 50% strength though and would have to be boiled to concentrate it.
Kroways
New Member
Posts: 19
From: Czech Republic
Registered: APR 2001
posted 04-17-2001 05:22 PM
--------------------------------------------------------------------------------
PGDN is not as shock sensitive as NG and nor as EGDN. The height of the fall of 2kg hammer is about 90-100cm, what is something between picric acid and TNT. The
manipulation safety is high. I also thought that the sensitivity will be around EGDN because of similar structure, but the reality is different(and better). Actually I cannot
compare, because I haven't made any other nitroesters, but I tried to ignite a small sample(~0.1g) by impact and failed. Literarure(Orlova - Chemistry and technology of
brisant explosives, Urbanski - Chemistry & Technology of explosives) says the same - so it isn't only from my own head.
The nitro-esterification of PGDN(1,2-propanediol dinitrate) can be made the same way as NG, but the safety and yield is low. Fortunately Urbanski write a few rows about this
reaction, I have tried it and can say it is very simple.
The temperature should remain below 10C and the nitration mixture should be NA-rich: 47.5% of HNO3, 45.5% H2SO4 and 7% water. When 10% excess of nitrating mixture
is used, min. 90% yield is obtained. I have made it about 3 times and used magnetic stiring and have had 93% yield. Good stiring is necessary, as the methyl(CH3-) group
oxidises readily when temperature rises above 20C, so you MUST stir very thoroughly and MUST NOT let the temperature rise even locally. The product is very stable if
washed sufficiently, but decomposes if remaining acid is present. I recommend to wash at least 10 times(first separate it from the acids in a separatory funnel, then wash 2x
with water, then 3-4x with 5% solution of Na2CO3 and then several times with fresh water). Then I add 0.5% diphenylamine as a stabilisator. The colour can turn a bit
yellowish, but MUST NOT turn blue(remaining acid). If the colour is blue, pour it out. The nitroester is much more volatile than NG, but not so volatile as EGDN. You should work
in a digester or in a good-ventilated room, if you want to prevent slight head-ache.
[This message has been edited by Kroways (edited April 18, 2001).]
shooter2
Frequent Poster
Posts: 56
From:
posted 04-17-2001 07:13 PM
--------------------------------------------------------------------------------
Kroways Nice photos on your website. Do you have a license, or do you sneak around like us? Is that first photo a pic. of a lead block or something harder?
[This message has been edited by shooter2 (edited April 17, 2001).]
Kroways
New Member
Posts: 19
posted 04-18-2001 09:31 AM
--------------------------------------------------------------------------------
Shooter: A lead block. But the explosive in a film can was weak. I tried also a mixture of 10% PETN, 10% RDX, 30% PGDN + CP-2 gelatine, 10% BaSO4 and 40% NH4NO3
and that performed MUCH MUCH better. Actually I don't have any licence and I'm now sneaking only on a theoretical level.
PYRO500
Moderator
Posts: 1465
posted 04-18-2001 04:38 PM
--------------------------------------------------------------------------------
what language is your page written in? and do you have a translation? what is that pager like device there? a remote detonator?
Kroways
New Member
Posts: 19
posted 04-18-2001 05:28 PM
--------------------------------------------------------------------------------
PYRO500> The page is written in Czech. Unfortunately i don't have English version, yet, though I plan it.
The "pager like device" is a detonator(now I don't know if the word is right - not included in web dictionary). It is a thyristor-switched device which I have made from old
Canon camera flash-addon. It is powered by 4 small 1.2V accumulators(the same as you put in a walkman) and transforms it first to 4.8V AC(high frequency - you can hear it)
and then to cca 330V AC which is then transformed to DC and a capacitor is loaded. When you press the red button, the P-N boarder(?) opens and you get about 10-100A
current through the whole wiring, depended on the resistance. The thyristor is used because of high currents. I tried several simple switches but have fried them:]
The_Rsert August 26th, 2004, 11:44 AM

You can destill ethylen glycol from antifreeze at 198.??C!
It's not very difficult!
You will get an oily subsatance.
Sometimes you can get technical concentratet 98%* ethylene glykol on tanking stations or in "car gadget shops"
Note: Ethylene glykol is the same like ethane diole or glykol!

a n d I m provised C hemistry > vacuum distilling? - Archive File
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Raven
New Mem ber
Posts: 14
From : the clouds of war
posted 04-13-2001 07:25 PM
--------------------------------------------------------------------------------
I'm sorry i'm not as smart as you guys but wha t is vacuum distilling what kind of vacuum should i use dirt devel a dust buster
hoover what????
Anthony
Moderator
Posts: 2306
From : England
posted 04-13-2001 07:55 PM
--------------------------------------------------------------------------------
Correct m e if I'm wrong, but the idea of vacuum distillation is to lower the boiling point of what you are trying to distill, m a k i n g
it easier to distill/not decom pose it.
Chainsaw
New Mem ber
Posts: 34
From : Estonia
posted 04-13-2001 08:38 PM
--------------------------------------------------------------------------------
I think it is way too com plicated to make this still at hom e... pro p e r l a b e q u i p p m ent is required ie. like real vacuum pum p...
not vacuum cleaner
Anthony
Moderator
Posts: 2306
From : England
posted 04-13-2001 09:22 PM
--------------------------------------------------------------------------------
It can all be improvised with a little effort.
pete
Freq uent Poster
Posts: 56
From : u . k
posted 04-14-2001 06:55 AM
--------------------------------------------------------------------------------
How can it be improvised, were the heck do you get a vacumm p u m p f r o m , i could use this knowledge for separating out
nitromethane from th e oils an d m ethanol they mix it with in m o d e l f u e l s .
nbk2000
Moderator
Posts: 1096
From : G u e s s
posted 04-14-2001 11:15 AM
--------------------------------------------------------------------------------
Refrigerators use com pressor pumps which (when hooked up in reverse) becom e c a p a b l e v a c u u m pum ps.
An amateur scientist article described how to do the conversion as part of m aking a particle accelerator. It's also in the
Am ateur Scientist projects book which you may find in a library.
Or, if you did a search on the 'net, like I did, you would have found an article like this one.
------------------
[ T h i s m e s s a g e h a s b e e n e d i t e d b y n b k 2 0 0 0 ( e dited April 14, 20 01).]
Raven
New Mem ber
Posts: 14
From : the clouds of war
posted 04-14-2001 12:23 PM
--------------------------------------------------------------------------------
T h a n k y o u a l l s o m u c h e x p e c i a l l y n b k 2 0 0 0 i a m now going to attem pt to m a k e a v a c u u m p u m p
thankyou.
10fingers
Freq uent Poster
Posts: 411
From : U SA
posted 04-14-2001 12:26 PM
--------------------------------------------------------------------------------
You can get a device which connects to your water faucet to create a mod erate vacuum , it's called an aspira tor and costs less
than $10.00. Pyrotek has them .

a n d I m provised C hemistry > W ater aspirator for vacuum ? - Archive File
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-A-
Freq uent Poster
Posts: 100
From :
posted 04-15-2001 04:59 AM
--------------------------------------------------------------------------------
I have the lu ck to have access to 98+% nitric acid, but I was wondering... If I have, lets say, 70% nitric acid, and I want to
distill it with h2so4 under vacu m m ... will a simp le water aspirator be enough for the vacuum ?
Bitter
Freq uent Poster
Posts: 290
From : 11 Downing Street, London, England
posted 04-15-2001 08:02 AM
--------------------------------------------------------------------------------
I h a v e n o i d e a h o w m uch vacuum is needed either. W ill it need a vacuum cleaner strength vacuum or what ? I have heard that
it can be sucessfully achieved by 'blowing dry air' throug h the apparatus. I assume by this, all that is needed is to rem o v e t h e
non-N03 vapours from the reaction in order to concntrate it.
By the way, -A-, how can you get 98% nitric ? Is it from the place you work or what ?
-A-
Freq uent Poster
Posts: 100
From :
posted 04-17-2001 02:54 AM
--------------------------------------------------------------------------------
I get it from a friend that works at a la b supply.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > hydrosilicons (or
silicon hydrogen chemistry)
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zeocrash May 14th, 2003, 06:40 AM

yesterday i was walking home after dropping my girlfriend off at the station, when i started thinking about alteriative fuels for cars. so anyway one of the ideas that i had was
using silicon based compounds instead of carbon based petrol (Si8H10 instead of C8H10). this seemed the perfect idea, until i realised that the silicon dioxide produced would
be a solid and would eat up a car cylinder in no time.
this idea got me thinking "you could use this idea for other things". the first thing to come to mind was a undetectable nerve gas.
from what i remember nerve gas detectors operate much like IR spectrometers, and the C-F and C-P bonds they look for causes absorbtion or interferes with a particular
frequency of light. Using Si - F and Si-P bonds would completely change the wavelength of the light refrected, causing the detectors to completely ignore the gas.
now i was wondering if anyone had any idea how to make Simple silicon hydrogen compounds. on any scale at all.
this topic is completely theoretical as i doubt i have/will ever have the means to manufacture such a chemical, i'm sure someone like 80r15 does though :D
simply RED May 14th, 2003, 07:58 AM

Actually this si a well ducumented phenomenon. Nerve gas uses complete analogue with ac-holine and inhibits holinesterase. Using Si, you will never have full alalogue
between ac-holine and your poison, not that it won't be toxic, but it won't have a high tox.
But if you manage to compose a good structure of your component (see natural toxins inhibiting holinest.). Then it will be very nice.

You are referring to silanes.
While silicon has the same bond properties as carbon, being tetravalent, it does not form the same amounts of Si - H based compounds.
The reason is quite simple, the radius of the Si atom is too large to form stable enough Si-H bonds, that's why most silanes are spontaneously flammable in air.
Polymers like:
CH3...CH3...CH3..CH3...CH3
|........|.......|.......|.......|
Si -O- Si -O-Si -O-Si -O-Si-O...
|........|.......|.......|.......|
CH3...CH3...CH3..CH3...CH3
are commonly known as "silicone".
Burning this is an easy way to get fairly pure SiO2.
Tuatara May 14th, 2003, 07:49 PM

I recall making a simple silane in chemistry class at school (SiH4?). Thoroughly useless as it decomposes instantly in air into SiO2 and H2O. Trouble is I can't remember how I
did it :o
Can't be too hard though ...

Another problem silicon has is it does not form Si-Si bonds like carbon. This pretty much limits the idea of hydrosilanes beyond SiH4.

It does form Si-Si bonds. In the silane produced by the method below, it is Si2H6 that causes ignition in air, not SiH4. So those bonds can form, but are very unstable, as shown
by the pyrophoric nature of the gas...
4 Mg + SiO2 -heat-> Mg2Si + 2 MgO

Mg2Si + 4 HCl(aq) --> 2 MgCl2 + SiH4
Silanes are toxic, just like all non-metal hydrides seem to be (arsenane, phosphane, selenane etc), but are probably not comparable to nerve gases. H2Se is around ten times
more toxic than HCN.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Extracting Potasium
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Teck
Frequent Poster
Posts: 146
From:
posted 01-23-2001 07:37 PM
--------------------------------------------------------------------------------
Ok I bought Green Thumb fertilizer and I need to extract KNO3 from it. I never did this because I usually bought the pure KNO3. What should I use to dislve it in boiling water
or alchohol (because it evaporates faster). And how much KNO3 would I have from a 50lbs bag (roughly)? If I use boiling water can I use a heat source to evaporate the
water? any answers would be apreciated.
ALENGOSVIG1
Moderator
Posts: 766
posted 01-23-2001 07:59 PM
--------------------------------------------------------------------------------
Is it actually kno3?, or does it have like 70% or something kno3? If it is just kno3, add it to water and filter off anything that floats and let if evaporate by itself.
------------------
Explosives Archive
Teck
Frequent Poster
Posts: 146
From:
posted 01-23-2001 09:35 PM
--------------------------------------------------------------------------------
Man its gonna take like hella long time to evaporate. Could I use an external heat source to make it evaporate faster? And thats why I was thinking if alchohol would work.
And its not pure Potasium nitarte its 75%. By doing this proccess will I have pure potasium nitrate or not?
MacCleod
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Posts: 217
From:
posted 01-24-2001 02:11 AM
--------------------------------------------------------------------------------
That depends on the other ingredients,bro.If they are water-soluble,it may be tricky seperating them.What else is in it?.
------------------
"That which does not kill us,makes us stronger"
the freshmaker
Frequent Poster
Posts: 175
From: Heaven
posted 01-24-2001 05:31 AM
--------------------------------------------------------------------------------
if it is KNO3 you can dissolve it in boiling water (alcohol won't dissolve KNO3!) and the let the soloution cool down - maybe put it in the fridge and the just filter the
recrystalized KNO3 out and dry it.
Anthony
Moderator
Posts: 2306
From: England
posted 01-24-2001 01:46 PM
--------------------------------------------------------------------------------
Like MacCleod said, it depends what the other chemical(s) are. You need to know their level of solubilty compared to the KNO3. Maybe you could even melt the fertilizer and
skim off what doesn't melt. That's assuming that the know hast he lowest melthing point of all the chemicals in the mix. It could be dangerous if one of the ingredients was a
fuel. Have you tried using the fertilizer as is? At 75% pure it should work for most things.
Mr Cool
Frequent Poster
Posts: 991
posted 01-24-2001 02:53 PM
--------------------------------------------------------------------------------
I've never seen that make of fertiliser, but I've heard that the rest is AN, in which case it could be used as-is, but it'll get damp easily. Gently heat some and see if you start
laughing! ( NH4NO3 -> 2H2O + N2O, which is laughing gas)
I think I might have heard that it contains AN from a cookbook when I was a newbie, so don't rely on that!
Teck
Frequent Poster
Posts: 146
From:
posted 01-25-2001 03:11 AM
--------------------------------------------------------------------------------
hey guys thanks for the info. That was really stupid I should have tried using it as is. But if it doesnt work I'l boil it and see what happens. Im also palnning on making some AP
but im having some after-thoughts after reading that its the most unstable high explosive. I dont know any precautions in making it other than Handle it with care and all that
stuff.
Anthony
Moderator
Posts: 2306
From: England
posted 01-25-2001 08:10 AM
--------------------------------------------------------------------------------
If you wan to serperate the KNO3 from the AN just make a hot saturated solution and cool it in the fridge. Since the AN is more soluble than the KNO3 it should stay in solution
and the KNO3 would crystalise out.
There are lots of explosive that are much more unstable than AP, If you stick to making small (gram or two) and treat it with respect, then you should come to no harm. A
gram may sound not worth making but even a gram detonating is impressive. especially if it's your first HE.
SATANIC
Frequent Poster
Posts: 237
From: australia
posted 02-11-2001 11:29 PM
--------------------------------------------------------------------------------
can you extract KNO3 fromn an all purpose fertilizer? it's 20 %, but all i have. what else could filter out aside from NH4NO3?
Anthony
Moderator
Posts: 2306
From: England
posted 02-12-2001 10:46 AM
--------------------------------------------------------------------------------
You should be able to extract it, how easy it will be depends on what else is mixed in with it, which could be all kinds of crap.
Fractional Crystalization should be able to do it, but you'd need to only collect a particular fraction, say, what precipitates between 0*C and 10*C. Because all the diferent
chemicals will be precipitating out at different temperatures.
It would be a lot easier to just buy some KNO3 fertilizer, or even a two part fertilizer that contains KNO3.
[This message has been edited by Anthony (edited February 12, 2001).]
J
Moderator
Posts: 602
posted 02-12-2001 08:00 PM
--------------------------------------------------------------------------------
I have a method for converting NaClO3 to KClO3 on my website. The method for converting (insert chemical here) nitrate to Potassium Nitrate is similar, although I must admit
I've never done it. I remember reading that Potassium Carbonate and NH4NO3 in solution will be converted to KNO3 by boiling until there is no Ammonia gas given off.
I'll be trying this in the summer, since it's such a hot (no pun intended!) topic.
------------------
"If the aquarium water has to be drunk don't waste the fish. In fact they'll probably be the easiest to eat even if you don't need the water. The cat is next in the pot." - John
'Lofty' Wiseman
Shadow
New Member
Posts: 4
From: NoWhere, NoState, NeverNeverLand
posted 04-05-2001 11:49 AM
--------------------------------------------------------------------------------
While on the subject of separating potassium nitrate, i got some but it has a fire retardent mixed with it.
Both of the chemicals are white, and about as fine as castor sugar. If tried dissolving them in water straight from the tap, nothing happened. I tried dissolving it with warm
water, nothing happened. I tried dissolving it with boiling water and they both dissolve. I also tried sieving it and all of it falls through, and i tried filtering it when it was
dissolved, nothing appeared.
So, i was wondering how on earth could i seperate these two?
--SHADOW--
P.S Kind of off the subject, but i was wondering what would be the best proportions for AP with 9% H2O2, pure acetone and battery acid?
J
Moderator
Posts: 602
posted 04-05-2001 02:07 PM
--------------------------------------------------------------------------------
What is the product meant for? The only common things I can think of would be fertilizer and chimney cleaner. You'll need to find out what the impurity is, if you tell us what
you bought someone might know.
There is a special section for explosive peroxides. But don't ask that question, find one of the many threads that cover the proportions.
------------------
'Lofty' Wiseman
Anthony
Moderator
Posts: 2306
From: England
posted 04-05-2001 04:35 PM
--------------------------------------------------------------------------------
Dissolve some of the product in the minimum amount of hot water and allow to cool. At some stage (might need to refrigerate it) one of the chemicals will crystalise out, filter
out the crystals and test to see what it is.
Jumala
Frequent Poster
Posts: 200
From: Germany
posted 04-05-2001 10:09 PM
--------------------------------------------------------------------------------
Hallo Teck,
when your fertilizer contains KNO3 I would suggest the following method:
Dissolve so much fertilizer as possible in boiling water.
Filter the solution to remove solid components.
Then let it cool down very slowly.
The KNO3 forms very large crystals with the form of more or less thick needles. ( Until many cm long)
Other salts will form other crystals.
Then you can collect the crystals and grind then to powder.
Dont wait the cold solution. Boil it again, poor in the fertilizer and so on.
Arthis May 23rd, 2003, 11:04 AM

I can't find any info about K2O: I bought some KNO3 at a agriculture store, and it's 14-0-45, the problem is that it's mixed with 48% K2O.
Would you know anything about K2O, it's solubility compared to KNO3, or whatever ?
Thanks
frogfot May 23rd, 2003, 02:35 PM

This was mentioned previously, content of potassium in NPK fertilizers is counted by K2O, so 14-0-45 is pure potassium nitrate.
About extraction of KNO3 from fertilizers, the main things that have to be removed from usual NPK fertilizers is phosphates and sulfates... I used to precipitate them with cheap
Ca(NO3)2 (btw, there must be high pH to remove phosphate).
BrAiNFeVeR May 23rd, 2003, 06:45 PM

I've made a page on the subject of KNO3 purification not very long ago, feel free to visit it here (http://www.geocities.com/brainfevert/kno3.html).
If you don't want adds on the pages, go trought the shorturl link in my sig and look in the syntheses section of my site.

a n d I m provised C hemistry > Am m onium Perchlorate - Archive File
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Bitter
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Posts: 290
posted 03-30-2001 03:40 PM
--------------------------------------------------------------------------------
I a m sure many of you are aware, it is possible to change sodium chlorate to potassium chlorate by m ixing it with KCl. The
potassium chlorate can be extracted because it is considerably less soluble in water than the sodiu m chloride by-product.
W ell how about this : Because am monium perchlorate is so difficult to acquire outside the US, then I was thinking could it be
m a d e u s i n g a s i m i l a r m e t h o d t o t h e o n e a b o v e f r o m p o t a s s i u m perchlorate by mixing it with am m o n i u m n i t r a t e .
I l o o k e d u p s o m e s o u r c e s a n d I f o u n d that it would probably work :

0 deg C 100 deg C
NH4ClO4 10.74 42.45

KClO4 0.75 21.8
NH4NO 3 118.3 871
KNO3 13.3 247
The numbers are the solubility (in gram s) per 100cc of water.
Therefore, if 80g of a m m onium nitrate was dissolved in 100g of boiling water and 138g of pure potassium perchlorate was
a d d e d , a b o u t 7 5 g o f a m m onium perchlorate would, in theory, be precipitated. The hot water would im m ediately have to be
tipped away (otherwise KNO3 m ight be precipitated alon g with the perchlorate).
The only problem I can see with this is the danger of potassium chorate being present in the perchlorate, which wou ld reduce
the possibility of safe ly using hom e - m a d e p e r c h l o r a t e t o z e r o .
Any opinions ?
Anthony
Moderator
Posts: 2306
From : England
posted 03-30-2001 06:15 PM
--------------------------------------------------------------------------------
My first reaction was am monium chlorate... Then I realised that you were u s i n g K C L O 4 i n s t e a d o f N a C L O 3 a n d I t h o u g h t t h a t
m ight be a waste of perfectly good KCLO4.
I agree, there is a risk of NH4C LO 3 o f f o r m i n g a s t h e r e ' s b o u n d t o b e s o m e K C L O 3 i n t h e K C L O 4 .
Is NH4C LO 4 really so great though? I understand that it gives better perform ance in rocket fuels than KCLO4 due to all the
combustion products being ga ses, but it sounds like hard work. If you're doing rocket fuels, have you considered NH4NO3?
IIR C it's got about half the perform ance of NH4CLO4 but its rediculously cheap and doesn 't require the work that NH4CLO4
t a k e s t o m ake. You could always just m ake bigger motors to overcome the power loss. It's soemthing I intend to experim e n t
with when the wheather gets a bit better.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 03-30-2001 06:25 PM
--------------------------------------------------------------------------------
If your using rocket fuels you wouldnt want AN would you? As far as I understand it can detonate at high tem peratures...??
firebreether
Freq uent Poster
Posts: 110
From :
posted 03-30-2001 09:16 PM
--------------------------------------------------------------------------------
no it DEFINITELY won't detonate. AN burns at lo wer tem ps than perchlorate, so it wouldn't be as good. Not to mentio n its sup er
hygroscopic.
Anthony
Moderator
Posts: 2306
From : England
posted 03-31-2001 08:56 AM
--------------------------------------------------------------------------------
I would think that NH4CLO4 is also very hygroscopic. If you using a plastic fuel/binder then it shouldn't be as m u c h o f a
p r o b l e m . Also have a "blast plug" (recom m e n d e d ) w o u l d m a k e t h e m oto r 100% water/air tight.
The main point is AN is veeeeeery cheap.
Bitter
Freq uent Poster
Posts: 290
posted 03-31-2001 01:32 PM
--------------------------------------------------------------------------------
I think you sould com pare the figures I have given above to compare the water solubility (and to some extent hygroscopicy) of
the chem ical. NH4ClO 4 is lowe r than KNO3 and about 10 tim es lower than NH4NO3
Anthony
Moderator
Posts: 2306
From : England
posted 03-31-2001 03:06 PM
--------------------------------------------------------------------------------
I s h o u l d h a v e b e e n m ore specific, I meant that NH4C LO 4 would be very hygroscopic compared to the origin a l K C L O 4 .
Agent Blak
Freq uent Poster
Posts: 766
posted 04-02-2001 10:00 AM
--------------------------------------------------------------------------------
If we are going to use Chemistry short hand when dealing with chem icals please do it right ; that way everyone know what each
other means.
i e . P o t a s s i u m C h l o r a t e i s K C l O 3 n o t K C L O 3 ; P o tassium PerChlorate is KC lO4 not KCLO 4... and so on and so forth.
T h i s s h o u l d h e l p c l e a r u p s o m e m isunderstandings between m e m bers.
------------------
"...T here Will Be No
Stand O ff At High Noon
... Shoot'em I n T h e B a c k
And, Shoot'em I n T h e D a r k "
firebreether
Freq uent Poster
Posts: 110
From :
posted 04-02-2001 09:56 PM
--------------------------------------------------------------------------------
All n itrates are verysoluble and hygroscopic. I thought chlorates and perchlorates could be for the NH4 and Na and Li forms. But
the K form s are not which is good.
firebreether
Freq uent Poster
Posts: 110
From :
posted 04-03-2001 09:30 PM
--------------------------------------------------------------------------------
Also, because KClO 4 is barely soluble, and NH4ClO 4 is soluble, you won't ever get NH4ClO 4 to precipitate from KClO 4.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
posted 04-05-2001 05:04 AM
--------------------------------------------------------------------------------
100% right firebreether!
BTW : here are processes to m a k e H C l O 4 a n d N H 4 C l O 4
For the Newbies: NH4ClO4 can ' t b e m a d e b y e l e c t r o l y s e o f N H 4 C l b e c a u s e y o u g o t h r o u g h t h e d a n g e r o u s
NH4ClO3(VOD=3300m/s, spontaneously, unpredictably, self detonating even in solution)!!!!
1 ) U s e C a C l 2 ( o r C a ( C l O )2) and electrolyse it the sam e way you would do to get KClO3 or NaClO3 from N a C l a n d K C l . Y e s C a C l 2
is not very soluble bu t it is good so believe me!
You will of co u r s e g e t s o m e C a ( C l O 4)2 aside with Ca(ClO 3)2.
Concentrate by evaporation and add diluted H2SO4 - or what is the sam e add conc. H2SO4 to the diluted m other liquor.
(DON'T ADD CO N C H 2 S O 4 T O A C O NCENTRATE SO LUTIO N O F CHLO RATE/PER CHLORATE!!!!! BECAUSE HCLO3 AND HC LO4 AR E
EXPLOSIVE W HEN CONCENTRATE!!!!!).
W hite clouds of unsoluble CaSO4 (plaster) will form and precipitate.Add until no more precipitate form while taking som e o f t h e
clear solution and testing it with H2SO4).
C a C l 2 + O + h e at+electricity--> Ca(ClO )2 + C a ( C l O 2 ) 2 + C a ( C l O 3 ) 2 + C a ( C lO4)2

T h e m o r e t h e t i m e o f r e a c t i o n the m ore you go to C a(C lO4)2!!!!
C a ( C l O 4 ) 2 + C a ( C l O 3)2 + 2 H2SO4--> 2CaSO 4 + 2HClO4 + 2HClO 3
Filter the plaster through glass paper filter (used to cover walls before pa int application to avoid irregularities-glass doesn't
react with oxydising a cid like perchloric and chloric what paper does!).
Now we have a diluted to medium concentration solution of HClO 3 and HClO4 in water.
To get rid of the HClO3 for further process boil the solution by slowly increasing the heat in a wel ventilated area avoiding
goin g over 150C.
By the magic of chem istry:
4HClO3(diluted)+heat--> 3HC lO4 + HCl
(this reaction looks pretty the same as
4NaClO3 + heat (not too much)--> 3NaClO4 + NaC l
did you notice that?)
Anyway,upon slow boiling HCl is driven away (reason why it has to be done outside otherwise all m etals and your lungs will be
corroded); So does water.
You end with a solution stil concentrating in HClO4 by evaporation of the water.
Since HClO4 has an eutectic with 79%HClO 4/21 %H2O a t a p p r o x 1 8 0 C a n d that it becom e s e x p l o s i v e w h e n m ore concentrate ,
stop at 150C , no use to loose the valu a b l e H C l O 4.
Now sim ply m ix concentrate NH3 (in excess) solution with the HC lO4 solution to get NH4ClO 4. Evap o r a t e i n t h e o p e n e x c e s s
NH3 will go away. You get your NH4ClO 4 from n ot to expensive starting m aterials.
BTW : DON'T USE a pan to boil the m ix since METALS AND ACID ARE NO T GOOD FRIENDS always use pyrex glassware.Also to
know HCLO4 is catalyticly decomposed by m etals when very concentrate over 79%, it explodes aslo upon contact with alcools
(and cellulose is a po lyalcool) making the dangerous organic perchloric e sters.
2)Even less expensive:

Mix under stiring sodium chlorate with concentrate HC l in excess (you can only reach m ax 37% HCl)and heat gently until it
dissolves. cool down NaCl cristallises out (solub ility of NaCl is 30g/100g H2O); filter out and keep the 37% HClO3 solution.
NaClO3 + conc HCl < == > HC lO3 + NaCl
Boil the HClO 3 slowly in an open space following the sam e reaction as in the first process:
4 H C l O 3 + h e at --> 3HClO4 + HCl
HCl is m ore volatile a nd fky away.
Go to 150C.
THen when cool add some excess NH3 solution.
HClO4 + NH4OH --> NH4ClO4 + H2O
------------------
Bitter
Freq uent Poster
Posts: 290
posted 04-05-2001 09:52 AM
--------------------------------------------------------------------------------
I was well aware of the insolubility of the KClO4 , but I was hoping it would gradually dissolve and turn to Am Per slowly.
I'll post the perchloric acid me thod shortly (that's using hypochlorite, not the ones posted by Philou ), I think you'll find that
works m uch better. But first I'll experiment to see if this hom e m ade perchloric acid of m ine is suce ssful as the com m ercial
stuff.
So far, I have only tried it with 60% com mercial perchloric acid.

a n d I m provised C hemistry > Heating H2O 2 - Archive File
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Sgt_Starr
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From : Petersburg
posted 04-15-2001 05:06 PM
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Hey guys,
I w a s w o n d e r i n g I f y o u c a n h e a t H 2 O 2 W i t h o u t a n y n o x i o u s g a s e s o r d a n g e r o f a n y k i n d t h a n k s ! ( d on't ask why I wa nt to now
=)~ )
------------------
"Oh Sh".::BO OM:(later
in front of sa int peter))
"it"
[ T h i s m e s s a g e h a s b e e n e d i t e d b y n b k 2 0 0 0 ( e dited April 16, 20 01).]
Shadow
New Mem ber
Posts: 4
From : NoW here, NoState, NeverNeverLand
posted 04-15-2001 05:39 PM
--------------------------------------------------------------------------------
This is just a guess, but i think that it'd just turn into water and give of oxygen or something.....
Don't believe any of this, because it is purely an assumption.
king s p a z
Freq uent Poster
Posts: 347
From : U K
posted 04-16-2001 05:50 PM
--------------------------------------------------------------------------------
H 2 O 2 o n l y h a s o x y g e n and hydrogen in it, neither of which are toxic so i think it would release oxygen and turn to H2O.
PYRO 500
Moderator
Posts: 1465
posted 04-16-2001 05:56 PM
--------------------------------------------------------------------------------
2(H202)+heat =2(H20) + O 2
zaibatsu
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Posts: 407
From : England
posted 04-16-2001 06:06 PM
--------------------------------------------------------------------------------
It does this in the sam e way that it would with other catalysts, heat being the catalyst in this place. Also, it will break down from
sunlight, and that is why it is kept in brown bottles
------------------
Visit m e at www.surf.to/eliteforum
Sgt_Starr
Freq uent Poster
Posts: 120
From : Petersburg
posted 04-16-2001 11:25 PM
--------------------------------------------------------------------------------
I thought so just wanted to be sure..another question if I m ay.....Ok hyd rogen is flamible right? so is oxegyn right? why isnt
H 2 O flam ible then? I'm not in the least sure but your going to say somthing like its in the composistion of the molocules rig ht?
------------------
"Oh Sh".::BO OM::((later
"it"
Spudgunner
New Mem ber
Posts: 33
From : M O , U S A
posted 04-17-2001 07:30 AM
--------------------------------------------------------------------------------
The reason it isn't flam m able is probably Na burns with water, Cl is poisonous, bu t NaCl is eaten all the time. A com p o u n d
u s u a l l y d o e s n o t h a v e t h e s a m e p r o p e rties of its com p o n e n t s .
------------------
Give m e i m m ortality or give m e d e a t h !
Sgt_Starr
Freq uent Poster
Posts: 120
From : Petersburg
posted 04-17-2001 11:18 AM
--------------------------------------------------------------------------------
Thanks (edited for co ntent)
[This message has been edited by Sgt_Starr (edited April 17, 2001).]
FadeToBlackened
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Posts: 201
From : Hell
posted 04-17-2001 05:05 PM
--------------------------------------------------------------------------------
O2 isnt flam m able. Think of it like this. If you burn a lo g in your fireplace, can yo u b u r n t h e a s h e s ? T h e y c o n t a i n p o t a s s i u m
a n d s o d i u m and carbon and o x y g e n a n d a l l k i n d s o f g o o d s t u f f . W a t e r i s m ade by hydrogen (or hydrogen containing
c o m p o u n d ) b u r n i n g i n o x y g e n . Water is kinda like the 'ash' of hydrogen.
king s p a z
Freq uent Poster
Posts: 347
From : U K
posted 04-17-2001 05:09 PM
--------------------------------------------------------------------------------
didn 't Sgt_Starr ask why H2O isn't flam a b l e ?
anyways the reaon it is not fla mable is that when things burn they com bine with o x y g e n . s o w h e n y o u b u r n h y d r o g e n o x y g e n
combines with it making water. thats a kinda sim ple way to put it but i think its right.
FadeToBlackened
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Posts: 201
From : Hell
posted 04-17-2001 05:20 PM
--------------------------------------------------------------------------------
Yeah, thats what he asked and i compared water to wood ashes...
PYRO 500
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Posts: 1465
posted 04-17-2001 06:35 PM
--------------------------------------------------------------------------------
you could say that the water is already burned H2
Sgt_Starr
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Posts: 120
From : Petersburg
posted 04-17-2001 09:18 PM
--------------------------------------------------------------------------------
T h a n k y o u s o m u c h g u y s . . . l o l I w a s w o n d e r i n g d o e s a n y o n e n e e d a c h e m student? I pay well hehe jking
------------------
"Oh Sh".::BO OM::((later
"it"
Spudgunner
New Mem ber
Posts: 33
From : M O , U S A
posted 04-17-2001 09:54 PM
--------------------------------------------------------------------------------
W ow, just went back and read what I wrote. Sorry about the horrible butchering of English. I think you figured out what I m e a n t
d e s p i t e t h e b a d g r a m mer though. O nce again, sorry.
------------------
Give m e i m m ortality or give m e d e a t h !
sim ply RED

Freq uent Poster
Posts: 240
From : HELL
posted 04-19-2001 03:19 PM
--------------------------------------------------------------------------------
Don't try to heat concentrated peroxide (m ore than 50%). It cou ld explode or burst into your face only by very sm a l l a m m ount
of catalyser. A lot of incidents have happened by distiling H2O 2 to get alm ost anhydridous... You know wha t h a p p e n s w h e n y o u
m i x s m a l l a m m ount 30% H2O 2 with KMnO 4. Try to imm a g i n e h e a t i n g l a r g e a m m ount and adding KMnO4 to it .
PHILOU Zrea lone

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Posts: 479
posted 04-20-2001 05:29 AM
--------------------------------------------------------------------------------
H 2 O 2 can de com pose catalyticaly but also auto catalyticaly this m e a n s i t h a s n o n e e d f r o m s o m ething else to react and
explode!
It happens from radicalar reaction between free radicals
INIT IATION:
H-O-O-H + h eat or light <====> 2HO*
P R O PAGATIO N:
H-O* + H2O2 <====> H2O + HO 2 *
H O * + H2O2 <====> H2O2 + HO*
H O 2 * <====> H* + O 2
H* + H2O2 <====> H2O + HO *
TERMINAISON:
H*+ H-O*--> H2O
H*+ H* --> H2
H O 2 * + H* --> H2O2
H O * + HO* --> H2O 2
T h u s a s a s u mary:
H 2 O 2 --> H2 O + O2 + H2 (tra ces)
Speed is a function of the T, of the concentration and thus if very concentrate, explosion or detonation (only under certain
circu mstances) can occur!
EP May 24th, 2003, 02:32 PM

Concentrating H2O2 w/heat:
http://krim zonpyro.com/ep/projectsdevicesdir/boilingh2o2test.html

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Calcium Carbide -
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FadeToBlackened
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Posts: 201
From: Hell
posted 04-02-2001 10:28 PM
--------------------------------------------------------------------------------
Calcium carbide is made by heating carbon with lime (calcium oxide)... right? How hot does this need to be to occur?
hodehum
New Member
Posts: 21
From: New Zealand
posted 04-03-2001 12:11 AM
--------------------------------------------------------------------------------
Calcium carbide is produced by heating lime and carbon in an electric furnace at a temperature of 2800 C
a little snipet in found in one of my chemistry books
Alchemist
Frequent Poster
Posts: 211
posted 04-08-2001 11:54 AM
--------------------------------------------------------------------------------
Hello,
I have made Calcim Carbide and it works pretty good depending on the quality of the Carbon! If still interested send me a e-mail at [email protected] and I will post it
on the form for all!
------------------
Alchemist
Frequent Poster
Posts: 211
posted 04-11-2001 09:37 PM
--------------------------------------------------------------------------------
Making Calcium Carbide
Hello all,
Well first of all it's been about five years or so since I last made some!
Yes, it did work and I did produce Acetylene with the Calcium Carbide that I made.
The quantities where small and I only needed it for use in a Potato Cannon that I was
Playing with at the time. Most chemistry books state that it is made by heating COKE
(Carbon) and Calcium Oxide -CaO (lime,quicklime,etc), in an electric furnace. Well
I could not get COKE, so I first used graphite powder, then activated Carbon. As I
recall both worked, but one worked better than the other. I forget what one was best!
I used 50% Carbon and 50% Calcium Oxide. Now comes the circuit. Below is a diagram!
12 to 15 ohm wire wound resistor, 650 to 750 watts
|-------/\/\/\--(- \ | |-/-----------(- 117 volts A.C. \ / --- Clay or Porclain Crucible
Ok, the first Carbon rods that I used where graphite pencil lead, but they burned away to fast.
Next I used Carbon rods from old batteries. Also I could not find a good wire wound resistor,
So after much looking I found a heating coil used in old heat lamps at the hardware store. It's 660 watts and measures 13 ohms. It uses Nichrome heating wire.This part of the
circuit is very important for it to work right!
I am not sure if these elements are still around, but anything that measures about 12 to 15 ohms
At 650 to 750 watts should be ok.
REMEMBER this circuit is using 117 Volts A.C., and this can KILL so use caution! In most cases I had to start the heating process by striking the Carbon rods together then slowly
separating them!
That means touching them at the ends (arching them) then pulling them apart. And of course this is done under the Carbon and Calcium Oxide mixture. If all goes right it will
start to arc and flame! Soon an orange/red glow should start to spread through the mix . It should become molten, almost white hot!
You may have to move the Carbon rods now and then to keep it going as they will burn up fast! After it has Fully melted (become molten) remove the 117 V.A.C.. You should
now have some Calcium Carbide after it cools. Remember to keep in air/water tight container. P.S., you may also have to break the crucible. Sometimes it just fell out after
cooling and sometimes it seemed to become part of the crucible.
As a last note, this maybe better with real COKE and someone may wish to improve on the circuit.
Any questions? Bye for now then..............
------------------
[This message has been edited by Alchemist (edited April 11, 2001).]
P.S., I do not know way the diagram does not come out ok. It looks fine before I post it.
It is subpost to be a crucible with two Carbon electrodes in it. A insalated wire goes from one end of a carbon rod to one end of the resistor a second wire from the other end of
the resistor goes to one side of the 117 volts A.C., and last another wire from the other rod to the other side of the A.C. to complete the circuit (series circuit).
Predator
Frequent Poster
Posts: 141
From: Unknown
posted 04-11-2001 11:08 PM
--------------------------------------------------------------------------------
Alchemist put in pre tags
(pre)
ascii drawing
(/pre)
replacing ( ) with < and > respectively
Anthony
Moderator
Posts: 2306
From: England
posted 04-12-2001 03:35 PM
--------------------------------------------------------------------------------
If the mix contains carbon/graphite then you shouldn't need electrodes or to strike an arc as the mix should be conductive.
I'll have to give this a go, calcium oxide is cement right?
Alchemist
Frequent Poster
Posts: 211
posted 04-12-2001 05:52 PM
--------------------------------------------------------------------------------
Hello Anthony,
Yes, I guess, but I really think they help to keep it going. Try it, experiment! Ask for a 20lb bag of lime or quiklime. I think 20lb's is the smallest you can buy, but it's cheap.
After you get the circuit working try different forms of Carbon. Good luck!
------------------
firebreether
Frequent Poster
Posts: 110
From:
posted 04-12-2001 11:09 PM
--------------------------------------------------------------------------------
I have a question about the battery electrodes. I have heard that you can't use alkaline batteries, since they have no carbon rod. But these are the only, type of battery there
is besides rechargeable. What kind did you use?
Alchemist
Frequent Poster
Posts: 211
posted 04-13-2001 12:10 PM
--------------------------------------------------------------------------------
Hello ,
I have a store near me called the 99 cent store. I can still get Carbon/Zinc batteries there. Also I did use graphite pencil lead from a stationary store for mechanical pencils, but
they do burn up fast! Also look at welding supply shops they carry carbon rods, but they are coated with copper so you must remove the copper first.

a n d I m provised C hemistry > Q uestions on lead azide precursors. - Archive File
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megalomania May 31st, 20 03, 10:4 7 AM

FadeToBlackened
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Posts: 201
From : Hell
posted 04-10-2001 08:51 PM
--------------------------------------------------------------------------------
I'm sure m any of you have seen this before(below). I'm a s s u m ing this is using 100% isopropyl alcohol. Ca n I just use norm al
rubbing alcohol? Im thinking m aybe add enough water to the alcohol so the 30% water + added water = 450 m L , a n d d i s s o l v e
the sodium nitrite in this mixture. Then, both containers cooled in an ice bath (anyone know tem perature lim its for this
procedure?), adding the H2SO 4 drop b y drop to the other solution, or m aybe the other way around . Would this work ?
Preparation of Isopropyl Nitrite
A mixture of 45 m l concentrated sulfuric acid, 3 0 m l water and 110 ml

isopropyl alcohol, previously cooled to 0 centigrades, was added to an ice
cold solution of 114 gram s of sodium nitrite in 450 m l of H2O. Slow
addition required abo ut two hours in order to m aintain a tem perature around
0 centigrades. The upper oily layer was separated and washed three tim e s
with 30 m l portions of 5 gram 100 m l sodium b icarbonate solution and 22
grams NaCl 100 ml solution respectively.
...and m y other question: I saw som e anarchist text a while back (i know better n ow, of course) that m e n t i o n e d t h e u s e o f
Lead Nitrate O R Lead Acetate. How do I get lea d nitrate, or would it be possible to make lead acetate?
O n e m ore question.. Anyone know about distilling hydrazine? I know som e people out there wouldnt com e within a m ile of it,
and with good reason . But when distilling it(by the m eth o d o n m e g a l o m a nia's site) is the xylene necessary, and could the
nitrogen atm ostphere be substituted for by a vacuum ?
-thanks for your time
[This message has been edited by FadeToBlackened (edited April 10, 2001).]
Rhadon
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Posts: 95
From : Germ a n y
posted 04-11-2001 07:50 AM
--------------------------------------------------------------------------------
L e a d a c e t a t e can be sim ply m ade by "m ixing" a lead salt with acetic acid. If you have elem ental lead the e a s i e s t a n d f a s t e s t
way could be grinding the lead up, burning it with sulfur and adding this to acetic acid. The drawback of this m ethod is that it
will produce H2S which is poisonous and stinks awfully.
It don't know about this surely, but distilling Hydrazine can be very dangerous sin c e t h e c o m p o u n d is explo sive itself if it's free
from water.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 04-11-2001 05:32 PM
--------------------------------------------------------------------------------
Yeah, I was thinking about that last night. I think i m ay (if i ever decide to put this into practice) just make dilute hydrazine as
d e s c r i b e d o n m e g a l o m ania's site, and adjust m y reactants accordingly...
And for acetic acid would white v i n e g a r b e s t r o n g e n o u g h ?

a n d I m provised C hemistry > Silane gas. - Archive File
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megalomania May 31st, 20 03, 10:5 7 AM

FadeToBlackened
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Posts: 201
From : Hell
posted 04-16-2001 07:25 PM
--------------------------------------------------------------------------------
Having recen tly m a d e m y way to rec.pyrotechnics, I couldn't help but notice the 'p yrophoric chem icals'(or so m e t h i n g ) p o s t . I n
it, som eone described a procedure the y saw at school. Making m a g n e s i u m silicide by heating magnesium with sand , this being
acco m p lis he d b y s im p l y b u r n i n g m a g n e s i u m i n s a n d . T h e r e s u l t i n g c o m p ound was then placed in "acidified water" (HCl) to
release the pyrophoric silane gas, which bubble s t h r o u g h t h e a c i d , a n d u p o n p o p p i n g m a k es little flashes. Has anyone tried
this? I think it would be kind of interesting just to see. Do you think burn ing a coil of magnesium ribbon in sand would work? I
was thinking to use vinegar, b ut i started thinking that m ight not work, since mon osilane is SiH4, it probably needs the H+
from an inorganic acid..?
endotherm
Freq uent Poster
Posts: 164
From : d u n n o
posted 04-16-2001 07:50 PM
--------------------------------------------------------------------------------
Maybe just highly diluted muriatic acid would do the trick

a n d I m provised C hemistry > Prep. of Benzoyl Chloride - Archive File
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megalomania June 1st, 2003, 12:19 AM

Alchem ist
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Posts: 211
posted 04-19-2001 09:08 PM
--------------------------------------------------------------------------------
Hello all,
Here is a excerpt from Pat. # 1,280,612 for those who do not want to down load it!
Benzoyl Chlo ride
Dry bleaching powder (calcium hypochlorite, or other equivalent hypochlorite,) and toluene are m ixed in proportions varying
acco rding to the extent of chlorination desired. For example, 200 kilogram s o f t o l u e n e a r e h e a t e d , a s i n a ' s t e a m jacketed iron
m ixing kettle to a high tempe rature, say 900 C . Dry ble aching powder is then slowly added to this, the temperature being
gradually raised until it approxim a t e ' - s t h e b o i l i n g p o i n t o f t o l u e n e . W h e n 2 0 0 k i l o g r a m s of bleach ing powder have been
a d d e d t h e m ixture is held at the high temperature attained, (i. e., to secure the best results, from 1000 C. to 1050 C.) for
about one hour, or, u ntil the reaction is effected, with continuous thorough m i x i n g . T h e e s c a p e o f t o l u e n e v a p o r d u r i n g t h e
operation m ay be prevented by m e a n s o f a r e f l u x c o n d e n s e r f i t t e d t o t h e m i x i n g v e s s e l . T h e r e s u l t i n g m i x t u r e i s t h e n c o o l e d
down and allowed to settle and as m uch oil as possible is siphoned off from the top. The oil left adhering to the line residue is
t h e n r e m o v e d b y s t e a m distillation and added to that siphoned off. In this way 200 to 210 kilos of oil are obtained, having a
specific gravity of .940 to .960 at 200 C. and containing from 30 to 35 per cent. o f benzyl chloride and from 70 to 65 per cent.
of toluene. T hese can then be separated by fractional d istillation. A higher percentage of chlorinated product can be o b t a i n e d
by u sing a greater proportion of the bleaching powder. In this ca se, however, som e benzal chloride and benzo-trichloride will be
form ed.
Or, if desired, sufficie nt bleaching powder
m ay be added to convert all the toluene directly to benzal chloride and benzo-trichloride a nd the resulting m ixture of lime and
the chlorides can be converted into benzaldehyde and benzoic acid by boiling with water.
P . S . , P l e a s e n o t e t h a t t h e a m o u n t s a r e f o r c o m mercial quanities, so for lab use, m a k e t h e m as required fo r your needs. The

ratio's are one to one!
------------------
[ T h i s m e s s a g e h a s b e e n e d i t e d b y A l c h e m ist (edited April 20, 2001).]
nbk2000
Moderator
Posts: 1096
From : G u e s s
posted 04-19-2001 09:33 PM
--------------------------------------------------------------------------------
I'm sure this is very interesting, but you need to post a lab scale, not industrial scale, sized reaction. You can find one in the
organic synthesis series or vogels organic techniques.
------------------
Alchem ist
Freq uent Poster
Posts: 211
posted 04-20-2001 12:40 PM
--------------------------------------------------------------------------------
Your VERY correct nbk2000. I am sorry about the error!

a n d I m provised C hemistry > Ethylchloride - Archive File
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Nitro
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Posts: 51
From :
posted 04-20-2001 01:54 PM
--------------------------------------------------------------------------------
C a n i t b e m ade bye the reaction of HC L and Ethyl alcohol?Or does it needs some Catalysts?I want use it for making Acetic acid
anhydrous.Oh and how do i purify it?Distillation or only boiling?
Thx for any answer.
sim ply RED

Freq uent Poster
Posts: 240
From : HELL
posted 04-20-2001 02:36 PM
--------------------------------------------------------------------------------
In theory it can be made by chlorating ethane : H3C-C H3 +CL2=H3C-CH2Cl + HC l, this reaction must be caried out under high
pressure, ultraviolet light(m ay be optional). Som e chem ical that absorbs the HCl is needed!
m ethod 2: By reacting ehtene with HCl: H2C-CH2 + HCl=H3C-C H3Cl (it needs high temperature, high pressure and catalyser).
m ethod 3: By reacting ethyl alcohol with with HCl: C2H5O H + HCl=H3C-CH2C l + H2O, it needs high temperatute,
pure(concentrated) in gredients (HCl and alcohol). I've never tried one of these processes...
nbk2000
Moderator
Posts: 1096
From : G u e s s
posted 04-20-2001 10:21 PM
--------------------------------------------------------------------------------
Bubble dry HC l gas through absolute e thyl alcohol till saturated at room temp, an d then distilling.
Pure ethyl ch loride boils at 51.8 F (11C) and is a clear, colorless, lim pid fluid.

a n d I m provised C hemistry > dextrin from starch - Archive File
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king s p a z
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Posts: 347
From : U K
posted 04-21-2001 05:15 PM
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i was reading in the com ptons encyclopedia on my PC and it said that starch turns to dextrin when heated to 182*C. i was just
wondering if anyone has succesfully done this.
ALENGOSVIG1
Moderator
Posts: 766
From : V a n c o u v e r , C a n a d a
posted 04-21-2001 05:18 PM
--------------------------------------------------------------------------------
Yes just put it in the oven and wait a few hours, or i just put it on max and watch it until It turns brown, then take it out. More
information on the subject is on J's site.
king s p a z
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Posts: 347
From : U K
posted 04-21-2001 05:45 PM
--------------------------------------------------------------------------------
thanks
sealsix6
Freq uent Poster
Posts: 154
From : NYC ,NYC,USA
posted 04-21-2001 06:44 PM
--------------------------------------------------------------------------------
W hat could someone do with dextrin?
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 04-21-2001 07:02 PM
--------------------------------------------------------------------------------
I t s u s e d a s a b i n d e r i n s o m e pyro com p s . a n d a s a d e s e n s i t i z e r f o r l e a d a z i d e .
sealsix6
Freq uent Poster
Posts: 154
From : NYC ,NYC,USA
posted 04-22-2001 08:46 AM
--------------------------------------------------------------------------------
Oh could someone put the dexitrin with BP and m ake like stars from them ? O r dexitrin + Gas to m a k e a d i f f r e n t k i n d o f
napalm?
DarkAngel
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Posts: 592
From : ?
posted 04-22-2001 09:40 AM
--------------------------------------------------------------------------------
I don`t think d e x t r i n e n a p a l m would work ,W hen a mix of dextrine dry`s it becom es rock hard
------------------
DarkAngel
For explosives and stuff go to Section1 http://www.section1.f2s.com And http://run.to/section1

s e n d t o s e c t i o n 1 @ h o t m ail.com
king s p a z
Freq uent Poster
Posts: 347
From : U K
posted 04-22-2001 05:04 PM
--------------------------------------------------------------------------------
d e x t r i n i s u s e d i n m o d e l r o c k e t e n g i n e s to bind the black powder fuel together. the dextrin is the reason why its hard as fuck
to grind rocket engine propellant up. so i would imagine it would be quite handy for making stars.
BoB-
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Posts: 679
From :
posted 04-22-2001 06:45 PM
--------------------------------------------------------------------------------
I use Dextrin to bind my BP stars together, its simple, and you can add *some* color to it.
urbana June 8th, 2003, 10:41 PM

Of course it works.
I h a v e m a d e dextrin from starch for at least 3 tim es. Every time by cooking starch in a oven and just
to m a k e y o u m ore co nfident about this, without a temperature control.
I just followed the conversion watching every quarter of hour, when i opened the oven for m ixing.
It re ally work s
urbana
jfk June 9th, 2003, 05:29 AM

yeah, i just oven bake corn starch into dextrin, mixxing it around every 20 m in till its brown.
as for colours - how would you go about oclouring it ?
- pigment?
- food colour?
or a chemical that burns with a coloured flam e? (strontium nitrate, CuSO4 ect..) ?
DBSP June 9th, 2003, 11:48 AM

when you bind BP with dextrine do you use water to bind it or can you use other solvent th at dry faster?
urbana June 9th, 2003, 02:05 PM

As long as I know water is the best substance to wet dextrin in BP. As a matter of fact I use a wate r and alcohol solution
(75:25)only to avoid growth of saltpetre crystals during drying.

a n d I m provised C hemistry > P h o s g e n e a s u b s t i t u t e f o r P C l 3 i n C H 3 C O C l p r o d u c t i o n ?
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FadeToBlackened June 1st, 2003, 01:09 AM

After reading that thionyl chloride can also be used for this reaction, I started looking around trying to find a synth for it. I had
no luck; all I found were uses of it. I d id, however, just find www.twinlakechem i c a l . c o m , a s u p p o s e d c o m p a n y t h a t s u p p o s e d l y
sells acyl chlorides and som e of their precursors. They claim t o a l s o u s e p h o s g e n e . I ' m n o t r e a l l y k n o w l e d g able on this though,
m aybe som eone else could think about it?
I also found www.chem icalland21.com , they have little b its of insight about a various m any chem icals and often a little
description of how they are m ade. Just thought I'd add that.
So aside from the inherent da n g e r o f u s i n g p h o s g e n e f o r h a l o g e n a t i n g a cids, (no t that PC l3 would be friendly..), wo uld it be
possible?
Edit: The mo re I search the m o r e I d o s e e C O Cl2 referred to for this.
Microtek June 1st, 2003, 12:54 PM

S e e i n g t h a t S O C l 2 i s u s e d i n m any chlorination reactions, I looked into p roduction as well. I found that the reaction of SO2 with
Cl2 produces it along with som e byproducts.
W hile both SO 2 and Cl2 are nasty, the y could be absorbed or destroyed without too much trouble. The question is how difficult
it would be to separate the SO Cl2 from the byp roduct.
FadeToBlackened June 1st, 2003, 04:29 PM

from http://www.xdhg .com.cn/article/2002/abs/e-abs-2002-03.htm l:
Abstract: Applications of thionyl chloride in pharmaceutical and p esticide sectors a nd application de v e l o p m e nts in organic
synthesis reaction and ring formation reaction are introduced. Synthesis m ethods of thionyl chloride such as HSO3Cl m ethod ,
S O 2 m ethod, SO 3 m ethod, co -production m eth o d a n d e n t e r p r i s e s a d o p t i n g a b o v e m e t h o d s a r e e v a l u a t e d . T h e d o m estic
p r o d u c t i o n , d e m a n d , i m port and export of thionyl chloride are analyzed. It is suggested that backward HSO 3 C l m e t h o d s h o u l d
b e e l i m i n a t e d a n d n e w plants should adopt advanced technologies. Factors such as feedstock source and scale effect should
be considered when new plants are being built.
HSO 3Cl, chlo rosulfonic acid.. possibly m ade from readily available sulfam ic (am id osulfonic) acid?
Al Koholic June 11th, 2003, 10:01 PM

By p assing C l2 gas in to molten sulfur at 295 degrees centigrade one can obtain S2Cl2: Cl-S-S-Cl. This can be used in a
synthesis of C H3COCl. I forge t the exact details of either synthesis...I believe I may have seen it on rhodium . T h e a p p e a l o f
this method of acyl chloride production is that all the ne cessary chemicals are easily obtainable. A simple chlorine generator,
s o m e pure sulfur powder, and the appropriate equipment is all that is required. I am thinking about adding the sulfur to a 5 0 0
m l two neck round bo ttom boiling flask. The Cl gas will be administered through the side neck via a length of bent glass tub ing
and a stopper. I haven't got the synth in front of m e but I believe it is fairly straightforward. Just h ad a look at Merck...you can
f i n d a s y n t h i n - F e h e r H a n d b o o k o f P r e p a r a t i v e I n o r g a n i c C h e m istry vol. 1, G. Bra uer, Ed. (Academ ic Press, New York, 2nd ed.,
1963) pp 371-372. Hydrolysis: H. L. Olin, J. Am . C h e m . Soc. 48, 167 (19 2 6 ) . M e r c k o n l y m e n t i o n s m o l t e n s u l f u r s o m a y b e m y
m emory of 2 95 centigrade is incorrect. The product has a boiling point of 138 C so it is ea sily purified by fractional distillation.
It m ustn't contact water though as nasties will form .
Al
FadeToBlackened June 11th, 2003, 11:54 PM

G o o d t o s e e s o m eone but myself replied to this!
I b e l i e v e m e g a l o m a n ia has a synth for C H 3 C O C l u s i n g P C l3, which says SO C l 2 m a y a l s o b e u s e d ( S 2 C l 2 a l s o ? ) . I d o n ' t s e e

how it would m ake much of a difference depending on which chlorinator you used. As I was thinking this, Nitrogen halides
(being discussed a bit now) and alum inum chlo ride also c r o s s e d m y m i n d .
FlaA lchemist January 28th , 2004, 12:22 AM

C a n P C l 3 b e m a d e b y a n y o t h er methods than reacting red or yellow pho usphous with Cl2?
nbk2000 January 28th , 2 0 0 4 , 0 5 : 3 5 P M

Passing chlorine through activated charcoal saturated with metaphosphoric acid produces PCl3.
vulture January 29th , 2 0 0 4 , 0 5 : 2 4 P M

How about m a k i n g P C l 3 f r o m PH3?
PH3 gas (itself very p o i s o n o u s ) i s m ade by reacting calcium phosphide with water:
Ca3P2 + 6H2O ---> 2PH3 + 3Ca(OH)2
C a l c i u m p h o s p h i d e c a n b e b o u ght as rodent poison or m ade by reducing C a3PO4 with aluminium , a reaction com m o nly used
for rodenticide sm o k e b o m b s .
2PH3 + 6Cl2 ---> 2PCl3 + 6HCl
P r o b l e m s:
1) Is this reaction feasible?
2) PH3 is extrem ely poisonous and autoignites on contact with a ir.
One could also burn the PH3, collect the form e d P 2 O 5 a n d m ake POCl3 with that...
Polverone January 30th , 2004, 01:43 AM

One could also burn the PH3, collect the form e d P 2 O 5 a n d m ake POCl3 with that...
T h e c o m bustion of PH3 is also going to produce H2O, and we all know how m uch P2O 5 loves water.
Al Koholic January 30th , 2004, 01:53 AM

Y e a h . P h o s g e n e w o u l d b e a n e x c e l e n t c h l o r i n a t i o n a g e n t . I a c t u a l l y f o u n d a m eth od of m aking acetyl chloride with phosgene
before...can't rem ember what I did with it though, could find it again if th eres any interest! I'll keep and eye on this thread...
P h o s g e n e i t s e l f i s m a d e b y s i m ply running a Cl2 stream i n t o a C O s t r e a m . T h e g a s e s m i x a n d f o r m phosgene just like that. In

fact, in old days chem i s t s u s e d t o u s e e q u a l f l o w i n g s t r e a m s o f t h e s e g a s e s i n s t e a d o f h a v i n g p h o s g e n e t a nks lying around.
I've never tried this b ut supposedly it works. You could just cool the gas stream d own to 8C and co n d e n s e t h e p h o s g e n e . I f
you did all this outsid e now you'd have no prob lem hehehe (NE US).
Anyway, I believe that the SO2 + C l 2 a l s o m a k e s a p p r e c i a b l e q u a n t i t i e s o f S O 2Cl2, another good chlorinating agent. Ahhhhh
the quest for the elusive acid chloride....
Sarevok January 30th , 2004, 04:00 AM

P C l 3 c a n b e m ade by chlorinating ferrous phosphide with anhydrous chlorine at 200-486C (less than 486C to avoid vaporizing
the product). The product is m ixed with non-chlorinated ferrous phosphid e , h e a t e d t o 2 7 0 C a n d t h e n t o 3 0 0 - 4 0 0 C with the
e v o l u t i o n o f g a s e o u s P C l 3 . 4 0 parts by weight chlorinated ferrous phosphide mixed with 18 parts by weight ferrous phosphide
should work well.
2 F e 2 P + 1 1 C l2 ---> 2 (FeCl3)2 P C l 5
7(FeCl3)2PCl5 + (4+n)Fe2P ---> 11PCl3 + 22FeCl2 + nFe2P
n e q u a l s a n u m ber greater than 0.
B o t h r e a c t i o n s a r e e x o t h e r m i c s o o n e s h o u l d n o t h a v e p r o b l e m s t o m aintain the temperatures between the required

temperature range. T h e c h l o r i n a t e d f e r r o u s p h o s p h i d e s h o u l d b e i m mediatly reacted with non-chlorinated ferrous phosphide
a n d t h e n i m m ediatly distilled (if one is going to store it, it m ust be stored at its liquid state: 100-486C).
Ferrous phosphide is stable, its only hazardous if you eat it or inhale its dust, so I think a chemica l supply store would seel it
without asking questions. The m ain problem would be generating and drying the chlorine:
Posted by nbk2000
Chlorine is m ade by dripping hydrochloric acid onto calcium hypochlorite (HTH pool shock, $50 for 40 pounds). Drying is done
by p assing through sulphuric acid or m a g n e s i u m sulpha te, though the acid is preferred.
B u r n i n g P H 3 t o m a k e P 2 0 5 t o m a k e P O C l3 see ms unlik e l y ( r e a d P o l v e r o n e ' s p o s t ) . P O C l 3 c a n b e m ade by reacting calcium
(ortho or meta)phosphate with anhydrous chlorine in the presence of carbon at 800C.
C a 3 ( P O 4 ) 2 + 6 C +6C l2 ---> 2 P O C l 3 + 3 C a C l 2 + 6 C O ( w i t h t h e o r t h o p h o s p h a t e )
C a ( P O 3 ) 2 + 4 C + 4Cl2 ---> 2POC l3 + C aCl2 + 4CO (with the m e t a p h o s p h a t e )
P C l 3 w o u l d b e l e s s h a z a r d o u s t o u s e t h a n p h o s g e n e . . . i f o n e r e a l l y w a n t s t o u s e p h o s g e n e , T h e W ar Gases shows various ways

about how to m ake it, how to detect it, how to decompose it, etc.
P.S.: Is my english getting an y better? I hope it is... I've always learned it on my own; now I'm studying this Gram mar,
Punctuation, and Spelling (http://owl.e n g l i s h . p u r d u e . e d u / h a n d o u t s / g r a m m a r / i n d e x . h t m l) website. Sorry if this is a silly
question.
kingspaz January 30th , 2 0 0 4 , 0 2 : 5 0 P M

Sarevok, yes, your english is getting m uch better :)

T h e c o m bustion of PH3 is also going to produce H2O, and we all know how m uch P2O 5 loves water.
Doh! W hat was I thinking! Atleast you'll have reasonably pure H3PO4 which isn't such a bad precursor after all.
W ould the m ethod to form PC l3 from PH3 work? Or will it form P C l 5 ?
Sarevok January 30th , 2 0 0 4 , 1 0 : 1 4 P M

I don't know if it would work, but if it doesn't work, sparks convert phosphine to hydrogen and red phosphorus (acco rding to
M o d e r n I n o r g a n i c C h e m i s t r y , p a g e 2 2 6 ) . T h i s p h o s p h o r u s c o u l d b e u s e d t o m a k e PCl3 or whatever.
Here is what I found on google (http://www.c-f-c.com / g a s l i n k / p u r e / p h o s p h i n e . h t m ):

P h o s p h i n e b e g i n s t o d e c o m pose into its elements at about 375C. It rea cts spontaneously with chlorine.
Perhaps the reaction is possib le, after all. If it m a k e s P C l 5 i n s t e a d o f P C l 3 , t h e r e i s n o p r o b l e m : PC l5 dissociates (probably to
chlorine and PCl3) at 600K (something like 32 0C, I th ink), according to the sam e b o o k I m e n t i o n e d a b o v e , p a g e 2 5 1 .
FlaA lchemist January 31st, 2004, 05:33 PM

Originally posted by nbk2000
Passing chlorine through activated charcoal saturated with metaphosphoric acid produces PCl3.
W ould this work if Bromine instead of chlorine?:cool:

megalomania February 1st, 2004, 0 1 : 2 4 P M

Do you have any details on th e p r o c e s s o f p a s s i n g C l t h r o u g h m etaphosphoric acid nbk? That sounds like a very prom ising
route if the yields are g o o d .
Sarevok February 1st, 2004, 1 1 : 4 9 P M

This process is described on U S Patent #2712494, but it does produce POCl3, not PCl3.
I think that it would work with any halogen (perhaps not very well with iodine).
nbk2000 February 2nd, 2004, 04:15 PM

My bad. :o
It's the ferro-phosphate proce s s t h a t p r o d u c e s P C l 3 . T h e m etaphosporic/carbon process produces the phosphoryl oxychloride
needed for tabun.
FlaA lchemist February 2nd, 2004, 08:07 PM

Originally posted by nbk2000
My bad. :o
It's the ferro-phosphate proce s s t h a t p r o d u c e s P C l 3 . T h e m etaphosporic/carbon process produces the phosphoryl oxychloride
needed for tabun.
Do you m ean Ferro Phosphide or Ferro P h o s p h a t e P r o c e s s : c o n f u s e d :
Very interesting info :cool:

a n d I m provised C hemistry > How to solve a stoichiometric ratio
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View Full Version : How to solve a stoichiometric ratio
klassasin June 4th, 2003, 08:52 PM

This was written to ex plain how to write and solve stoichiometric ratios. For m y e x a m ple I will use the synthesis of HNO 3 usin g
H2SO 4 and a nitrate (KNO3).
1) write the equation down
H2SO 4 + KNO3 -> HNO3 + KHSO 4
2) W rite down how m any moles of each reactant/product
1 1 1 1
3) W rite down their atomic weights (g/m ol)
98 101 63 136
4 ) F o r t h e e x a m p l e l e t s s a y y o u h a v e 1 9 6 g o f H 2 S O 4. Lets see how much KNO3 you'll need

(Write down known values, in gram s)
196 x1 x2 x3
5) W rite the proportion and solve
196 98
----- = ----
x1 101
* The ratio 9 8:101 is the am ount of H2SO 4 to KNO 3
6) If you solved corre ctly you would have gotten 202g of KNO3 for 196g of H2SO 4
* To apply to other m e t h o d s m ake sure to m a t c h u p t h e n u m e r a t o r s a n d d e n o m inators right

196g of H2SO4 lines up with the 98g/mol of H2SO4
* T o s o l v e f o r o t h e r a m o u n t s o f H 2 S O 4 r e p l a c e the 196 in the proportion with the grams of H2SO4 you will be using
* I write down how m any moles of each because it helps on writing the proportion write. Writing the known values helps by you
know what you can or need to solve for.
P.S. I am sorry if you get m ad at me for this new topic because I am still new at posting here. I just wanted to make a
contribution to this forum com munity. I hope this is a contribution and th a t s o m e o n e f i n d s i t u s e f u l.

and Improvised Chemistry > Methods of extracting NM - Archive File
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View Full Version : Methods of extracting NM - Archive File
megalomania June 8th, 2003, 01:02 PM

TylerDurden
Frequent Poster
Posts: 94
From:
posted 04-24-2001 11:24 AM
--------------------------------------------------------------------------------
I needed a method to get NM out of race fuel mixtures (methanol with nitromethane). I know that you can distill the mixture
under reduced pressure. Another method is to add smokeless powder to gel the NM (with the nitrocellulose).
But I found a new and very simple method: just add a lot of water to the race fuel mixture. The water dissolves in the
methanol and NM sinks to the bottom because it no longer can dissolve in the methanol. The only disadvantage is that water
also dissolves a little in NM (to about 2.5%). So this NM should be "dried" before it can be used in ANNM explosives. Maybe
this can be done simply by filtering the "wet" NM through a little dry AN. Or maybe just a little AN can be added.
Do you guys have any comments on this method? Or any suggestions for improvements?
And I thought of another method: just letting the race fuel evaporate overnight at room temperature. Because methanol will
evaporate faster than NM. It would be "distilling" at room temperature, but what kind of mixture would result? Will it lead to a
mixture with high(er) NM content? (Tim Lewis let's his distilled NM stand overnight to let the remaining methanol evaporate
which results in a 80-90% mixture. That's where I got the idea from). Is it possible?
[This message has been edited by TylerDurden (edited April 24, 2001).]
Anthony
Moderator
Posts: 2306
From: England
posted 04-24-2001 02:51 PM
--------------------------------------------------------------------------------
I tried vacuum distilling model fuel (20% NM, 20% castor oil, 60% methanol) the other day.
I basically follwed the instructions in KIPE2, it claims to heat the retort to 50*C, I couldn't get an noticeable amount of vapour
being produced untill the temperature was raised to 65*C. The process was very slow and I only colletced a few ml of purified
fuel, although my collection vessel may not have been cold enough.
I left the purified fuel to stand over night, nearly all of it evaporated (room temp was about 15*C), what was left would not
burn. An oily residue was also in the evaporating dish - probably castor oil.
Tyler, your method sounds very easy, but won't the castor oil also settle out to the bottom? Maybe if the NM and castor oil
formed noticable layers then the NM could be sucked off with a pipette. Could NM be dried by placing in a dessicator with
H2SO4 or NaOH?
Leaving the fuel to evaporate would probably leave a mixture of NM and castor oil an you'd probably loose some of the NM to
evaporation.
pete
Frequent Poster
Posts: 56
From: u.k
posted 04-24-2001 02:56 PM
--------------------------------------------------------------------------------
I have tried to do this myself, never worked. It should do but it didn't, the problem that i experienced was that i couldn't
separate the nitromethane from the water as the oils in the nitromethane stained the water a green colour which i could not
get rid of. I also added NaCl to the water before i mixed it with the fuel, as this reduces nitormethane solvation. I know that
the nitromethane had separated out as if you but a rod in the mixture it came out covered in nitromethane.
Anthony
Moderator
Posts: 2306
From: England
posted 04-24-2001 03:34 PM
--------------------------------------------------------------------------------
If you knew the nitromethane was seperating at the bottom of the solution, couldn't you just drain it off from a tap at the
bottom of the vessel?
fightclub
New Member
Posts: 39
From: none
posted 04-25-2001 02:00 AM
--------------------------------------------------------------------------------
Tyler Durden is a great man.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-25-2001 05:22 AM
--------------------------------------------------------------------------------
THus your problem is only to separate NM from methanol and castor oil!
1)With an exces of water, you would take methanol away because NM is not very soluble in water ( especially if there is some
acid; just add a little H2SO4 or whatever acidic), shake and decantate ; you collect the NM and the castor oil. Yes you loose a
little NM but not that much.
2)With evaporation at room temp, you loose both NM and methanol since both are very volatile! Maybe you increase a little
the % of NM but you loose much more NM than in the first process....but you stil have castor oil!
3)By distillation is one of the best ways; just add water to the mix like 0.5Vol/1Vol mix and distill at ambiant temp whit a
cooling flask!
-First the methanol will come out because it has a boiling point of 65-67C...that's what those guys making a distillation has
obtained...it burns but it is not NM!!!!So disgard everything passing under 80C(or keep if you want methanol to make
methanol nitrate or as a solvant).
-Then comes water and NM between 95C and 110C
Since NM is not soluble in water, in the cooling flask you should see a turbidity and a decantation; one of the layer is water
(upper) and the other is NM (pure).
-In the bottom of your distillating flask will remain castor oil with very little NM and water since it has a much higher boiling
point...it will burn before distilling so stop when you get white fumes inside the distilling flask!
Under reduced pressure the same order of outcome for the products, same procedure but temperatures are lower...I don't
know them since it depends on the pressure!
------------------
TylerDurden
Frequent Poster
Posts: 94
From:
posted 04-25-2001 07:27 AM
--------------------------------------------------------------------------------
I didn't think about the castor oil because the race fuel I used didn't contain castor oil (or at least it wasn't mentioned on the
label). But it would indeed settle down with the NM (or does the castor oil float on top of the water layer like some other oils?
in that case castor oil is no problem at all). But if it settles down dissolved in/with NM that would only be a problem if the race
fuel contains a lot of it. But I thought that when castor oil is used it would be in the range of 1-2%. 20% seems to me a very
high percentage but if so it would render the very simple method useless. Because the result would be a NM/castor oil mixture
(50/50).
By the way, I would not recommend adding acid to the water because it will sensitize the NM (making it unstable). The use of
NaCl or acid is also not necessary because it would reduce the amount of methanol that will dissolve as well.
And drying the resulting NM (which you get by just decanting the water off or letting the NM drip out of the bottom of the
container) with AN seems to me the most handy. You need AN anyway so why use other chemicals.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 04-25-2001 08:15 AM
--------------------------------------------------------------------------------
I was wrong about the castor oil content. It is indeed used in 10-20% range. So this method would only be usefull if the
amount of NM exceeds the amount of castor oil a lot. For example a mixture of 10% castor oil, 50% NM and 40% methanol.
This would result in a mixture with about 20% oil. Maybe this can be used for ANNM explosives. But I'm not sure.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-25-2001 09:25 AM
--------------------------------------------------------------------------------
My guess is that castor oil is almost fully soluble in NM (or the contrary!) that means that no way to separate them by droping
in water!Only distillation can help!
NM sensitised by acids??? I have never seen this in any book I have on nitrocompounds!
What I know is that the solubility comes from a partial decomposition into nitronate...nitronic acid is soluble slightly in water
and its solubility decreases when there is a trace of acid in the media!
------------------
Anthony
Moderator
Posts: 2306
From: England
posted 04-25-2001 03:36 PM
--------------------------------------------------------------------------------
I poured some of the NM fuel I had into water. It immediately turned cloudy white and a thick layer of yellow castor oil went
stright to the top. I've left it so hopefull the NM will settle out at the bottom.
Thanks philou, I will try again soon. I had presumed that you needed to distill the NM under vacuum or it would decompose
from the heat. I was using a pretty strong vacuum (for re-gassing fridges). I will do it without the vacuum next time so that I
can tell when the different fractions are coming off by reading the temp. I'll also make a condensor instead of using a cooled
flask.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 04-26-2001 07:15 AM
--------------------------------------------------------------------------------
Yes there is no need of vacuum for the distillation of NM; no risks of explosion! You don't even need a glass rod distillator; a
simple wooden (i guess its is that in french we say "liege" a kind of agglomerated wooden foam that is used to close wine
bottles)stop rod will do the thing since NM is non reactive substance (not acidic like HNO3) towards wood. The thermometer
must be placed near (in front of) the top of the cooler/condenser pipe so it gives the temp of the gas that is condensing
there!
Don't put the thermometer in the mother liquor since that has a higher temp (overheated castor oil/water mix)!!!
------------------
Anthony
Moderator
Posts: 2306
From: England
posted 04-26-2001 04:43 PM
--------------------------------------------------------------------------------
In English it is "cork"
I just tried again with a cork bung with a glass tube through it and then some PVC hose leading to a cooled flask (I found the
vapour condensed in the tube as soon as it left the retort so no need for a condensor). I had the thermometer in the heating
water bath for the retort, I know it's not very accurate but it was all I could do. I had the methanol coming off nicely but didn't
have time to get it all out.
I got some rubber bungs for wine making which fit my thermometer with a short piece of pvc hose over the thermometer to
make it fit tightly in the bung. I managed to make a small (approx 3mm) parallel to the original hole for the glass tubing (I
only have small diameter stuff at the moment). So now I can have a thermometer in there to read the vapour temperature.
Only trouble is that the bung is far too big to fit into the bottles I use for a retort. So I'll punch a hole in a metal jar lid and
use the jar as a retort.
This stuff sure is hard when you don't have proper lab supplies!
The NM fuel in water: it is still cloudy white (caused by the methanol) and I cannot see any kind of seperation that would be
the nitromethane. So I think it's not going to work.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 04-27-2001 04:56 AM
--------------------------------------------------------------------------------
Philou, I didn't say you could separate NM from castor oil with this method. I said you can separate NM from the methanol by
adding water to the race fuel (about as much as the amount of fuel, and not by pouring the fuel in a lot of water). The mixture
will turn cloudy white and letting it stand 10 minutes results in a layer of NM at the bottom.
Now, if castor oil is present it will most likely settle down with (dissolved in) the NM (or maybe float on top). And if the amount
of castor oil is low you get a mixture of NM/castor oil that can be used (after drying) for explosives.
By the way you can separate the NM from the castor oil by adding pingpong balls (celluloid) this will gel the NM (adding PPB's
directly to the race fuel will not work becuase celluloid dissolves in methanol. If you want to gel NM out of race fuel you need
guncotton/smokeless powder).
And NM is sensitized by acids! NM is sensitized by almost anything! alkalies, acids, oxidizing agents, reducing agents, and lots
more.
And the advantage of this method is that it's EASY. You only need water. Of course destillation yields a better, purer product
without the castor oil but you need glassware , heating source, thermometer, and time. If you have it I would recommend
distilling race fuel. And remember that castor oil is probably just as good as fuel oil for producing ANFO, so a bit of castor oil in
NM will probably have no negative effect when used to make the ANNM explosive.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-08-2001 06:44 AM
--------------------------------------------------------------------------------
Anthony, I think the yellow layer at the top is NM with castor oil. Since no layer is formed at the bottom and NM dissolves
castor oil. So the mixture of NM/castor oil in this case is lighter than water/methanol and therefor floats on top.
The race fuel I used resulted in the NM settling down (probably with some castor oil), but I think it depends on the ratio of NM/
castor oil wether it settles down or floats on top. It's impossible that NM stays dissolved in the methanol/water mixture.
So you ended up with a 50/50 mixture of NM/castor oil. This is probably not very usefull but you can get NM out if the mixture
with celluloid. And if you use race fuels with less castor oil the resulting mixture contains mostly NM and can directly be used in
ANNM explosives.
Anthony
Moderator
Posts: 2306
From: England
posted 05-08-2001 02:25 PM
--------------------------------------------------------------------------------
Maybe it does float with castor oil dissolved in it, I don't know. I've got the seperation by distillation sorted now some I'm not
really worrying about it. An easy way to tell what fraction is coming off is to drop a drop of the distilate into water, if it's
methanol it'll form a little white cloud. If it's NM it'll sink to the bottom in a little ball.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-09-2001 06:30 AM
--------------------------------------------------------------------------------
Yes, distillation is by far the best method (if you got the glassware and thermometer and stuff). But I was just wondering
about an easier way to extract NM, so...
By the way, if you distil race fuel you will end up with a NM/methanol mixture (80-90%)(depending on the quality of your
distillation equipment: with bad equipment it's impossible to separate the two and you'll end up with a mixture with a lot of
methanol) because the boiling points of methanol and NM are too close together. And methanol has some serious
disadvantages: it's poisonous and atracts water from the air quite quickly (a drop of race fuel spilled will turn cloudy white
within a short time because of the water that is absorbed from the air!).
But if you would distil the NM/castor oil mixture that you get after adding water to race fuel, you would get PURE NM without
methanol and without castor oil! (and the distillation is much easier and can be done with some improvised equipment since
you just have to evaporate the NM and somehow cool it and collect it).
So my method proves to be handy after all: it will give you a route to pure NM without methanol (or a usefull NM/castor oil
mixture if you don't want to distill).
"one can make all kinds of explosives using a few simple household items"
[This message has been edited by TylerDurden (edited May 09, 2001).]
Anthony
Moderator
Posts: 2306
From: England
posted 05-09-2001 03:48 PM
--------------------------------------------------------------------------------
I agree with what you're saying but I'd hardly say it's difficult or impossible to seperate NM from methanol with improvised
equipment! Methanol B.P = 65*C NM = 101*C that's a fair amount of difference. I usually discard the first NM drawn off as it
could contain the last dregs of methanol.
If you add race fuel to water and draw off the NM/castor oil layer and try to distil it, you're going to have water in your "pure"
NM.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-10-2001 05:15 AM
--------------------------------------------------------------------------------
Yes, you're right, the NM would contain water (max. 2.5%). But it's easy to dry, with some AN. And then you have 99% NM.
Besides, your resulting NM/methanol mixture will probably also contain water since the methanol atracts it from the air (before
or during the distillation or when in the receiving flask with NM, or afterwards). Maybe that's why it should be done under
reduced pressure? And stored airtight.
Even if you dry it, you would have a hydroscopic NM/methanol mixture of max 90%.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-14-2001 11:46 AM
--------------------------------------------------------------------------------
Any comments on that? Getting water in the NM/methanol mixture would be a problem I think.
Anthony
Moderator
Posts: 2306
From: England
posted 05-14-2001 02:17 PM
--------------------------------------------------------------------------------
OK, I'll try both methods and compare the results.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-15-2001 06:03 AM
--------------------------------------------------------------------------------
OK, thanks. Let me know.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-24-2001 07:10 AM
--------------------------------------------------------------------------------
Don't want to rush you, but are there any results already?
Anthony
Moderator
Posts: 2306
From: England
posted 05-24-2001 03:02 PM
--------------------------------------------------------------------------------
Ah yes, my conclusion: Bollocks to the both of them I'm going to just buy some pure NM.
You're right, seperating NM from methanol is difficult having to work at low temperatures to stop them both coming off takes
forever.
Seperating the castor oil collected from pouring the fuel into water seemed to work, except the "NM" extracted didn't smell
right, dissolved in water and was flame retardant!
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-25-2001 06:16 AM
--------------------------------------------------------------------------------
I can accept that my idea doesn't work. Sometimes a perfectly good idea turns out to be bullshit. But what I don't understand
is WHY it doesn't work. And I can't stand that. So does anyone have an explanation for this result??
Maybe the NM is still dissolved in the methanol/water mixture (and makes it turn cloudy white)? But this seems unlikely. It
would prefer the castor oil wouldn't it? And it can't stay all in the water/methanol can it?
And if the resulting "NM" is not nitromethane (and it clearly isn't) what the fuck is it then? And how can it dissolve in water when
it is distilled from the layer that is separated by the water?!
This makes me crazy. So please help me.
Teck
Frequent Poster
Posts: 146
From:
posted 05-27-2001 02:57 AM
--------------------------------------------------------------------------------
why not just buy the NM its $30 for a gallon at http://www.worldwideracingfuels.com/products/fuel.htm
ezekiel
Frequent Poster
Posts: 110
From:
posted 05-27-2001 06:50 AM
--------------------------------------------------------------------------------
Nitromethane boils at 101'C, and is soluable in water.
Methanol boils at 64.6'C, and is miscible in water.
Thus bisolvent extraction with water won't work, or at least won't work very well at all.
Much better is distilation. You don't even need one of those expensiv vacuum pumps. The difference in Bps is so great that it
should be piss easy.
Admittedly I have never done it, and certain parts of the fuel may piss around with the boiling points.
Step by step guide:
Boil of methanol at 65'C
Distill off nitromethane at 102'C, discarding residue.
Dry the distillate with calcium chloride to remove any water picked up.
Filter... you now have hopefully pure-ish, 0% water Nitromethane.
Remember to use a closed flame, or oil bath or double boiler for heating as both NM and Methanol are flammable.
Anthony
Moderator
Posts: 2306
From: England
posted 05-27-2001 10:18 AM
--------------------------------------------------------------------------------
Ezekiel, if you heat to 65*C you get left with nothing but the castor oil.
ezekiel
Frequent Poster
Posts: 110
From:
posted 05-27-2001 05:29 PM
--------------------------------------------------------------------------------
I don't know what to say: nitromethane boils at 101'C.
Is this s general consensus opinion or just anthony's experience?
Anthony
Moderator
Posts: 2306
From: England
posted 05-27-2001 07:58 PM
--------------------------------------------------------------------------------
I don't claim to know what I'm doing, I'm learning as I go along. I don't see why NM shouldn't vaporise and condense at
65*C, afterall, BP of water is 100*C and it evaporates at room temperature.
TylerDurden
Frequent Poster
Posts: 94
From:
posted 05-28-2001 06:02 AM
--------------------------------------------------------------------------------
Nitromethane isn't soluable in water! The solubility in water is about 10%. It is of course completely miscible with methanol.
And about 2.5 % of water will dissolve in NM.
And water and methanol are also completely miscible. So far the facts.
Now what the effects are of adding water to race fuel I'm not quite sure anymore (I assumed that nitromethane was totally
insoluble in water). The amount of water is probably important just like the percentage of NM in the race fuel.
If to 100 ml of race fuel (20%NM, 20% castor oil, 60 methanol) 100 ml of water is added what happens? Maybe the NM stays
dissolved partly in the methanol partly in the water and only the castor oil separates. Who knows?
Maybe using another solvent is helpful?
By the way, you should distil under reduced pressure because otherwise the methanol attracts water from the air.
The resulting NM/methanol (80-90% NM) mixture you get after distillation has the same problem. (Distillation won't lead to
100% pure NM!)
CodeMason
Frequent Poster
Posts: 383
From: Your Nightmares
posted 05-28-2001 06:13 AM
--------------------------------------------------------------------------------
To get the water out of a mix of NM and water, try chilling it to 0C. NM can remain liquid at temperatures as low as -25C, so
the water will become ice but not the NM. All you'd have to do then is filter out the ice.
gcic
Frequent Poster
Posts: 80
From: Germany
posted 05-28-2001 08:36 AM
--------------------------------------------------------------------------------
Isn`t it a danger to cool the nitromethane to 0? Cooling down nitroglycerine is also dangerous, so I could imagine, that NM
probably behaves in the same manner(?)
PHILOU Zrealone
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Posts: 479
posted 05-28-2001 11:00 AM
--------------------------------------------------------------------------------
No because nitromethane is a nitrocompound while nitroglycerine is a nitrate ester...and thus is much more sensitive and high
detonating explosive!
Nitroglycerine is actually propantriol trinitrate ester!
------------------
gcic
Frequent Poster
Posts: 80
From: Germany
posted 05-28-2001 12:50 PM
--------------------------------------------------------------------------------
Yes, I know what nitroglycerine is. Philou, could you tell me, please, what is exactly responsible for the increasing sensitivity of
very cold NG? I mean, what chemical background does that have?
10fingers
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From: USA
posted 05-28-2001 01:26 PM
--------------------------------------------------------------------------------
Actually, nitroglycerine is less sensitive when cold.
Mr Cool
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posted 05-28-2001 02:25 PM
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I think it's just friction between crystals of frozen NG. Also, crystaline explosives are always more sensitive than amorphous
forms (look at crystaline TNT and quickly cooled cast TNT).
gcic
Frequent Poster
Posts: 80
From: Germany
posted 05-28-2001 05:22 PM
--------------------------------------------------------------------------------
ah yes, thx. That sounds like a reasonable explanation. Do you know, at which temperature nitroglycerin starts freezing?
My book says +10C, but I can`t imagine this.
Well, let`s better close this topic. It has nothing to do with the original discussion anymore.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 05-29-2001 11:08 AM
--------------------------------------------------------------------------------
Actually it is irregularities in the cristals that generates such a sensitivity (innerstresses)! Also since when frozen the density is
higher for most of the substances (water is an exception yes; ice of other products goes to the bottom of the fluid!), then the
VOD is as high as 8000m/s!
------------------
Mr Cool
Frequent Poster
Posts: 991
posted 05-29-2001 11:21 AM
Oh yes, stresses. Like when big crystals of lead azide form if you don't add dextrin or whatever, and they spontaneously
detonate. And when AP sublimes and re-crystalises, forming vey sensitive crystals.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 05-30-2001 05:15 AM
Precisely!
tom haggen February 16th, 2004, 06:54 PM

Ok, I have a crapy distillation setup. Can I take some water add it to my 30% nitro racing fuel, remove the methanol water
mix with a eye dropper. then distill the remaining castrol oil and nitromethane solution? Also should I or shouldn't I add an
acid to the water i'm adding to the racing fuel so it will absorb less nitromethane. So many conflicting opions on this thread its
hard to make a choice. Any advice would be greatly appreciated.

Well I think I sucessfully extracted Nitromethane with this method today. It was a big pain in the ass. My yield was very low. I
didn't let all of the nirtomethane distill off all of the way though. My pure nitro appears to be a pinkish color. When a light is
shined directly on it It appears to be a greenish yellow color. It still needs to be dried with some calcium chloride.

a n d I m provised C hemistry > Methylamine.
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Mr Cool June 8th, 2003, 01:11 PM

I was just gathering some stuff on forming salts of m ethylamine earlier, and thought that since I had this lovelly little nugget
of informatio n, I'd po st it here, in case anyone was interested.
Taken from patents and the Hive/Rhodium's site.
( M o n o ) m e t h y l a m ine Nitrate.
----------------------------------------------------------------------------------
NH4NO 3 + 2 CH2O --> CH3NH3NO3 + HC O O H ,
NH4NO 3 + CH2O + HCO OH --> CH3NH3NO 3 + H2O + CO2
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8 0 0 g o f a 3 7 % by weight aqueous formaldehyde solution were m ixed with 48g of urea and to the resulting mixture were added
8 0 0 g o f s o l i d a m m o n ium nitrate. On warm ing the m ixture to 60*C, an exotherm ic reaction set in and the tem perature rose to
90-95*C. The reaction mixture was m aintained at a tem perature of 95-100*C by applying heat when necessary for a period of
3 to 4 hours.Considerable quantities of carbon dioxide were released and at the end of the reaction period the reaction
m ixture had the following com position:
Solids : 67%
Form ic acid : 1%
W ater : 32%
The reaction mixture so form ed, containing unreacted a m m onium nitrate and me thylam in e nitrate, can be evaporated in any
suitable evaporation system to a water content that is d esired in the final explosive.
----------------------------------------------------------------------------------
A mixture of 800 parts by weight of am m onium nitrate, 620 parts by weight of 37% com m e r c i a l g r a d e f o r m a l d e h y d e a n d 5 0
parts by weight of sodium formate is h eated slowly till the tem perature reaches about 70* C to 80* C and as the reaction is
e x o t h e r m ic, it can m aintain itself between 95*C and 100*C. The reaction is, however, m a i n t a i n e d a t 1 0 0 * C to 105* C for 2
hours. At the end of this perio d the water conte nt of the reaction m ixture is reduced by vacuum distillation to about 12% by
weig ht to give after neutralisation with amm o n i a a n o x i d i s e r b l e n d .
----------------------------------------------------------------------------------
Methylam ine Hydrochloride from HMTA and Paraform ald e h y d e
70 gram s h e x a m ethylenetetramine (0.5 m o l e ) a n d 3 0 g r a m s p a r a f o r m a l d e h y d e ( 1 m o l e ) w a s d i s s o l v e d i n 2 0 0 m l water and
2 0 0 m l 3 7 % H C l ( 2 m o l e s ) w a s a d d e d . T h e m ixture was slowly heated, and at approximately 80C, all paraform a l d e h y d e
dissolved. The contents was slowly distilled, and the tem perature rose slowly over 1-2 hours to 109C . During this tim e, a lot of
C O 2 was evo l v e d , a n d a p p r o x 7 5 m l of form aldehyde-smelling distillate was collected. The solution was concentrated under
vacuum until a lot of solids precipitated, which were filtered off, and the solution was further concentrated, filtered etc until
everything was crystallized. The white solids were placed in 150m l warm MeOH, and filtered. The insoluble portion was
recrystallized from wa ter, to give 40 gram s of a m m onium chloride. The m ethanol solution was evaporated and recrystallized
from m ethanol and washed with acetone, to give a deliquescent crystalline m ass, which was dried in a desiccator over CaCl2, to
give 49 gram s of m ethylam ine hydrochloride (0.72 m ole). Calculated on the two m o l e s o f a m i n e n itrogen put into the
e q u a t i o n , 3 6 % b e c a m e m e t h y l a m ine, and 37% (0.75 m o l e ) b e c a m e a m m onium chloride. The net yield of m ethylam ine is
therefore 58%.
Methylam ine Hydrochloride from Amm o n i u m C h l o r i d e a n d P a r a f o r m a l d e h y d e
27 gram s o f a m m onium chloride, 30 g ram s of paraform a l d e h y d e ( m o l a r r a t i o 1 : 2 ) , a n d 9 0 m l of water were gradua lly heate d.
At 80C a cle ar solution was obtained, and the tem perature was maintained at 10 4C for four hours. Slightly more than one-
third (9.06 grams) of the am monium chloride was recovered, whilst 18.96 gram s o f p u r e m e t h y l a m m o n i u m chloride were
o b t a i n e d . T h i s e q u a l s 8 6 % o f t h e t h e o retical am o u n t . T h e a m ount of dim ethylam monium chloride produced was not
estim ated. It is not suggested from the results of this experiment that paraform a l d e h y d e c a n e c o n o m ically be used on a large
scale with advantage, since, quite apart from the relatively high cost, neither form ic acid nor part of the unchanged aldehyde
can be recovered as by-products.
Methylam ine Hydrochloride from Hexam ethylenetetram i n e ( H M T A )
140 gram s HMTA (1 mole) was slowly dissolved in 400 ml water and 400m l 37% HCl (4 m oles) was added. If the hydrochloric
acid is added directly to the HMTA, a lot of it is lost, as am m o n i u m chloride starts to separate alm o s t i m m ediately. The
m ixture was heated on a tem perature controlled heating plate, and the contents was slowly distilled while the tem perature
slowly rose from 100C to 109 C during 1-2 hours, during which tim e a lo t o f C O 2 w a s e v o l v e d , a n d a p p r o x 7 5 m l o f
form aldehyde-smelling distillate was collected. The solu tion was concentrated under vacuu m until a lot of solids precipitated,
which were filtered off, and the solution was further concentrated, filtered etc until everything was crystallized. The la st crop o f
crystals was very hard to crystallize, an d care m ust be taken not to burn the contents of the flask, it m ust not be allowed to
rise over, say 75C. The white solids were placed in 150m l warm methanol (cheaper than denatured ethanol), and was filtered.
The insoluble portion was recrystallized from water, to give 40 grams of pure am monium chloride, which looked like very large
snowflakes. The methanol solution was evaporated, recrystallized from m ethanol and washed with acetone, to give a
deliquescent crystalline m ass, which was dried in a desiccator over CaC l2.
----------------------------------------------------------------------------------
Am m o n i u m C h l o r i d e i s n o t s o l u b l e i n a l c o h o l .
Methylam ine.hcl is much more soluble in hot alcohol than cold.
Both are soluble in water. Minimizing water aids separation.
Methylam ine.hcl is not soluble in chloroform .
----------------------------------------------------------------------------------
John A shcroft June 13th, 2003, 11:13 PM

Reduction of nitrom ethane with Al/Hg am a l g a m is a che ap, high-yielding, m ostly O TC process for preparing m e t h y l a m i n e .
Mr Cool June 14th, 2003, 10:54 AM

Yeah, that does work well, but m any people here would consider converting MeNO 2 to MeNH2 a crime :).
Also there's the Hofm a n n d e g r a d a t i o n o f a c e t a m ide which I'll add to it, but the ones above seemed like the cheape st, with the
easiest to get chemicals.
MnkyBoy June 19th, 2003, 09:08 AM

The neighbor downstairs claim s that th e following results in exce llent yields:
Place HMTA into a flask with a stirbar on top of a m agnetic stirrer. Slowly add HCl until the HMTA barely disolves. Keep contents
< 25 C . To this over the next say 24hrs with stirring add Zn + HCl (Zn = dust or from pennies) . Filter, distill off the MeAm.
Condense till crystals are percipitated, wash with chloroform to rid di-MeAm .
Y e a h I h e a r d a b o u t a dding Zn/HCl to increase yields. I've heard it mentioned as a catalyst, but ha ve never read a specific
procedure which uses this.

W ouldn't the Zn/HCl be a necessary re agent as a reduction agent, reducing the HMTA to methylam i n e ? B e c a u s e Z n / H C l i s t h e
SOP for reducing organics.

Yes, reducing agent was m y first thought, but I was reading a procedure that IIRC was posted by Rhodium , and at the end it
said something along the lines of "Oh, I forgot the proportions of Zn and HCl? No, I didn't ;)." If it was a reducing agent, then
p r o p o r t i o n s s h o u l d h a v e b e e n m entioned, or at least stated that they were used in excess or whatever. Also I heard "catalyst"
m entioned, but I can't think o f a m e c h a n i s m for its action :confused:.
Form a l d e h y d e or form ic acid are the reducing a g e n t s i n t h e m e t h o d s I m entioned. eg Hyd rolysis of hexam ine produces NH3
a n d C H 2 O i n a 2 : 3 r a tio. They then react in a 1:2 ratio, thus form i n g a m m onium salts from t h e e x c e s s a m m o n i a . O n e C H 2 O
combines with the NH3, the other reduces the interm ediate to form m e t h y l a m i n e a n d f o r m ic acid.
NH4NO 3 + 2 CH2O --> CH3NH3NO3 + HC O O H
This form ic a cid then takes the place of the reducing C H2O in further reactions:
NH4NO 3 + CH2O + HCO OH --> CH3NH3NO 3 + H2O + CO2

a n d I m provised C hemistry > NO acetic anhydride - Archive File
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sim ply RED
Freq uent Poster
Posts: 240
From : HELL
posted 04-28-2001 12:14 PM
--------------------------------------------------------------------------------
C a n s o m e o n e t e l l m e how to m ake pure acetic anhydride from anhydridous acetic acid?
Another easy synthesis will also be appreciated since I can't get the acetic anhydride from my chem suplier.
btw: I know this could have been discu ssed in previous tim e s b u t I can't find it.
c0deblue
Freq uent Poster
Posts: 229
From :
posted 04-28-2001 01:45 PM
--------------------------------------------------------------------------------
L o o k h e r e h t t p : / / r o g u e s c i . o r g / m e g a l o m ania/synth/synthesis1.html#acetanhy
and here http://rhodium .lycaeum.org/chem istry/anhydrides.txt
There'll probably be some question as to why this is in High Explosives though.
[This message has been edited by c0deblue (edited April 28, 2001).]
Lem
New Mem ber
Posts: 3
From : Austin, Tx
Registered: MAY 2001
posted 05-09-2001 03:54 PM
--------------------------------------------------------------------------------
W ell, I know this thread is kinda old, but I just wanted to say, you can use acetic anhydrid e to m a k e t e t - n i t r o m e t h a n e , a n
extrem ely unstable, powerful com p o u n d m ade by dripping acetic anhydride into fum ing nitric acid and distilling.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 05-09-2001 05:41 PM
--------------------------------------------------------------------------------
Actually megalomania's page says tetranitrom ethane is of low sensitivity.. but high sensitivity when not pure!

a n d I m provised C hemistry > A Crazy Idea... (Reactions with NX3)
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MrSamosa June 9th, 2003, 05:16 PM

A crazy idea cam e to me the other day... Normally we think of NX3 com pounds, such as Nitrogen Triiodide as too un stable to
think of and a waste of chem icals to synthesize. For the m ost part, this is in fact true. However, have you ever considered the
potentially powerful halogenating properties of such com p o u n d s ?
Thin k about it... on their violent decom p o s i t i o n , t h e y r e l e a s e h e a t e d H a l o g e n f u m e s . T h e r e f o r e , I s e e a c h e m ical such as NCl3

a s a potential Chlorin a t i n g a g e n t , i f m e a s u r e s a r e t a k e n c a r e t o m i n i m ize its handling and it is only produced as ne e d e d . D o
you suppose that such compounds could be used as substitutes for PCl3 or PI3 in certain reactions?
I can find very little inform ation regard i n g s u c h c o m p o u n d s , a n d m ost of it is from the Anarchist Crapbook. I did find a neat
little site whose author did experim ents on the stabilization of NI3, but had little success. It is for this reason that I am
interested- b e c a u s e n o b o d y h a s d a r e d to try it. It is tha t bit of m ystery that excites me :) .

Hm m m .... isn't there a m etho d in which NCl3 is m ade from AN solution and chlorine gas?
W hat I am imagining is some AN solution, floating over DCM or other dense, inert non-polar. Chlorine is allowed to react with
the AN, NC l 3 f o r m s a n d s i n k s t o t h e b o t t o m of the AN solution, where it meets the DCM and dissolves.
Thus it never has to be handled in the pure form , only as a dilute solution.
jfk June 9th, 2003, 09:41 PM

i s n t P h o s p h o rus very rare and hard to com e by?

SW IM gets R phosphorus from match box sides. Very kewl cause there is about 0 .1g of re d P o n e a c h b o x b u t h e y 1 0 0 b o x e s
= 10g. And how m u c h d o e s a 1 0 p a c k o f m a t c h es cost you? 2 - $3

Inorganic synthesis has a m ethod for producing a dilute solution of NC l3 in organic solvent, I think carbon tet. Its fairly stable
but very slowly evolves phosgene on standing.
Ive also read a few suggestions in the literiture about using NCl3 as a chlorinating agent, m ainly while I was trying to find out
m ore inform ation on it. Its certainly useful, but I failed to see any advan tage over existing chlorinating agents. No specific
reactions were given in what I read, on ly fairly theoretical arguments based on its decomposition. I have the feeling , that if it
were a suitable replacement for phosphous chlorides that it would react rather mo re rapidly with water than it does.
Theres always sulphur chlorides as an alternative. They arnt pleasent to handle, but then neither is NCl3.
drednort June 11th, 2003, 05:07 PM

I dont think they're a good so urce of halogen.
Most of the NX3s are pretty unstable and a bit tricky to use.
But I rem ember that NC l3 can be used in reactions, when dissolved, and when you hydrolyse the product it substitues a NH2
onto a tertiary C-H bond for you. Not g reat yields but otherwise difficult reaction. So, to answer your questio n it is more likely
that they're better for difficult aminations.
MrSamosa June 12th, 2003, 12:59 PM

Yes, NX3 com pounds are indeed tricky to use... But, I'm sure we all like a bit of a dventure- why else would we be at
Roguescience?? ;) .
I like the ide a of it being dissolved in the Dichloromethane, because that is a rea dily obta inable solvent. But what a bout NI3 ?
I n d e e d , t h a t i s e v e n m ore unstable than NCl3, but still - the purpose of m y interest in the se compounds is for their possible
u s e i n H a l o g e n a t i o n s ( s a v e f o r NF3, which is qu ite stable); not just Chlorinations in particu lar.
Could NCl3 o r NI3 perhaps be used in synthesizing Phosphorus Trichloride or Phosphorus Triiodide, respectively? I don't see
m uch of a purpose fo r doing it this way, since Cl2 or I2 could be added d irectly to the Phosphorus instead of the Nitrogen
first...but just out of curiosity :) .

a n d I m provised C hemistry > Freezing water out of weak H202 solutions - Archive File
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phyrelord
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From :
posted 05-17-2001 10:38 PM
--------------------------------------------------------------------------------
I don't know if this has been m e n t i o n e d b e f o r e but I found it interesting. I found this while looking for info on H202 rockets.
you can approach 62 percent pure hydrogen pe roxide.
Can I concentrate H2O 2 m yse lf by freezing?
Yes, you can, but there are has lim its on how m uch water/H2O2 that can be remo v e d b y s i m p l e f r e e z i n g . T h e p r o b l e m is that
at 62% H2O2/H2O solution the peroxide and water freeze together to form an H2O/H2O2 ice. Thus whether you are freezing a
water rich solution or a hydrog en peroxide rich solution the rem aining liquid tends to becom e a 62% solution where both
substances blend and freeze together.
Can I concentrate H2O 2 m yse lf by freezing out the water?
Yes, you can, when H2O 2 is a small percentage of the solution i.e. less than 40%, the ice that forms is mainly water, so that
t h e p e r c e n t a g e o f H 2 O 2 left in solution steadily increases as mo re ice forms. However, som e o f t h e H 2 O 2 f r e e z e s i n t h e i c e
also, so there is a loss that gets worse a s t h e p e r c e n t a g e o f H 2 O 2 a p p r o a c h e s 6 2 % . T h i s i s a u s e f u l a n d e a s y w a y t o
concentrate very weak H2O2 solutions however. Notice will this process really tends to leave any contaminates in the solution.
Can I concentrate H2O 2 m yse lf by freezing out the H2O 2 ?

Yes, you can, but there are has lim its on how m u c h H 2 O 2 c a n b e r e m oved by sim ple freezing. If you start with a 90% or higher
H 2 O 2/H2O solution the ice that form s is almost pure H2O2, however the same limits still apply. As you freeze m ore a n d m o r e
of the H2O2 the percentage of water in solution clim bs, and so does the amount of water that freezes in the ice. Again, the
freezing will balance at 62%.
CragHack
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Posts: 618
From :
posted 05-18-2001 10:32 AM
--------------------------------------------------------------------------------
this has actually been m entioned before, but you provided a VERY usefull peice o f info. W hen we talked ab out it earlier no one
knew the percentage with which your H2O 2 could be frozen too. You said 62%. If this is co rrect then kudos to you. May i ask
where you got your in formation?
------------------
"If you m ust, do it with intelligent people, at least they know how to talk to the cops."
PYRO 500
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Posts: 1465
posted 05-18-2001 04:05 PM
--------------------------------------------------------------------------------
s o m ething that will cause you trouble is that H2O2 freezes right after water so it complicates things.
zaibatsu
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Posts: 407
From : England
posted 05-18-2001 04:10 PM
--------------------------------------------------------------------------------
W hy (other than rockets) would you want to go to the trouble of increasing the % of H202?
phyrelord
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Posts: 135
From :
posted 05-18-2001 04:14 PM
--------------------------------------------------------------------------------
I was searching a site on H2O2 rockets, it was som e site on yahoo. It had a lot of info and seemed pretty acurate so I would
trust it. I would treat the process a lot like distillinging by keeping the tem perature very close to freezing point of water but not
high enough to freeze the H2O2. If I'm right I think 62 percent would get you a lot higher yield than 3 or 6 percent when used
in m a k i n g A P .
zaibatsu
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Posts: 407
From : England
posted 05-18-2001 04:23 PM
--------------------------------------------------------------------------------
I t w o u l d I F y o u h a d s a y 1 0 0 m l 3 % h 2 0 2 a n d 1 0 0 m l 62%. But yo u are just rem oving the water, leaving you with the sam e
a m ount of H202, just less water. Say you had 100ml 3% H202, and you concentrated that to 62%. You would be left with about
4.8ml of 62% H202 (if my calculations are correct). In the first case you have 3ml of pure H202, and in the second case you
have 3ml pure H202. The only thing that differs is the amount o f water.
------------------
Visit m e at www.surf.to/eliteforum
FadeToBlackened
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Posts: 201
From : Hell
posted 05-18-2001 05:07 PM
--------------------------------------------------------------------------------
A while back there was a post (i think there was anyway) about boiling a weak solution so m uch and getting about 1 2 % H 2 O 2 .
Does anyone have any info on this? I haven't been able to find the post...
blackadder
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Posts: 313
From : L o n d o n
posted 05-18-2001 06:55 PM
--------------------------------------------------------------------------------
At m y school they have som e lab concentration H2O 2 which I would like to "borrow".
Does anyone know what perce ntage of that would be H2O2? It has a "corrosive" sign on it, and it's inside a brown bottle (to
prevent deco mpostion of the hydrogen peroxide upon contact with light). Since it has a "corrosive" sign on it, I'm thinking it's
pretty high concentration of H2O2.
CodeMason
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From : Your Nightmares
posted 05-19-2001 08:59 PM
--------------------------------------------------------------------------------
It is alm ost certainly 30% (lab grade), but perhaps they needed some really conc. H2O2 for som e special purpose...
drshneb June 13th, 2003, 04:25 AM

H 2 O 2 with a concentration anything above 8% is counted as corrosive

a n d I m provised C hemistry > Fe2O 3
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mongo blongo June 12th, 2003, 10:33 AM

Found a site which shows how Fe2O 3 is m ade in industry for pigments. It also shows why Fe2O3 is a different colour every tim e
it is prepared which is som e t h i n g t h a t I h a v e b e e n p o n d e r i n g f o r s o m e tim e now.
http://clutch.open.ac.uk/schools/deanshanger99/pages/ox_processvid.html

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > White Phosphorus -
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nbk2000
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Posts: 1096
From: Guess
posted 03-16-2001 01:30 PM
--------------------------------------------------------------------------------
To Obtain Phosphorus: Ground bone-ash, 12 parts; water, 24 parts; mix to a pap in a large tub, and add in a slender stream (still stirring) sulfuric acid, 8 parts; work w ell
together, adding more water if required; in 24 hours thin with water, agitate well , and, if convenient, heat the mixture in a leaden pan, and as soon as the paste has lost its
gramular charracter, transfer it into a series of tall casks; largely dilute w ith water; and, after settling, decant the clear portion; wash the residue well w ith water, mix the clear
liquids, and evaporate in a copper or lead pan, till the calcarious deposit (gypsum) becomes considerable, then cool, decant the clear, and drain the sediment on a filter;
evaporate the clear liquid to the consistence of honey (say to 4 parts), add 1 part of pow dered charcoal, and evaporate to dryness in an iron pan or till the bottom of the latter
becomes red hot; the dry mixture, when cold, is put into earthen retorts w ell covered with luting and property dried, and heat is applied sideways rather than at the bottom, by
means of an air furnace. The beak of the retort is connected with a copper tube, the other end of which is made to dip about 1/4 inch beneath the surface of lukewarm water
placed in a trough or wide-mouthed bottle. The distilled product is purified by squeezing it through chamois leather under warm w ater, and is then moulded for sale by melting it
under water heated to about 145 F, plunging the wider end of a slightly tapering but straight glass tube. into the water, sucking this up to the top of the glass, so as to warm
and w et it, next immersing the end into the liquid phosphorus, and sucking it up to any desired height. The bottom of the tube is now closed with the finger, it is w ithdrawn, and
transferred to a pan of cold w ater to congeal the phosphorus, which will then commonly fall out, or may be easily be expelled by pressure w ith a piece of wire. Keep it in places
where neither light nor heat has access, in phials filled with cold water which has been boiled to expel all air, and enclose the phials in opaque cases.
------------------
Agent Blak
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Posts: 766
From: Sk. Canada
posted 03-17-2001 11:26 AM
--------------------------------------------------------------------------------
Exactly what are the uses of white/yellow Phosphorus(P)?
------------------
Bandit
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From: U.K.
posted 03-17-2001 12:29 PM
--------------------------------------------------------------------------------
I dont know about yellow , but white is used in grenades. It lights with contact with air. Tracer round use this as well.
Bandit
c0deblue
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From:
posted 03-17-2001 01:54 PM
--------------------------------------------------------------------------------
Just be very careful making/handling this stuff - in addition to its obvious dangers it's highly toxic. Despite strict regulation of white phosphorous production in 1906, munitions
workers in both wars suffered the effects of chronic exposure such as phosphonecrosis (phossy jaw), and acute exposure effects that included liver and kidney damage from
inhalation and skin absorption. The fatal dose for humans is ridiculously small - on the order of 15 to 100 mg.
http://ww w.epa.gov/ttn/uatw/hlthef/whitepho.html
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 03-21-2001 01:47 PM
--------------------------------------------------------------------------------
I Don't have earthen retorts, but say i did want to make this what is luting?
nbk2000
Moderator
Posts: 1096
From: Guess
posted 03-21-2001 09:19 PM
--------------------------------------------------------------------------------
Luting is a fireproof material used to seal the gaps between the retort and the condenser. The material used to seal fireplace cracks would work well.
Steel pipes would be suitable replacements for earthen retorts.
WP would be excellent for breaking contact with LEOs. Since the army WP grenade has a radius of more than 20 yards, and WP burns down into the flesh, is highly toxic, and
provides excellent screening smoke, a WP grenade w ould be an ideal urban criminal weapon.
------------------
Go here to dow nload the NBK2000 videos.
SATANIC
Frequent Poster
Posts: 237
From: australia
posted 03-21-2001 11:38 PM
--------------------------------------------------------------------------------
is bone ash just ash from burning bone?
what would the WP be mixed with in a grenade? does it really explode in contact with air?
A WP grenade would really kick ass. from pics i have seen, it would really kill. even ruin night vision from a distance aw ay. really a good screening / getaw ay weapon.
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 03-21-2001 11:44 PM
--------------------------------------------------------------------------------
Bone ash is 'calcined bone' and the way i understand it is basically destructive distillation in the open. Roasting it like a mineral kinda. I read WP ingites @ 10-15 degrees above
room temp. There still the chance that it w ould ignite below that though.
c0deblue
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Posts: 229
From:
posted 03-22-2001 12:22 AM
--------------------------------------------------------------------------------
A useful reference on White Phosphorous properties: http://chppm-www .apgea.army.mil/dts/docs/detwp.pdf
According to this, WP ignites spontaneously w ith air *or* at 30 degrees C.
nbk2000
Moderator
Posts: 1096
From: Guess
posted 03-22-2001 06:21 PM
--------------------------------------------------------------------------------
Here's a picture showing the results of "phossy jaw ".
------------------
[This message has been edited by nbk2000 (edited March 22, 2001).]
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 03-22-2001 10:06 PM
--------------------------------------------------------------------------------
ouch.. yuck..i mean fuck..that sucks
Donutty
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Posts: 228
From: UK
posted 03-23-2001 01:32 PM
--------------------------------------------------------------------------------
This is probably of no use, but:
Today I found a bottle of 30% Phosphoric Acid... any use??
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 03-23-2001 06:33 PM
--------------------------------------------------------------------------------
Well, don't quote me on this but you might be able to react it w/ a base and get a phosphate, and then use the phosphate *somewhere* in the process above.
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 03-24-2001 12:38 PM
--------------------------------------------------------------------------------
May in an acid Cat. rx
FadeToBlackened
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Posts: 201
From: Hell
posted 03-24-2001 10:05 PM
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Agent Blak: w hat does that mean?
CragHack
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From:
posted 03-24-2001 10:23 PM
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i.e. acid catalyzed reaction. like w hen you make AP
------------------
...
SofaKing
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From: YEAH RIGHT !!
posted 03-25-2001 01:07 AM
--------------------------------------------------------------------------------
There are other self-igniting compounds around. One I have heard mentioned is diethyl-zinc does anyone have info on that ?
Rhadon
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Posts: 95
From: Germany
posted 03-26-2001 08:06 AM
--------------------------------------------------------------------------------
I found sth. on diethyl zinc:
Prepd by the interaction of zinc and ethyl iodide
from zinc and ethyl bromide / ethyl iodide;
Properties: Mobile liquid. Stable in sealed tube and carbon dioxide. Ignites in air, burns w ith a blue flame, giving off a peculiar, garlic-like odor. Miscible with ether, petroleum
ether, benzene, other hydrocarbons.
Use: In organic synthesis; in preservation on archival pape.
SMAG 12B/E5
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Posts: 61
From:
posted 03-26-2001 11:39 PM
--------------------------------------------------------------------------------
White phosphorus and yellow phosphorus are the same. It is not mixed w ith anything in most rounds. It is sometimes submerged in a petroleum liquid. The hermatically-sealed
rounds are exploded by a burster charge, usually centrally located in the device. Don't allow air to contact this material. WP can "mess up your whole day".
WP can be converted to red phosphorus, for igniters, by sustained heating in a closed vessel for (?) hours at (?) degrees.
FadeToBlackened
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Posts: 201
From: Hell
posted 04-30-2001 09:22 PM
--------------------------------------------------------------------------------
I have seen another method for making WP that involves heating tricalcium phosphate (main in gredient of bone ash) with carbon and silica. Is the sulfuric acid part just used to
purify the phosphate? What purpose does silica serve? Is it a sort of flux or something to reduce the temperature needed?
nbk2000
Moderator
Posts: 1096
From: Guess
posted 05-02-2001 10:10 AM
--------------------------------------------------------------------------------
The sulfuric acid is used to remove all the organic and acid soluble material from the bones. If you're using bone ash than you don't need to use the acid step.
The silica is used to bind the calcium into a non-volatile silicate, freeing the phosphorus. I believe it also lowers the reaction temperature too.
------------------
Alchemist
Frequent Poster
Posts: 211
posted 05-11-2001 11:08 AM
--------------------------------------------------------------------------------
Hello NBK2000,
Have you made WP using the method you posted? If so w hat was the yield. Has anyone else tried it. Also I have seen many types of Phosphate fertilizers (example; Calcium
Phosphate).Will any of these w ork if they are rich in Phosphate?
P.S.,White phosphorus is metastable and slow ly changes to a stable form, red phosporus,in the presence of light or upon heating. Red phosphorus is far more stable than the
white form. It does not catch fire in air at temperatures below 240C whereas white phosphorus ignites at about 40C. Red phosphorus cannot be converted into w hite
phosphorus except by vaporizing it.
Thanks.......................................
------------------
nbk2000
Moderator
Posts: 1096
From: Guess
posted 05-11-2001 01:25 PM
--------------------------------------------------------------------------------
No I haven't. I found this process in an old book about how to do just about everything yourself from the 1800s.
Calcium or ammonium phosphate will work in the process quite w ell. The ammonium salt is prefered because of the low er temperatures needed to break it up into phosphorus.

The sulphuric acid steps arnt purifying the calcium phosphate, they are converting it into phosphoric acid. Strongly heating phosphoric acid drives off water, and leaves a
polymeric metaphosphoric acid, doing this while mixed w ith carbon is a very cunning idea. The metaphosphoric/carbon mixture will produce phosphorous at a lower temperature
than the calcium phosphate/carbon/silica process that requires an arc furnace.
Phosphoric acid can be used in the add carbon and bake step directly, so can ammonium phosphate, as this loses ammonia and water to produce metaphosphate under the
same conditions. 'Distill' is a bit of an understatement in moden terms, some of the references I have on this process speak of the rhetort being heated to 'w hiteness' to get the
reaction to run the reaction.
Myrol October 9th, 2004, 12:09 PM

Well, some minutes ago I made some white Phosphorous...with nearly zero yield :( I put some red P into a 180x18mm Test tube around 2g and plugged the End of the tube
with a paperplug (he w as 4cm far from the P away.)
So I started to heat that stuff......it worked w ell the red P vaporized into a yellow smoke and condensed inside the tube to give yellow w axy like P. The Heat was hold on till I
got a bad surprise......I remind a disturbing odor like garlic and saw some fumes coming out of the tube and three secs later...WOOOMM....
a dull WHOOFF beside my right Ear. The vaporized white P ignited spontaneusly to make a fucking FAE beside me!! I felt a pressure in my Ear it was not to loud but loud
enough to scare the Neighbour running on his Balcony :D well, my ear is now ok but again....this is to strange for me :o
Making white P this w ay DONT works with satisfactory results.....The risk of a sudden fire or like me a FAE is VERY strong. Also white P is extremly Toxic, its very hazardous to
handle it but I LOVE it due to its fantastic shining and the low flashpoint. So, has someone a good Idea how to make white P out of the Red one without vaporizing it out of the
Apparatus and being poisoned trough the toxic fumes.
How Poisonus is white P really? Orally very but via inhalation? I dont know, but its everytime a great risk to make him, better be blown into Fishfood as to decay slowly within
and die as a human w reck. (IMO)
You used a PAPER PLUG?!
And then you wonder why you failed. :rolleyes:
I did it once using a flame-sealed length of pyrex tubing. One end was heated, the other not.
I would use w ater to keep teh WP end well chilled, so there'd be little pressure buildup from the heating of the RP end.
Myrol October 24th, 2004, 09:36 AM

Well, Paper can be wasted, it's cheap. An expensive sublimation apparatus should be good cleaned out after use. No one would trash him. WP is a w hore in cleaning glassw are.
Its toxic volatile and stinks like garlic. I prefer to dump the contaminated Test Tube after making him because due to the toxicity it's not worth the risk of cleaning out.....Paper
is just a cheap choice to keep the Tube *a little* Airtight. Due this stupid failure, I never make WP ever again.
FU TI October 25th, 2004, 04:19 PM

Use copper-sufate solution to neutalize its toxicity to clean labware!
Rest of the written here is true.
SmoLL June 18th, 2006, 01:54 PM

Hello all, i found some to the process make some white Phosphorous.
Red phosphorus is slight hycroscopic, red to dark red crumbs, sensitive againt friction, much more stable than the white form, pulverization in airtight ball-mills. Red phosphorus
can be converted into white phosphorus in a sublimation apparatus.
White phosphorus is unstable on the open air, most reactive with oxygen, similar like white w ax scales, very toxic, stabel in airtight glas bottles at low temperatures. White
phosphorus can be converted into red phosphorus by a burning process.
Process making white phosphorus:

Put some powdered red phosphorus into a 500 ml distilling flask, connect the beaker to a simple condenser. Connect the condenser to a 500 ml receiving flask, set the distilling
flask to a hotplate and put the receiving flask to a salt ice bad. The red phosphorus is careful vaporized and a little icy air is pumped into the receiving flask. This should form
some crude w hite phosphorus on the bottom of the flask.
++ +++
A perfect example of n00b copy/paste
What happens when vaporized white phosphorous is exposed to a stream of oxygen in the confines of a flask?
:rolleyes:
NBK
a_bab June 19th, 2006, 06:18 PM

icy air... now that's something [stupid].
Normaly CO2 it's used, and it works even if not being "icy".

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > ammonia and bleach
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phyrelord
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From:
posted 04-22-2001 10:58 PM
--------------------------------------------------------------------------------
what gas forms when you mix them together? I know it's a white cloud and it makes you sick as shit when you breath a little bit of it. Secondly is there any way of
concentrating it or making it more potent. I was thinking of two ziploc bags, one filled with bleach and the other with ammonia, in a duffel bag would make a nice cloud when
slammed and be inconspicuous, not to mention fuck people up. Any comments or ideas
BoB-
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Posts: 679
From:
posted 04-23-2001 02:11 AM
--------------------------------------------------------------------------------
Chlorine gas, nasty smell, and as little as 3.5ppm can be smelled by a human, it irritates the mucous membranes and makes it hard to breath, it can cause brain damage and
1000ppm is fatal.
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 04-23-2001 05:28 PM
--------------------------------------------------------------------------------
White? I thought chlorine was green. A post a while back said that white clouds produced by (something i cant remember) is ammonium chloride vapor. It also makes
hydrazine according to:
NaOCl + 2NH3 > N2H4 + H2O + NaCl
...but that takes a little work...
green beret
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Posts: 101
From: Australia
posted 04-24-2001 08:52 AM
--------------------------------------------------------------------------------
I also thought chlorine gas was green??
FadeToBlackened
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Posts: 201
From: Hell
posted 04-24-2001 05:24 PM
--------------------------------------------------------------------------------
Yep. It isnt chlorine, its ammonium chloride. blackadder said this in the HTH+ Naphtha post a while back:
"Because of its high chlorine content, loads of chlorine (LOADS!!!) will be given off when you mix it with an acid or ammonium hydroxide (household ammonia)
sorry if that sounded kewl, I just had to say it.
I mixed a HTH tablet from the pool with ammonium hydroxide, and absolutely tons of Cl was given off, it was like everywhere!
Oh yeah, and I always get thick white chlorine, it is never a little greenish, like it's supposed to be. Why?"
...then nbk2000 responded with:
"Blackadder, I'd imagine that the chlorine is reacting with the ammonia to form ammonium chloride, which looks like white smoke.
Use hydrochloric acid with HTH and you'll get the green gas."
They were talking about HTH, which is Ca(OCl)2, and bleach is NaOCl.
blackadder
Frequent Poster
Posts: 313
From: London
posted 04-24-2001 05:43 PM
--------------------------------------------------------------------------------
Cl2 IS a pale greeny colour, but since it is heavier than air, it goes back into the solution and forms NH4Cl, ammonium chloride. Which is white! Which isn't as heavy as Cl2,
and thus moves around in the air and this is the gas you see.
What we're doing is the following:
NH4OH + Substance* ==> Ammonium compound + Cl2

* When I said "substance" that means sodium hypochlorite, calcium hypochlorite, etc.
The above is the initial reaction, then later we get:
NH4OH + Cl2 ==> NH4Cl + other irrelavant shit
Now, that's because (I think) some of the unreacted NH4OH is reacting with the Cl2 and it form NH4Cl.
So, to prevent this shit from happening, we do the following:
Hcl + substance* ==> Cl2 + irrelavant compounds

There ya go, just replace the NH4OH with HCl and you won't get the NH4Cl coming out.
[This message has been edited by blackadder (edited April 25, 2001).]
BoB-
Frequent Poster
Posts: 679
From:
posted 04-24-2001 11:55 PM
--------------------------------------------------------------------------------
Blackadder:
"Hcl + substance* ==> Cl2 + irrelavant compounds"
"Substance" could be MnO2:
MnO2 + 4HCl -> MnCl2 + Cl2 + 2H2O
The same process used by Scheele when discovering Chlorine.
I still cant figure out how you guys write the formula's like that, HTML?
nbk2000
Moderator
Posts: 1096
From: Guess
posted 04-25-2001 01:04 AM
--------------------------------------------------------------------------------
I tried the HTH and ammonia thing today and got white fumes too.
From the smell of it, it didn't seem too much like ammonia so I'm thinking ammonium chloride. But I'll have to test it with muriatic acid. If I get additional "smoke" than there's
free ammonia.
Did you guys know that free ammonia also "smokes" in air?
------------------
Ezikiel
Frequent Poster
Posts: 66
From: New Delhi, India
posted 05-17-2001 09:54 PM
--------------------------------------------------------------------------------
Hey I had tried it too but I used (NH4)2CO3 instead of NH4OH. I got Quite dense white fumes and when I sniffed a sample of the gas I didn't find it as pungent as Cl2 and
NH4Cl vapours aren't pungent. And the solution left behind was somewhat like a dirty greenish yellow (similar to Nitrobenzene). the reaction was very vigourous and bubbly
with no white fumes in the bubbles but the fumes seemed to from on contact with air. I could still smell NH3, after I blew off all the fumes, when I sniffed it. I added a lot of
bleach (I didn't achieve the "no more reaction" state) and it also starts to heat up. That's when I quit adding more bleach.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Chloroacetone:
warm or cold? - Archive File
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FadeToBlackened
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Posts: 201
From: Hell
posted 04-29-2001 08:38 PM
--------------------------------------------------------------------------------
To anyone who knows about making it, does being warm or cold favor a more efficient reaction?
Also does anyone know how to remove the methyl (CH3) group and replace it with a benzene ring to make chloroacetophenone?
CH3-CO-CH2Cl > C6H5-CO-CH2Cl.
I have seen chloroacetone listed as 'vesicant, highly destructive to mucus membranes, and possible mutagen'. The only information i could find about chloroacetophenone was
actually about dibromoacetophenone. Thats the closest info i have found, and it sounds about as bad. Which would be less harmful in terms of mucus membrane destruction
and mutagenic properties?
I have just learned that all of these compounds can cause pulmonary edema. Would diluting them (greatly) eliminate this risk?
Mr Cool
Frequent Poster
Posts: 991
posted 04-30-2001 02:13 PM
--------------------------------------------------------------------------------
I wouldn't mess with any form of chemical weapons, except things like lacrimants. They're almost all carcinogenic and cause birth defects.
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 04-30-2001 05:06 PM
--------------------------------------------------------------------------------
Yes, I know that. The above mentioned chemicals are lachrymators/lachrymants, whatever you want to call them. Chloroacetophenone is CN type tear gas (used to be the
most used. Now CS is). Chloroacetone is similar but has some quite bad side effects. I assume you would use the chloroacetone in making the chloroacetophenone.
-I now see little or no point in making the chloroacetone into chloroacetophenone, as they are both about as bad as each other. CN (latter) is a co-carcinogen (cancer
promoter). CS tear gas (which i believe is now in use) IS a carcinogen. They are all vesicants.
Hmm..still they are interesting
nbk2000
Moderator
Posts: 1096
From: Guess
posted 05-02-2001 10:13 AM
--------------------------------------------------------------------------------
Chloroacetone is in no way used for making CN (chloroacetophenone).
The NBK2000 PDF has a section on making chloroacetone that you may want to check out.
And chloracetone is very corrosive to skin, just like any strong acid.
------------------
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
posted 05-02-2001 06:36 PM
--------------------------------------------------------------------------------
Yeah I have your PDF and it rocks. I just thought MAYBE chloroacetone could be made into CN. Its kinda hard finding CW synthesis on the net unless you know where to look
(which I don't).

a n d I m provised C hemistry > Extracting KNO3 from Sucro se/KNO3 m ixture? - Archive File
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megalomania June 15th, 2003, 11:34 AM

John456
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Posts: 105
From :
posted 05-04-2001 08:42 PM
--------------------------------------------------------------------------------
Hey,
I ' v e e x h a u s t e d m y K N O 3 s u p p l y a n d c a n t s e e m to get any m ore , a n d i h a v e s o m e m elted sucrose with KNO3 stirred in laying
around. I was wondering if anyone knew of any solvent that dissolves sugar but n ot kno3, or vice versa, or maybe a m ethod of
extraction? By the way: I know this sounds like something that would be in another topic in search, but i spent a good 20
m inutes searching around and found nothing. -John
Agent Blak
Freq uent Poster
Posts: 766
posted 05-05-2001 02:46 AM
--------------------------------------------------------------------------------
It will be a pain do do this because both com pounds are quite easily disolved. you could try to disolves the mix in H20 then
chill it until it starts to precipitate out you. you will have to find out which is m ore sol. than th other. I think it will be alm ost
im p o s i b l e .
None-the-less it will b e a tedious job and i don't envy you. good luck
------------------
"...T here Will Be No
Stand O ff At High Noon
... Shoot'em I n T h e B a c k
And, Shoot'em I n T h e D a r k "
John456
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Posts: 105
From :
posted 05-05-2001 08:29 AM
--------------------------------------------------------------------------------
yes, im hoping they would pre cipitate at different tem peratures or the crystals of each will form in different sizes. Another
question, i am going to be using the KNO3 in the production of nitric acid , will the sugar affect anything if i just use the m ixture
f o r m a k i n g n itric? Thanks. -John
Anthony
Moderator
Posts: 2306
From : England
posted 05-05-2001 10:35 AM
--------------------------------------------------------------------------------
I f y o u ' r e g o i n g t o m a k e H N O 3 with H2SO4 + nitrate, you'd end up nitrating the sugar.

a n d I m provised C hemistry > NC FROM PAINT LACQUER - Archive File
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YTS
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Posts: 61
From :
posted 05-06-2001 04:22 AM
--------------------------------------------------------------------------------
W hen i was a aprentice m echanic i found some paint lacquar so thought i would try to extract the NC so i added petrol to it .
the solution had what looked like cotton wool floating in it but when i fish ed it out it was like putty & when d ry it burnt with a
black smoke so i gave up on it this was 15 years ago.But just recently when i found out about ap ping ball putty i fo ught it
could be used for that so i tried it & it works & it only takes abou t 10 m inutes to gel with acetone.I thought they use d 1 2 %
nitrogen content in cellulose p aint lacquer & if it is why does it only burn or is it because there is something else i need to
r e m o v e f r o m it if any one kno ws it could be a usefull so urse of NC but if it is only low grad e celliod it m a k e s a g o o d p u t t y
quickly.The putty i m a d e f r o m it was the size of a m arble i put it in a bean can then poured a mix of coarse potasiu m chlora te
and icing sugar on top of it. it made nice fountain & when it got to the putty there was massive bang a lot louder than i
e x p e c t e d f r o m such a sm all am ount of putty & know remains of the tin. Thats why i was wondering if it was high % NC & i hadnt
purified it enough. has any body heard of this being done before & if so how was it done CHEERS ps the lacquer is very cheap
in 5 litres cheaper than ping p ong balls by the way i only dream t this

a n d I m provised C hemistry > Iron oxide problem s - Archive File
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A-BOMB
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Posts: 137
From : wouldn't you like to know
posted 05-15-2001 09:23 AM
--------------------------------------------------------------------------------
I'm having trouble with m a k i n g i r o n o x i d e
for therm ite. I m ake it by taking a ac transform er and put two pieces of steel wool
on the leads. Then put them in a salt water solution and leave it sit for a week and filter it out. Is there any other way to m a k e
it, m aybe easier or one that m a k e m o r e p r o d u c t . ( m y way produces about 8 tablespoons)
------------------
live by the bom b
die by the bomb
Alchem ist
Freq uent Poster
Posts: 211
posted 05-15-2001 10:19 AM
--------------------------------------------------------------------------------
Hello A-BO MB,
If ya live in the USA look for a ceramics supply shop in your area. They should se l l b o t h r e d a n d b l a c k I r o n O x i d e a t a r o u n d a
$1.00 or so a pound.
P.S., W here are ya getting your Aluminum?
------------------
DarkAngel
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Posts: 592
From : ?
posted 05-15-2001 02:30 PM
--------------------------------------------------------------------------------
I live in Europe and i bought a kilo Iron Oxide in a pottery shop the guy thought i whas crazy and keep saying to me that only
a few gram s is m o r e t h a n e n o u g h
------------------
DarkAngel
For explosives and stuff go to Section1 http://www.section1.f2s.com And http://run.to/section1

s e n d t o s e c t i o n 1 @ h o t m ail.com
sealsix6
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Posts: 154
From : NYC ,NYC,USA
posted 05-15-2001 05:09 PM
--------------------------------------------------------------------------------
what is it used for coloring in the pots?
Foodos
Freq uent Poster
Posts: 210
From :
posted 05-15-2001 05:36 PM
--------------------------------------------------------------------------------
yeah, iron oxide is used to 'stain' the pots, they take a color (like red = red) before you fire them , (high te mpuratures to
m a k e t h e p o t hard, rather the n clay), after you fire ride-iron oxide it norm ally tak es a blue-ish color, due to the iron (m y
teacher said).
Alchem ist
Freq uent Poster
Posts: 211
posted 05-15-2001 06:03 PM
--------------------------------------------------------------------------------
Hi gang,
Do a search on Therm ite! There a lot here on Oxides to use and etc..
------------------
A-BOMB
Freq uent Poster
Posts: 137
From : wouldn't you like to know
posted 05-15-2001 07:05 PM
--------------------------------------------------------------------------------
W ell thanx, but I'll stay with the tried and true oxidisers, and any other ideas?
PS: alchemist I use b ars of AL ground down,and the bars are m a d e f r o m m e l t e d p o p c a n s .
jin
Freq uent Poster
Posts: 111
From : u k
posted 05-15-2001 09:51 PM
--------------------------------------------------------------------------------
you can just set fire to the ste el wool and i think you wo uld get black iron oxide a lot quicker than electrolysis.
SATANIC
Freq uent Poster
Posts: 237
From : austra lia
posted 05-16-2001 02:47 AM
--------------------------------------------------------------------------------
i had some steel wool that got wet, leaving a crumbling pile of red iron oxide. People have said that this is actually a
d a n g e r o u s m ix of oxides and hydroxides, but is this really the case? I'd expect that if it was washed with water it wo u l d o x i d i s e
any rem aining particles. (it wa s alm ost flour consistency)
BoB-
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Posts: 679
From :
posted 05-16-2001 03:20 AM
--------------------------------------------------------------------------------
DC power should be used in electrolysis
Alchem ist
Freq uent Poster
Posts: 211
posted 05-16-2001 10:56 AM
--------------------------------------------------------------------------------
Hello,
Bob is correct, you ne e d D . C . n o t A . C . t o m a k e i r o n o x i d e . S O R RY I missed that! I use a old computer power supply and it
works great.
Arthis June 15th, 2003, 12:21 PM

Does that m ethod work well ? I mean how long do you have to let the electrolisys go on with a 6 V - 400 mA to get, say 100 g
iron oxyde ? Because A-Bomb had to let it for very long, though I know this is because of the AC transformer...
You put 2 iro n electro lyte ?
Btw, I'm not sure but the voltage shouldn't change anything as long it's higher that the redox value, right ?
2 Fe + 3 H2O --> Fe2O3 + 3 H2 I think.
frogfot June 15th, 2003, 05:56 PM

Theres required 960Ah to dissolve 1 kg iron, couple percents of power will be lost as heat.
yt2095 August 4th, 2003, 07:33 AM

if yo u look in an electronics hobby catalogue, you`ll see ferric ch loride crystals sold in bags or plastic jars quite chea p as well!
dissolve these crystals in wate r, add some caustic soda, still well and wait.
filter this and disgard the liquid, wash in clean water the n allow the iron h ydroxide to dry and powder it, hea t it on a cooker in
an iron pot o r on a tin lid, until there is a color change.
there`s your pure and alm ost atom ised iron ox ide.
it only costs pocket change to make quite large am ounts as well :)
blindreeper August 4th, 2003, 08:36 AM

Frog fot has a very nice way of preparin g .rust (http://www.geocities.com/frogfot/synthesis.html#rust) . He presents the
electrolitical m ethod and iron + HCl m ethod. Personally I have I tried the iron + HCl m ethod with p leasing results but why
bother when (if your aussie) can buy 1kg for $10 at you r local bunnings for cem e n t d y e .
yt2095 August 4th, 2003, 08:44 AM

Blindreaper,
sure I`m in total agreement, with rega rds to his method, I in fact use a sim ilar m ethod when I extract m etals from t h e s e a .
but if you can already BUY the ferric ch loride ready made for only pocket change, it allows you keep your HCl for other
purposes :)
as for the cem ent coloration, fair play to you :) some m a y n o t b e a b l e t o g e t t h a t o u t s i d e O z ?

whereas Electronics and PCB m aufacture is worldwide :)
frogfot A ugus t 4t h, 2003, 05: 10 PM

For som e reason, several electronics supplyers here, carry only sodium persulfate PCB etchants (SP?). Don't have a clue why
they banned iron chloride.. it sure would be the fastest way to ru st :)
GibboNet August 8th, 2003, 04:51 AM

Here they ha ve Iron Chloride, but the price is u nbelieveably huge, I wouldn't pay it. $18.95 for 500ml of 42% Ferric Chloride
(by weight) It sounds cheaper to buy from suppliers, as crystals.
I finally found the tubs of oxide at bunnings, I will be purchasing there whenever I need Iron O x i d e .
There is also a method involving a large bucket, starting with Iron Sulphate, which I believe NBK originally posted.
Tuatara August 8th, 2003, 06:00 AM

Frog fot, I doubt the ferric chloride has been banned. It's just that am m o n i u m p e r s u l p h a t e is m uch cleaner to use - it doesn't
stain everyth ing yellow, and the waste from pcb etching is a m i x o f a m m o n i u m a n d c o p p e r s u l p h a t e s , w h i c h a l s o d o n ' t l e a v e
nasty stains.
It re ally should be po ssible to buy iron oxide anywhere on the planet - either for colouring concrete or for colouring ceramic
g l a z e s . r e m e m b e r i t a l s o g o e s b y t h e n a m e Bu rnt Um b e r I I R C

a n d I m provised C hemistry > generating chlorine gas - Archive File
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Psychedelic Physicist
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Posts: 5
From : Austra lia
posted 05-16-2001 05:48 AM
--------------------------------------------------------------------------------
Hi,I was thinking if you m i x h o u s e h o l d a m monia with a bleach would that m a k e c h l o r i n e g a s ?
Thanks for your help. PP
CodeMason
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Posts: 383
posted 05-16-2001 07:09 AM
--------------------------------------------------------------------------------
Y o u s h o u l d h a v e d o n e a s e a r c h , y o u K e W l n e w b i e . T h i s h a s b e e n d i s c u s s e d n u m erous tim e s b e f o r e .
Anyway, yes it will, bu t all chlorine gas produced will readily be transform e d i n t o a m m o n i u m chloride, which will blow away as a
white dust that appears to be a gas. Cl2 is a pale green.
S o i n s t e a d o f a m m onia, use hydrochlo ric acid, com monly called pool or "m uriatic" acid, available at all good hardware stores.
Cl2 is extrem ely toxic and an irritant.
New Mem ber
Posts: 5
From : Austra lia
posted 05-17-2001 02:16 AM
--------------------------------------------------------------------------------
I'm not KeWl i hate that shit, but i am a new which everyone has to be at som e p oint since everything has to START
s o m ewhere. I don't even plan on making the stuff i just wanted to know of the procces.
Thanks.PP.
Cipolla
New Mem ber
Posts: 37
From :
posted 05-17-2001 07:31 AM
--------------------------------------------------------------------------------
when you m ix bleach with am m onia yo u'll get fine Hydrazine, be ing very toxic...
You can generate chlorine by m ixing the bleach with citric acid or so. The better ways are to m ix KMnO4 with HCl solution or to
put KClO3 or NaClO3 into HCl!
Bitter
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posted 05-17-2001 01:21 PM
--------------------------------------------------------------------------------
Erm , Cipolla, m ixing chlorates with HCl is a no-no. It generates chlorine dioxide (very explosive, very sensitive and very
dangerous).
FadeToBlackened
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Posts: 201
From : Hell
posted 05-17-2001 05:07 PM
--------------------------------------------------------------------------------
Philou Zrealone once made a post which described adding HCl to a chlorate to m ake chloric acid, which was then heated to
m ake perchloric acid.
Bitter
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Posts: 290
posted 05-18-2001 01:15 PM
--------------------------------------------------------------------------------
Yes, and when heated, the m ixture gives off some ClO2 gas.
Read the bottom of this page :
http://www.geocities.com/CapeCanaveral/Cam p u s / 5 3 6 1 /chlorate/destroy.html
[This message has been edited by Bitter (edited May 18, 2001).]
firebreether
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From :
posted 05-18-2001 02:38 PM
--------------------------------------------------------------------------------
The easiest way to make Cl2 gas would be to electrolise a solution of NaCl. You would have the electrodes under different
outlets, so you could collect the Cl2 at one part in a baloon or som ething, then the H2 at another spot.
New Mem ber
Posts: 5
From : Austra lia
posted 05-18-2001 08:50 PM
--------------------------------------------------------------------------------
Thanks for all of that. PP.
blackadder
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From : L o n d o n
posted 05-19-2001 06:42 PM
--------------------------------------------------------------------------------
U m m , C l O 2 e x p l o d e s o n f o r m ation, that's why when you add HC l to KClO 3, ClO 2 is form ed, and burns, and that is what is
happening when you see the burning.
I m a d e a b i g f a t p o s t o n t h e t r o u b l e s o f t h e u n reacted NH4O H reacting with the Cl to form NH4Cl.
Cipolla
New Mem ber
Posts: 37
From :
posted 05-19-2001 07:10 PM
--------------------------------------------------------------------------------
I've tried mixing Chlorate with HCl and what I got was surely no C lO2. Even thoug h t h e F l a s k e x p l o d e t b u t t h a t w a s b e c a u s e
the pressure was too high and the flask have h ad m uch fissures....
I believe that the ClO 2 oxidizes the HCl to H2O and Cl being a very strong oxidizer. W ith KMnO4 it works this way too.
frogfot June 17th, 2003, 06:15 PM

Theres lot's of ways to produce chlorine but what about equipem ent. In lab they're producing chlorine (as m a n y o t h e r g a s e s ) i n
a flask with a pressure-equalising funnel, everything of glass.. I had som e thoats on how to im provise the pressure-equalising
funnel from o t h e r l a b e q u i p e m ent where I need inert and elastic pipes.. But, what m ateria l can stand up to chlorine?
W hat pipes do they u se in lab to lead this nasty gas? The teflon is not elastic btw..

KClO3 + HC l will merely produce chlorine gas, mainly because your HCl will not ha ve a concentration above 38% and HClO3 is
stab le up to 40%. So the form ation of Cl2 gas is favored.
IIR C, PVC tubing can be used to transport Cl2.

a n d I m provised C hemistry > W hite fum es? - Archive File
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FadeToBlackened
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Posts: 201
From : Hell
posted 05-18-2001 05:23 PM
--------------------------------------------------------------------------------
A couple days ago I made a sort of trial run with a chlorate cell (using very little NaCl). Last night i decided to make a bigger
run, so i had a few hundred m L of electrolyte in a jar, with a carbon rod a nd nail for electrodes. I turned it on a took a shower.
About a half hour later when I came back into m y room, I got a huge whiff of Chlorine gas. It wasnt very strong but you could
definitely sm ell it. I p ut my fan in m y window and slept in a different room .
Now I've electrolysed NaCl many times, but never smelled chlorine outside the m outh of the jar, so I have until now ignored
warnings about the gas.
Also, when i was setting it up, i noticed when i cranked the voltage up to 12 (instead of 3) i got a slow stream of a white gas
that looked kinda like cigarette sm oke except it moved real slow. W hen I put my nose over this stuff it burned like amm o n i a .
It was white so it wasnt Cl, was it m a y b e H C l?
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 05-19-2001 11:08 PM
--------------------------------------------------------------------------------
The reason I was wondering is because if it was m aybe it could be used to m ake hydrochloric acid.
I tried it today, using quite a poor setup. It consisted of the electrolytic cell, a larger jar laying horizontally, and som e s a r a n
wrap to direct the gas into the larger one (which had som e water in it). The water was warm . I dont know if it should have been
warm or cold but it was warm.
I let it run for a while, not a lo ng tim e, and when i picke d the big jar up, there were som e white fumes com ing out.
Then I poured a little acetone and a little H2O 2 in there, as a te st (probably better ways, but oh well). In a day or two I will
post results if anything has happened.
If nothing has happened, I will put some work into mak ing what would be a m ore efficient setup, because I'm pretty sure
s o m ething like this would work.
CodeMason
Freq uent Poster
Posts: 383
posted 05-20-2001 06:30 AM
--------------------------------------------------------------------------------
Yes, it was m ost likely HCl, unless there were som e unforseen impurities in the water/salt you used. Electro lysing NaCl is a
g o o d w a y t o o b t a i n e l e m e n t a l s o d i u m . You first heat the NaCl up to its m elting point, then electrolyse it. Cl2 will be liberated,
and what's left is sodium metal.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 05-20-2001 11:21 AM
--------------------------------------------------------------------------------
Overnight an d no results. W hen I sniffed the cell it sme lled m ore like chlorine and didnt b urn (nose), so i dont think there was
sufficient light to break up the H2 and Cl2 (its supposed to do that.)
Ill try again someday.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > I haven't been able to
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Dhzugasvili
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From:
posted 05-22-2001 06:17 PM
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I tried mixing 36% formaldehyde, 200ml w ith 100ml 25% ammonia w ater. Left solution to sit, It got hot, but no crystals precipitated and still have not precipitated after weeks
its been out there. the recipe said to "let the solution evaporate" If anyone has been able to make hexamine, *PLEASE* tell me how !!
CodeMason
Frequent Poster
Posts: 383
posted 05-22-2001 07:03 PM
--------------------------------------------------------------------------------
1. There are probably impurities in either the ammonia or formaldehyde, when concentrations like that are mixed, it does more than get hot, it make sparks and clouds of
smoke! Unless you added them SLOWLY, of course.
2. All the liquid needs to evaporate.
Zero
Frequent Poster
Posts: 93
From: ...
posted 05-22-2001 09:05 PM
--------------------------------------------------------------------------------
And shoot me if this sounds stupid, but...
Can't you just buy the stuff? I think Cheaperthandirt.com has it.
~Zero the Inestimable
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 05-22-2001 09:31 PM
--------------------------------------------------------------------------------
I salt shaker of tablets is like $5-$7CND doesn't sound very cheap to me. If you have access to a chemical supplier(Fire Fox, Pyrotek.org, etc.) I don't think it is that expensive.
but to buy it as fuel tablets itis not cheap.
------------------
"...There Will Be No
Stand Off At High Noon
... Shoot'em In The Back
And, Shoot'em In The Dark"
Jumala
Frequent Poster
Posts: 200
From: Germany
posted 05-22-2001 10:52 PM
--------------------------------------------------------------------------------
Here in germany you get hexamine in white cubes under the trade brand "Esbit".
This is also expensive.
But Omikron sells it in plastic bags 500g for 3$.
Mr Cool
Frequent Poster
Posts: 991
posted 05-23-2001 11:48 AM
--------------------------------------------------------------------------------
I get about 150g for 3 as fuel tablets, w hich isn't very expensive. I prefer buying it because it's pure and takes no time or effort.
Dhzugasvili
Frequent Poster
Posts: 64
From:
posted 05-25-2001 09:15 PM
--------------------------------------------------------------------------------
People, thanx for the info, but I haven't tried obtaining it (probably should according to your replies), and as I wright this response excuse the inaccuracies because i am drunk,
but tell me, CODEMASON < HAVE YOU EVER TRIED MAKING THIS SHIT?? If so, w hat formula did you use?
I have some dirt cheap fuel tablets, they are KOrean, they say, "non-toxic, use for heating toys, etc." tell me, how can I tell if this is hexamine?? I guess It would be toxic if it is
hexamine, or am I wrong?
CodeMason
Frequent Poster
Posts: 383
posted 05-26-2001 12:20 AM
--------------------------------------------------------------------------------
Yeah, I made it, I used household ammonia (5%) and Formalin (37% formaldehyde). I used around 25ml formaline and 200ml ammonia, and let it sit in the sun for a while. As
the liquid evaporated, the inside of the bowl that was dry had a thin coating of white crystals that looked like salt. Finally, after about 2 days, it had all evaporated. The crystals
formed a hard cake on the bottom. I oxidized it and it made HMTD, so I knew it was proper hexamine.
Lem
New Member
Posts: 3
From: Austin, Tx
posted 05-26-2001 01:01 AM
--------------------------------------------------------------------------------
well, check out:
http://rhodium.lycaeum.org/chemistry/eleusis/zwit.menh2.html
it is a paper about making methylamine, but it goes through hexamine to get there. it has some good stuff about possible problems and stuff. (NO kewl spelling [stuph]
NBK2000)

stanfield
Frequent Poster
Posts: 166
From: FRANCE
posted 06-11-2001 05:56 AM
--------------------------------------------------------------------------------
I tried to make hexamine by mixing
100mL ammonia (22%) and 160 mL formaldehyde (30% ). The reaction is exothermic (80C) but no field appears...
Now, I'm trying to boil the olution to evaporate all the water but i don't think it will w ork....
what's wrong ?
thanx !
Mexican Pizza
New Member
Posts: 23
From:
posted 06-11-2001 10:06 AM
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you only have to post it once my friend
John456
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Posts: 105
From:
posted 06-11-2001 05:25 PM
--------------------------------------------------------------------------------
I dunno why everyone says this, i have no problems making hexamine. I use 140mL 40% ammonium hydroxide solution and 280mL 37% methanal (Formaldehyde) in a big 5
gallon tub (because the reaction is so heavy). Usually when i mix them it starts fuming, gets VERY hot and once some sparks even came off it. When this is done and it starts to
cool some hex usually settles to the bottom, and the rest forms in about a w eek of standing in the garage. Boiling w ill probably destroy the hexamine so i wouldnt try it.
[This message has been edited by nbk2000 (edited June 11, 2001).]
Dhzugasvili
Frequent Poster
Posts: 64
From:
posted 06-12-2001 04:36 PM
--------------------------------------------------------------------------------
You know , Stanfield, that I can completly identify with you in this search for how to make this stuff. Check out my post below, but since the last reply i have not attempted to
make it again though that last reply is pretty good, go to the site that they recommend, that method might work, I still have to try it though, Will reply again when I do.
stanfield
Frequent Poster
Posts: 166
From: FRANCE
posted 06-12-2001 04:56 PM
--------------------------------------------------------------------------------
"Boiling w ill probably destroy the hexamine so i wouldnt try it."
Damn, I obtained hexamine (white crystals) but I obtained them by boiling the solution !!! How can I make sure it's really hexamine ?
a_bab June 20th, 2003, 06:32 AM

Well, since hexamine will hidrolise in hot w ater there is no way of getting hexamine by the means of boiling the solution.
(CH2)6N4+ 6H2O---> 6HCHO^ + 4NH3^
So the correct recipe is :
In a formaline solution of 40 % add ammonia until the reaction is basic, at a temperature of max. 35 dedrees C .(sidenote: the concentration of the ammonia seems it has no
effect). In theory the resulted substance contains 90 % hexamine. The solution should be evaporated UNDER VACUUM at no more than 40 degrees C. The obtained hexamine is
dried at 30-35 degrees C. In order to get a pure product, the obtained hexamine is recrystalised from alcohol.
This recipe is a translation taken straight from a russian chemistry book.
FANATICO January 22nd, 2004, 11:55 PM

Originally posted by a_bab
Well, since hexamine will hidrolise in hot w ater there is no way of getting hexamine by the means of boiling the solution.
(CH2)6N4+ 6H2O---> 6HCHO^ + 4NH3^
So the correct recipe is :
In a formaline solution of 40 % add ammonia until the reaction is basic, at a temperature of max. 35 dedrees C .(sidenote: the concentration of the ammonia seems it has no
effect). In theory the resulted substance contains 90 % hexamine. The solution should be evaporated UNDER VACUUM at no more than 40 degrees C. The obtained hexamine is
dried at 30-35 degrees C. In order to get a pure product, the obtained hexamine is recrystalised from alcohol.
This recipe is a translation taken straight from a russian chemistry book.
Hexamine not will denatured by boiling water. this only happen at temperature above 280 Celsius.There's no problem in eliminate water in excess by this method. I get 150 gr
of hexamine in this very minute ffrom that way. See at w ww.chemicalland21.com/arokorhi/industrialchem/ organic/HEXAMETHYLENETETRAMINE.htm
Ropik April 23rd, 2004, 07:53 AM

I used this methode twice and everytime I got good yield.
This is excerpt from Uncle Fester's Home w orkshop explosives:
To make hexamethylenetetramine, 2000 grams (1850 ml) of 37%

formaldehyde solution is poured into the enamelled dish. Then to this is
added 1100 grams (1200 ml) of ammonium hydroxide solution. As was mentioned
before, this material is just ammonia dissolved in water, and may be sold
under such monikers as strong ammonia solution 27% , or 58% NH4OH or ammonia
water 26 degree balme. The ammonia solution should either be cooled down in
the freezer before use, or have 250 grams of ice added to it.
The ammonia is added slowly to the formaldehyde w ith good stirring. A
fair amount of heat is given off in the reaction, and the reek of
formaldehyde and ammonia w ill get intense for a while until all the ammonia
has been added. Then all the formaldehyde will be tied up, and only a weak
smell of ammonia will remain. Stir some more to be certain that an even
solution has been obtained.
The solution in the pan or dish contains about a pound and a quarter of
product dissolved in a bunch of w ater. The task now is to obtain the
hexamethylenetetramine, which is a crystalline solid, from the water. To do
this, first the dish is placed on the hotplate, then heat is applied to it
to bring it to a slow boil. As the water boils aw ay, portions of about 15
ml of the ammonia solution are added to it every ten minutes or so. This is
to ensure that enough ammonia is present to keep any formaldehyde which may
be floating around unreacted, tied up.
When about half of the solution is boiled away, the heat should be
removed from the pan and the solution is allowed to cool dow n to the point
where it is about as hot as hot tap water. Then it is filtered through a
coffee filter placed inside a plastic funnel. This is to remove any gummy
material which may have been formed from the formaldehyde. This gummy stuff
will quickly plug the filter, so be prepared to change the filter several
times.
The liquid which filters through still contains the product. It is

returned to the pan. Its volume should be a little over 2000 ml. It is once
again boiled away until its volume is around 800 ml (1/3 or so of the
previous volume). Now the first crop of product can be obtained. Remove the
pan from the heat and allow it to cool, then cool it further either by
packing the pan in ice or putting it in the freezer. As it cools, a large
mass of crystals will appear.
These crystals are then filtered out by filtering them through the
vacuum filtering apparatus shown in the nitromannite chapter. Feel free to
pack them dow n a little w ith a spoon to help squeeze the liquid out of
them. Then the crystals are dumped out onto wax paper. The liquid should go
into a separate jug for temporary storage until all the crystals are
cleaned out of the pan. A rubber spatula w ill be very handy for scraping
the cling-one off the w alls of the pan.
When the first crop has been collected, the liquid is returned to the
pan. Then the crystals of product are rinsed off. To do this, they are
packed back into the filtering funnel, and rinsed off with 190 proof grain
alcohol. A few rinses should remove the smell of ammonia from them. Then
they should be spread out on fresh wax paper until they are dry. They
should have no smell. They should also be clear or white in color.
The liquid which has been returned to the pan still contains a lot of
product. To get it, first pour the liquid into a glass beer pitcher or
similar container. Then about 10 grams of powdered activated charcoal is
added to the liquid. If the lab brand of charcoal called Norite is
available, this is best. Otherwise, the various other types of activated
charcoal will w ork so long as they are powdered up before use.
This activated charcoal will take up the yellow ish color from the
solution. First stir it in for a few minutes. Then set up the vacuum
filtration system again, with double layers of filter paper. Pour the
solution through it. A clear solution should result. If it is still black,
all the charcoal isn't out of it. Wash up the system, change the filters,
and filter some more. If it is still yellow ish, add some more activated
charcoal and continue.
The clear solution can now be returned to the original dish, and heat
reapplied to it. The goal here is to evaporate the liquid to dryness and
collect the crystals which are left w hen the water is gone. Heat it
reasonably strongly at first, then steadily back off on the heat as the
volume of liquid goes down. One does not want to burn the crystals.
Finally, end up with just a warm setting, and drive off the last of the
water. Then scrape out the crystals of product from the pan. The total
yield of hexamethylenetetramine should add up to around 560 grams.
All the hexamethylenetetramine should be spread out onto w ax paper

sheets and allowed to dry.
I scaled it a bit dow n, how ever.

Is their any way to substitute paraformaldehyde for the formalin solution

a n d I m provised C hemistry > Potassium -Kalium - Archive File
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Jumala
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Posts: 200
From : Germ a n y
posted 05-23-2001 09:51 PM
--------------------------------------------------------------------------------
Perhaps it sounds stupid but I dont know where the na m e s S o d i u m a n d P o t a s s i u m c o m e f r o m because they dont fit to their
chemical sho rt form s. K for po tassium (kalium ) or Na fo r sodium (Natrium).
Does anyone know something ?
FadeToBlackened
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Posts: 201
From : Hell
posted 05-23-2001 10:06 PM
--------------------------------------------------------------------------------
I m g u e s s i n g t h e y a r e foreign.. Like Pb is lead, Hg is m ercury, Sn is tin, etc...
CodeMason
Freq uent Poster
Posts: 383
posted 05-24-2001 03:55 AM
--------------------------------------------------------------------------------
" P o t a s s i u m " c a m e from the word "potash", which was a substance, mainly com p o s e d o f v a r i o u s p o t a s s i u m salts. It was called
"potash", because it was the residue left from the burning of certain plan ts.
"Sodium " cam e from the word "soda", which described certain so dium salts. I don 't know where "soda" itself cam e f r o m .
John456
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Posts: 105
From :
posted 05-24-2001 03:04 PM
--------------------------------------------------------------------------------
The names are latin, im guessing.
Lagen
Freq uent Poster
Posts: 174
From :
posted 05-24-2001 06:58 PM
--------------------------------------------------------------------------------
T h e L a t i n ' k a l i u m ' c o m es from Arab 'qali' m eaning alkali (prob. caustic potash KO H). The English 'soda' comes from m e d i e v a l
L a t i n ' s o d a n u m ' m e a n i n g s o m e s o r t o f h e a d a c h e r e m edy. I'm not sure about 'natrium ', m aybe it's from natron, a sodium
containing m ineral named after the Egyptian W adi an Natrun where there are large deposits. Just a specula tion, though. Davy
was the first to deal with those elemen t s i n 1 8 0 7 s o h e c o u l d h a v e m a d e t h o s e n a m es up, there probably don't exist any in
native Latin.
SATANIC
Freq uent Poster
Posts: 237
From : austra lia
posted 05-24-2001 09:10 PM
--------------------------------------------------------------------------------
They all came from latin - K, Na, Pb, Hg etc.
PYRO 500
Moderator
Posts: 1465
posted 05-24-2001 09:21 PM
--------------------------------------------------------------------------------
I herd several stories about why Latin is used a lot in science today. one says tha t since a lot of discoveries about science
c a m e f r o m the Renaissance in Europe where they spoke Latin and thus kept the original Latin nam e s / s y m b o l s t o h o n o r t h e
discoverers. another one I heard is that to give the Latin language a purpose for existence because it was extinct, I personally
believe the firs over the second.
Arthis
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Posts: 203
From :
posted 05-25-2001 11:14 AM
--------------------------------------------------------------------------------
L a t i n i s u s e d b e c a u s e f i r s t p e o p l e i n R e n a i s s a n ce used to use it, then be cause it is lot easier to name things with a latin name,
a n d n o t s e v e r a l d i f f e r e n t n a m e s . L o o k p l a n t s : t h e y a l l h a v e l a t i n n a m e to take care about each va riety, over generic names we
use to call th e m .
Bitter
Freq uent Poster
Posts: 290
posted 05-25-2001 03:28 PM
--------------------------------------------------------------------------------
Hg isn't latin it's greek. There are a few others like that aswell.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > NH4NO3 + KCl ->
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fire stilzchen
New Member
Posts: 10
From: de
posted 05-29-2001 05:03 AM
--------------------------------------------------------------------------------
can anyone tell me if this reaction is true, does it work ?
NH4NO3 + KCl -> NH4Cl + KNO3
because i need tons of potassium nitrate and i have lots of fertilisers [NH4NO3 100kg , KCl 80kg]
i thinks thats a cheap method of making KNO3, tell me if i'm wrong
- stilzchen -
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 05-29-2001 10:07 AM
--------------------------------------------------------------------------------
just to bad it won't form a ppt. they both been alkaline are souble no matter what they are linked with.
Thanx for coming out eh.
------------------
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 05-29-2001 10:44 AM
--------------------------------------------------------------------------------
To reply to you w e need the solubilities (saturated solutions) in grams per littre at 0C and at 80C of KCl, KNO3, NH4Cl and of NH4NO3!
------------------
"Chemistry is all w hat stinks and explode; Physic is all what never works! ;-p :-) :o)"
fire stilzchen
New Member
Posts: 10
From: de
posted 05-29-2001 03:50 PM
--------------------------------------------------------------------------------
so, here are the solubilities (saturated solutions) in grams per littre at 0C and at 100C of KCl, KNO3, NH4Cl and of NH4NO3.
[sorry i didn't found it by 80C but from KCl and NH4Cl i found it]
0C 100C 80C
NH4NO3 118,0g 871,0g ?
KNO3 13,0g 246,0g ?
NH4Cl 29,4g 77,3g 65,6g
KCl 27,6g 56,7g 51,1g
I hope its helpfull - sorry about my ... english
- stilzchen -
[This message has been edited by fire stilzchen (edited June 02, 2001).]
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 05-30-2001 10:44 AM
--------------------------------------------------------------------------------
Following w hat you have w ritten it should work wel!
But it is a lot of w ork!
First take 200g of NH4NO3 in a volume of 1 liter (complete w ith water!) heat this until 20C-25C under stirring everything should dissolve!Continue the stirring w ith an addition of
55g of KCl! Heat until 100C (the solution must be clear no cristals in it so heat a little higher if needed until clear)!Then cool the mix down fast until 0C!A precipitate of KNO3 w ill
occur!
To assert this I have used your datas!
MMNH4NO3= 80g/mol
MMKCl= 74.55g/mol
MMKNO3= 101.1g/mol
MMNH4Cl= 53.45g/mol
Solubilities in mol/l of:

NH4NO3:
at 100C= 10.8875
at 0C= 1.475
KCl:
at 100C= 0.7605
at 0C= 0.3702
KNO3:
at 100C= 2.4332
at 0C= 0.1285
NH4Cl:
at 100C= 1.4462
at 0C= 0.5500
From this you can see that KCl is (slightly) less soluble than NH4Cl at all temps!
That NH4NO3 is the more soluble of all at all temps!
That KNO3 is the less soluble at 0C!
Knowing that the less soluble salt will drive the precipitation prior to all the others salts!
At 100C you can't go over 56-57g of KCl because it is the less soluble salt at that temp (by security I have put 55g)!
I have also used the rule of common ion (by adding a slight excess of NH4NO3:
when in a saturated solution of a salt another common ion enters the system the solubility of the first salt decrease follow ing the solubility equilibrium constant(Ks(T))!
Thus follow ing those laws:

Ks(KNO3)(at OC)= (conc K+)exp1 *(conc NO3-)exp1
=(0.1285)*(0.1285) (in a pure water solution)= 0.01651 sqre mol/sqre liter
Here w e have 200g/l NH4NO3 and thus 200/80 mol/l NO3(-)= 2.5 mol/l nitrate anion!
And 50g/l KCl that makes 50/74.55 mol/l K(+ )= 0.6707mol/l potassium cation!
Multiplying those two numbers we have the Ks'(at OC) value =2.5*0.6707 sqre mol/sqre l = 1.6767 sqre(mol/l)
Since this value is 100 times much over the permitted solubility we will have a precipitation of nearly all the permited KNO3
Then the remaining conc of K(+)= Ks(OC)/2.5 mol/l NO3(-)= 0.01651sqre(mol/l)/2.5 (mol/l) = 0.006604 mol/l and we had 0.6707mol/l potassium cation in solution thus we
precipitate 0.6707-0.006604 mol/l of KNO3= 0.664096 mol/l!
This means 0.664096 mol/l * 101.1g/mol= 67.14g of KNO3!
After collecting those batches it is a good idea to recristallise them via the same process (since some KCl may coprecipitate-not a lot): saturation at 100C then fast cooling to
0C!
Thus to make 670g you would need 10 liters of the above mix of 2000g NH4NO3/500g KCl!
Enjoy!
------------------
Agent Blak
Frequent Poster
Posts: 766
From: Sk. Canada
posted 05-30-2001 02:03 PM
--------------------------------------------------------------------------------
what about this. Calcium nitrate is avaible as a fertilizer also, it also w ill arose less suspician than asking for NH4NO3. you could use a Rx that would look like this and w ould
even give you a ppt.
Ca(NO3)2(sol) + K2SO4(sol)---> 2KNO3(sol) CaSO4(ppt.)
That should w ork unless I am over looking something.
------------------
fire stilzchen
New Member
Posts: 10
From: de
posted 05-30-2001 03:37 PM
--------------------------------------------------------------------------------
thanx,
in germany its hard to get calciumnitrate as fertilisers. so i buy ammoniumnitrate in 100kg in "czech land".
PHILOU w here do you learned to calculate the reactions so good ?
- fire stilzchen -
Jumala
Frequent Poster
Posts: 200
From: Germany
posted 05-30-2001 08:24 PM
--------------------------------------------------------------------------------
The solubility table is fine.
I looked for it several time because I need it to calculate the kalkammon salpeter quantity in a saparation process.
But pure AN would be better. What quality is your AN from czech rep. ?
In germany it should be possible to get KNO3 as food additional under the E252 number.
At Ebay someone sells this KNO3 in 1,5 Kg bags w ith 99,5% purity.
But I dont know the damn source.
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 05-31-2001 05:49 AM
--------------------------------------------------------------------------------
I'm a chemical engineer in chemistry and biochemistry specialised in organic chemistry! I was a chemistry autodidact, so I knew a lot about nearly everything before starting my
5 years university!I never read books(I find them borring), except science ones (I can stay hours reading them!)!
------------------
fire stilzchen
New Member
Posts: 10
From: de
posted 05-31-2001 03:41 PM
--------------------------------------------------------------------------------
my AN from czech rep. is 17%NO3 and 17%NH4. i never found a code like 34-0-0 but 17%+ 17% =34% so i think its a good stuff. the smoke bombs with AN + newspaper are
very nice they smoke very well and sometimes when the smoke bombs are too hot they will fizz and burn very fast.
also i tried to make ammonpulver and it w orked.
a 50kg bag was 8$[usdollar]
- fire stilzchen -
Jumala
Frequent Poster
Posts: 200
From: Germany
posted 05-31-2001 11:44 PM
--------------------------------------------------------------------------------
Hallo Philou,
do you mean you read absolute no books or only no books like KIPE.
I bought "Nitroglycerine and Nitroglycerine Explosives" by Phokion Naoum (450pages) some weeks ago.
It is really interesting to read about old techniques in every detail. The book is original from 1923 but still up to date.
The Ammoniunnitrate from Cz is 34-0-0.

AN = NH4NO3 = 17% +17%
8$ for 50Kg is really cheap. Especially when no separation is nessesary. Is it prilled (little pearls) or cristallized.
Perhaps you can get nitromethane also in Cz?
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 06-01-2001 03:17 AM
--------------------------------------------------------------------------------
I just meaned I read only science books...all the rest is crap to me (w hen reading those poetry, love stories,...books, it feels like loosing time!).
So everyday my science knowledge grows more and more!
------------------
fire stilzchen
New Member
Posts: 10
From: de
posted 06-01-2001 11:23 AM
--------------------------------------------------------------------------------
the czech AN is prilled but i never asked for nitromethane because the name of the chemicals are different, so nh4no3 is azotan.
in poland the names like the czechs and the price is allmost the same.
can i ignite natriumchlorate with electrical power like a car battery? and can i use it to let ANFO or ANNM go off?
in 1 or 2 days i'll send you a link w ith pictures from one of my 50kg AN bags.
- fire stilzchen -
Lagen
Frequent Poster
Posts: 174
From:
posted 06-01-2001 09:33 PM
--------------------------------------------------------------------------------
Agent Blak: That Rx works, just the K2SO4 is a pain to dissolve. It's best to boil it. This way you can get a very pure product even without recrystallization, as the impurities can
be pptd too. (Provided one has access to things like BaCl2.)
fire stilzchen: If you cannot get the Ca(NO3)2 in Germany it can be had in the "czech land" too but the largest bags I've seen are 3 kg. Sometimes it has small stones in it, but
nothing dramatic. Upon dissolving it forms some sludge but the Rx makes a lot more (CaSO4) so filtration is necessary anyw ay.
NH4NO3 solubility data (haven't tried!):
Mass of solute per 1000g solvent H2O
0C 1173,9
10C 1506,3
20C 1898,6
30C 2367,0
40C 2891,0
50C 3484,3
60C 4208,3
70C 5024,1
80C 6042,3
90C 7474,6
100C 9309,3
Source: Shnel, O., and Novotny, P., Densities of Aqueous Solutions of Inorganic Substances, Elsevier, Amsterdam, 1985.
Therefore I think you must be mistaken as the values given look rather like "mass of solute/100g of solvent". The other figures for KNO3 etc. also are very low for the litre!
The reason why I am giving so many numbers is that the soly curve is quite nonlinear and I wouldn't interpolate it from 0 and 100.
Nitromethane can be bought here as an additive for model plane racing fuel but the price is prohibitive. I believe 25$/1l.
"Azotan" is a Polish term not Czech and it means "nitrate".

Czech for nitrate is "dusicnan", fertilizer grade is "ledek".
Hope that helps.
fire stilzchen
New Member
Posts: 10
From: de
posted 06-02-2001 03:52 PM
--------------------------------------------------------------------------------
shit i've made a BIG mistake the solubilities i have post was not for 1 litre it was for 100g h2o2 -> 100ml. sorry
i changed my old message that it is 100ml h2o not 1litre
lagan: thanx, and in czech rep. they have sold me polish fertiliser. but it w as really cheap.
- fire stilzchen -
fire stilzchen
New Member
Posts: 10
From: de
posted 06-03-2001 02:23 PM
--------------------------------------------------------------------------------
http://people.freenet.de/stilzchen/fertiliser.html my AN bag
PHILOU: must i calculate the reaction again, or can i multiply it with 10 because 1 litre = 10*100ml ?
- fire stilzchen -
Lagen
Frequent Poster
Posts: 174
From:
posted 06-04-2001 02:14 PM
--------------------------------------------------------------------------------
fire stilzchen:
Here are the solubility data you should use (mol/l: KNO3,NH4Cl,KCl,NH4NO3):
0C 1.348756344 5.558921824 3.726200527 14.66594943
10C 2.112615115 6.271500461 4.145777629 18.81810257
20C 3.157774308 7.009535016 4.564699447 23.71900464
30C 4.506325175 7.781279832 4.971281875 29.57148477
40C 6.218044992 8.580888868 5.370338354 36.11851994
50C 8.324368498 9.417612589 5.759657440 43.53017477
60C 10.80133742 10.28481814 6.139769386 52.57561811
70C 13.65883409 11.19766719 6.505633526 62.76712227
80C 16.84122786 12.15461639 6.867035458 75.48717948
90C 20.35645916 13.16942994 7.219552903 93.38149724
100C 23.98199637 14.24167129 7.561557290 116.3028269
Okay I will make one daring statement here: The coprecipitation of KCl cannot it be reduced? Because KCl is the least soluble until some point above 30C. To calculate that
point:
Tx=30C+ 10x; x*1,711719817+ 4,506325175=x*0,399056479+ 4,97128187 5
x*1,312663338=0,4649567; x = 0,3542086; Tx = 33,542C
KNO3;Tx => 5,112631129 M; KCl => 381,15176 g/l
So I think it's sufficient to add cca 380g KCl to the NH4NO3 solution per 1000g H2O then heat it to 40-50C to be safe and it should all dissolve. Then as PHILOU said cool to
0C:
Ks(KNO3;0C)=(1,348756344)exp2= 1,819144[(mol)exp2/(l)exp2]
For example: Using 1000ml w ater, 500g NH4NO3 (some excess included) follow PHILOU's procedure and add 380g KCl. After dissolving it and cooling to 0C, follow ing the rule
of common ion we have:
[K+],[NO3-]:
initial=5.112631129;6.2466080918
equilibrium=x;1.1339769628+ x
x*(1.1339769628+x)= Ks(KNO3,0C)=1.819144
1.1339769628x+(x)exp2= 1.819144; (x)exp2+1.1339769628x-1.819144=0; D= 8.562479752
x1,2= (-1.1339769628 +- 2.9261715)/2; x1=0.8960973
4.216533829 moles or 426.305 g KNO3 precipitate.
But! You also loose the excess NH4NO3 in the residual solution and the overall efficiency is only 426.305/516.90357)*409.23258/500=67.5% To find out if it can be improved:
If w e put c for [KNO3] and y for the "molar excess" of NH4NO3 then moles of precipitate x= (sqrt(y^2+ 4Ks)-y)/2 and overall efficiency of conversion n=[c/(c+y)]*[c-x]/c=(c-
x)/(c+y). Now what excess of NH4NO3 to put in to acheive maximum efficiency?
n'= 0 < => [two pages of deriving snipped]
No sensible extreme of n found! (except for y=0) That means: adding too much excess of NH4NO3 is inefficient! The more you add the more you w ill waste! Maximum
efficiency 73.6% is achieved at minimal excess NH4NO3 (at 409g), in other words not using the common ion effect. You should use it if you wanted to recycle the NH4NO3 from
your residual solution but that will contain impurities (chances are it will be sulfates w hich would be hard to remove by recrystallization), to calculate with those impurities the
calculations would be WAY more complicated and practically you would get unpredictable results. I remember I tried it once and it w as really too much w ork separating the KNO3
so I prefer the Ca(NO3)2+K2SO4 method.
fire stilzchen
New Member
Posts: 10
From: de
posted 06-07-2001 02:31 PM
--------------------------------------------------------------------------------
thanks that was very helpfull.
yesterday i tryed this procedure an it worked.
i used 2kg NH4NO3 & 4000ml H2O & 1,5kg KCl and i was filtering about 1,7 kg KNO3 but it's not that quality. i think it's cheaper to buy it because thats a hard work.
- fire stilzchen -
Lagen
Frequent Poster
Posts: 174
From:
posted 06-07-2001 08:06 PM
--------------------------------------------------------------------------------
Congrats!
As to the poor quality... this S..T always happens when using this reaction, it's kinda unpredictable (see the "potassium nitrate from ammonium nitrate" topic in this section),
you'd have to recrystallize it or otherwise clean it, but I can't suggest a procedure without knowing the properties of your materials (for example, 1% CaSO4 is harder to remove
than 20% Ca(NO3)2). Your NH4NO3 is probably pretty clean, but KCl fertilizer usually holds 10-15% impurities of the hard to remove kind.
Yep it's alw ays better to buy it if you can, without showing your ID... :-(
PHILOU Zrealone
Frequent Poster
Posts: 479
posted 06-08-2001 08:06 AM
--------------------------------------------------------------------------------
Yes multiply by ten to get mol/l conc
If you play with 100ml batches, then, you would get 67.5g/100ml!Playing with 1000ml w ould lead you to 67.5g/100ml+ 67.5g/100ml+...+67.5g/100ml --> 675g/l

a n d I m provised C hemistry > filtering - Archive File
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skunkdude
New Mem ber
Posts: 30
From :
posted 06-22-2001 09:11 AM
--------------------------------------------------------------------------------
hypotheticly speaking, if som e o n e h a d r e a d K I P E a n d h a d a t t e m pted to m ake sodium chlorate with HTH chlorinating granules,
tried to filter it with a T-shirt and then a towl, both of wh ich were eaten away by the solution, how would they go about filtering
it?
ANTI-SYSTEM
Freq uent Poster
Posts: 77
From : FL. USA
Registered: JUN 2001
posted 06-22-2001 01:51 PM
--------------------------------------------------------------------------------
goes in MISC.
try nylon insted of cotton. its not organic. the hth is m ent to break up and kill org anics.
grandyOse October 9th, 2003, 11:24 AM

I know that potassium perchlorate is m uch preferred over the chlorate, and that the HTH method is not well regarde d here. I
have a couple of questions about it, though.
1 ) T h e e q u a t i o n d o e s n o t s e e m t o b a l l a n c e . W h e r e d o e s the extra oxygen com e f r o m ? I f s o m e H 2 O 2 w e r e in the m ix, would

you get PERchlorate?
2 ) A c c o r d i n g t o t h e C R C h a n d b o o k o f c h e m & p hysics, C a C l i s m o r e s o l u b l e t h a n K C l O 3 a t b o t h 2 0 a n d 1 0 0 C. Why would the

C a C l c o m e out of solution at boiling?
metafractal October 10th , 2003, 10:39 AM

That m ethod refers to Sodium Hypochlorite, not Calcium Hypochlorite as you have assum e d .
In this way, the reaction blances fine: 3NaO Cl + KCl -> KClO3 + 3NaCl
So it is Sodium Chloride that is filtered out, not Calcium Chloride.
Chlorates m a y a l s o b e m ade by the th erm a l d e c o m p o s i t i o n o f C alcium Hypochlorite, though.
A s t o a d d i n g H 2 O 2 t o the solution to yield perchlorates, I am en ticed by this idea. It does not seem like it would wo rk to me ,
but I cannot provide an explanation as to why. Its worth a try:
3 N a O C l + KC l + H2O 2 -> KClO 4 + 3NaCl + H2O
Therefore, 223g NaOCl + 74.6g KCl + 34g H2O2 -> 138 .6g KClO 4 + 175.5g NaCl + 18g H2O
If anyone actually carries this out, they m ight wish to recheck those calcu lations, I'm quite tired.

a n d I m provised C hemistry > would this work to get hydrochloric acid - Archive File
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phyrelord
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Posts: 135
From :
posted 05-09-2001 10:30 PM
--------------------------------------------------------------------------------
If you put hook two e lectrodes up to two different chambers that were connected by a pipe and seperated the water into
h y d r o g e n a n d o x y g e n ( I f o r g e t t h e t e r m for this, too m any bong hits) Th en run the hydrogen side out to another container
filled with chlorine granuals, when exposed to light they react with each other to form HCL mix this with water and voila. I don't
know the ratio of water to HC L any help is appreciated. Any com m ents are welcom e
------------------
W inseln Sie fr mich
CragHack
Freq uent Poster
Posts: 618
From :
posted 05-09-2001 11:25 PM
--------------------------------------------------------------------------------
i dont know if this would work exactly. i am also curious to know why you can't just buy the shit. it is easy to find. bu t hey,
s o m etimes we need to improvise. I think if you dum ped granular "Cl" into water it would stay in the form of C l 2 a nd th u s
unabvle to react with the hydrogen gas that got bubbled through the containter. I am sketchy on h ow the C l2 would act though,
when put in water. does anyone know if it would dissolve or any way break up into ions?
------------------
"If you m ust, do it with intelligent people, at least they know how to talk to the cops."
phyrelord
Freq uent Poster
Posts: 135
From :
posted 05-10-2001 04:16 PM
--------------------------------------------------------------------------------
the Cl will bond with the H as long as there is light present. The weak single covalent bond will break up with the addition of
energy and all that's needed is that of light. and the C l would not be in the same container as the water bu t in a different one
and the Hydrogen would be vented over to it. T he reason I would do this is Cl is less conspicuous than hydrochloric acid so it
would be more difficult for the piggies to track it to you
------------------
W inseln Sie fr mich
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
posted 05-10-2001 05:15 PM
--------------------------------------------------------------------------------
The word your looking for is electrolysis. It produces H2 quite slowly. You m ight also be interested in this:
2NaCl + 2H2O >>elec.>> 2NaO H + H2 + Cl2
Saltwater electrolysed produce s e q u a l a m ounts of chlorine and h ydrogen, which i suppose could react according to
H2 + Cl2 >>>> 2HCl
Oh by the way, watch what you use for electrodes. Read m y 'Am m onium hydroxide/various sulfates/nitrates' post way way down
in m isc to see what im talking about.
ftsm a n
Freq uent Poster
Posts: 55
From : m elb
posted 05-22-2001 10:34 PM
--------------------------------------------------------------------------------
just buy som e
Mr C ool
Freq uent Poster
Posts: 991
posted 05-23-2001 11:52 AM
--------------------------------------------------------------------------------
A so lution for cleaning stonework/brick etc. is very com mon in DIY/hardwear store s. You can get co ncs. between 10% and 30 %
(38% is about the m ost conce ntrated HCl you can get), and 2L costs a few pounds.
PYRO 500
Moderator
Posts: 1465
posted 05-23-2001 03:27 PM
--------------------------------------------------------------------------------
HELL! I get m y HCL for .38$! at hom e d e p o t
sealsix6
Freq uent Poster
Posts: 154
From : NYC ,NYC,USA
posted 05-23-2001 07:07 PM
--------------------------------------------------------------------------------
Pyro what is the nam e that you buy it under?
PYRO 500
Moderator
Posts: 1465
posted 05-23-2001 07:50 PM
--------------------------------------------------------------------------------
itm is sm art brand and the na m e i s P Y R O 5 0 0 !
sealsix6
Freq uent Poster
Posts: 154
From : NYC ,NYC,USA
posted 05-24-2001 05:27 PM
--------------------------------------------------------------------------------
Is there any chance of me getting the real nam e of the brand and product? PLZ PLZ PLZ im begging you i baught this toilet
bowl cleaner shit that said con tains HCL but when I had my dream o f m a k i n g a p i t d i d n t w o r k a n d I h a d p u r e a c i t o n e a n d t h e
3% peroxide.
Anthony
Moderator
Posts: 2306
From : England
posted 05-25-2001 03:07 PM
--------------------------------------------------------------------------------
T o s a v e P Y R O 500 repeating h im self, It is "sm art" brand! And his name is "PYR O500" not "pyro" which is what you called him .
Lem
New Mem ber
Posts: 3
From : Austin, Tx
posted 05-26-2001 01:04 AM
--------------------------------------------------------------------------------
If you are trying to generate HCL gas, why not just drip H2S04 on to a sat. NaC l sol.
http://rhodiu m.lycaeum.org/chem istry/hcl-gas.txt
Mr C ool
Freq uent Poster
Posts: 991
posted 06-09-2001 05:52 PM
--------------------------------------------------------------------------------
Distil H2SO4 (98 grams) with NaCl (117 gram s ) , a n d b u b b l e t h e g a s ( 7 3 g r a m s) through HCl solution until it fum es strongly.
This works well.
Foodos
Freq uent Poster
Posts: 210
From :
posted 06-10-2001 08:04 PM
--------------------------------------------------------------------------------
O n e b r a n d n a m e that is even available at Fred Meyers (for christs sake, its not hard to fin d) is Muriatic Acid. The on e I h a v e
seen is 31.6%
CragHack
Freq uent Poster
Posts: 618
From :
posted 06-10-2001 08:26 PM
--------------------------------------------------------------------------------
the HC l(a) here is also Muriatic, and has a concentration of 32.25%. You can find it at lowes

I would not advise reacting C L2 + H2 in the pre sence of light. This is radical reaction which m eans it can becom e explosive very
quickly. The sunlight generates the necessary radical and once you've got one you start a chain reaction.
metafractal June 20th, 2003, 11:31 AM

Just bubble Cl2 gas through water to g et a weak HCl solution. Then boil to this solution to concentrate (H2O: B.P. = 100*C,
HCl: B.P. = 230*C therefore water will boil off first till ~32% HCl when it forms an azeotropic m ixture with water). Much easier
than this messy method :).
yt2095 June 20th, 2003, 11:44 AM

m etalfractal,
forgive m e if i`m wrong, but i though bubbling C l through water gave Chloric acid? (HO Cl) or does the further heatin g t h e n
convert it to Hydrochloric acid?
and yes i know i shouldn`t be asking questions this early on with my current new status, b ut it m aybe helpfull to others if i`m
corrected in m y thinking
all the best :)

You are correct.
Cl2 in water will form H O C l u p o n e x p o s u r e t o l i g h t .
Cl2 + H2O ---> HOC l + HCl
However, when heated, the hypochloric acid will decompose:
2 H O Cl ---> 2HCl + O2
Still, yields are going to be ba d as effectively dissolving the chlorine gas in water is not on ly difficult, but also dangerous.
Metafractal, the boiling point of HCl that you stated is way too high, considering that pure HCl is a gas under standard
conditions.
EDIT: It has just come to m y m ind tha t boiling HOCl will probably produce some HClO3. However, this only happens when
heating very slowly, n orm al boiling will favor direct decom position of the HO C l I I R C .
knowledgehungry June 20th, 2003, 12:44 PM

You would have to bo il off the HCl out of the solution and then bubble th e HCl ga s through water until the water cou ld acccept
no more.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > questions about
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John456
Frequent Poster
Posts: 105
From:
posted 05-30-2001 05:28 PM
--------------------------------------------------------------------------------
Hey,
Decided to buy some jointed glassware anyway since i wont have to deal with stoppers and can use it for vacuum distillation. The stuff i bought has 24/40 joints and looks like
this:
I am thinking of buying an oil vacuum pump so i can make high concentration nitric acid among other things, and have a few questions before i do. Number one, can i just
hook the pump directly up to the vacuum adapter, or would i need something to prevent gas and liquid from going into the pump? Also, does anyone have a web page or can
provide any info on which model pumps are suitable for distillation, pricing, etc? On a related note, would i need any sort of special clamps to hold the joints together and
prevent leaks, or will grease work fine?
Thanks! -John
[This message has been edited by John456 (edited May 30, 2001).]
PYRO500
Moderator
Posts: 1465
posted 05-30-2001 06:24 PM
--------------------------------------------------------------------------------
I would get a bubbler just to make sure the nitric acid reminant vapors dont ruin the pump
10fingers
Frequent Poster
Posts: 411
From: USA
posted 05-30-2001 07:17 PM
--------------------------------------------------------------------------------
Did you get this from U.G.T? I have one that looks identical to it. You do need a trap to keep acid vapors from going into the pump.
I have a refrigeration type vacuum pump. There is a aspirator type pump that hooks up to your faucet. There about $10.00 at Pyrotek. With them you would not need any
type of trap for vapors but I have never tried one so I do not know if they would supply enough vacuum for what you want to do.
I have been able to obtain a high vacuum without using any kind of joint grease.
John456
Frequent Poster
Posts: 105
From:
posted 05-30-2001 07:37 PM
--------------------------------------------------------------------------------
Yes, it was from UGT Damn, how much does a trap run and where can i get one? I already have an aspirator and the vacuum is not even worth using. What would be the
purpose of the bubbler Pyro? Recycling the vapors back into the liquid?
Edit: A trap is a sort of condensor cooled by liquid Nitrogen or solid CO2 right? If so i can probably make one, but i dont know if i want to risk it since vacuum pumps are quite
expensive. Also, when people say "X Inches of Mercury" what does that measure? Would 23" of Hg be suitable for distillation?
PYRO500
Moderator
Posts: 1465
posted 05-30-2001 09:11 PM
--------------------------------------------------------------------------------
b trap we mean somethign to keep the vapors away form the pump, It dosent have to use cold temps, That is a cold trap. what I was taloking about is something like this:
glassware ======|| ||===========vacuume pump tubes || || -^^^^^^^^- | ! ! | | ! | Water |--------| | ! o oo | | ! o o | ----------
the water absorbs harmful vapors from reaching the pump.

this U.G.T do they have a page on the web?
there I fixed it
[This message has been edited by PYRO500 (edited May 30, 2001).]
John456
Frequent Poster
Posts: 105
From:
posted 05-30-2001 09:23 PM
--------------------------------------------------------------------------------
The picture kinda got messed up in the posting but i think i see what it was supposed to look like. Sort of like a bottle of water between the vacuum and the glassware , right?
this seems like it could be easily made. UGT's page is www.unitedglasstech.com , but check out their auctions on ebay, they have the same stuff they are selling their for a lot
less.
John456
Frequent Poster
Posts: 105
From:
posted 05-30-2001 10:43 PM
--------------------------------------------------------------------------------
Ahh, i see. That can be easily made. My next question is: Will a vacuum pump that can pull 23" of mercury be good for distillation?
PYRO500
Moderator
Posts: 1465
posted 05-30-2001 10:56 PM
--------------------------------------------------------------------------------
can you list the part numbers of the stuff you ordered? I am also looking into setting up a general purpose distillation rig for making nitric acid with amonnium nirtate and
H2SO4. their prices at u.g.t are pretty good too.
10fingers
Frequent Poster
Posts: 411
From: USA
posted 05-30-2001 11:31 PM
--------------------------------------------------------------------------------
I was having the same problems with acid vapors getting into my pump and ruining the oil. I tried a water trap but the water readily evaporates at low pressure and that gets
into your oil. I am now using 2 in.x 8 in.piece of pvc pipe with hose fittings on each end. The pipe is filled with baking soda. There are several layers of filter paper in the pipe
to prevent the baking soda from being sucked into the pump. I have only used this two times and it seems to be working. The soda would have to be replaced periodically.
The pump I have is a refrigeration type which I picked up at a pawn shop for $30.00, it is capable of pulling 30 in. of vacuum, but It seems the whole system works better at
around 15 or 20 in. At high vacuum there is a tendency for the mixture to erupt and spill over into the condenser.
PYRO500
Moderator
Posts: 1465
posted 05-30-2001 11:48 PM
--------------------------------------------------------------------------------
I was thinking of using one of those nitro fuel pumps (for use in nitrus oxide car systems) it can presurize fuel to 100 psi, I was thinking of using one in a water aspirator? do
you think it would work?
nbk2000
Moderator
Posts: 1096
From: Guess
posted 05-31-2001 12:44 AM
--------------------------------------------------------------------------------
You can't use a water trap in a high vacuum system because the water boils off at room temperature or less. It's been ages since I last dealt with such things so I don't know
what you could use to catch the nitric vapors besides a cold trap.
But, I can tell you that grease and pure nitric equals bad! If the grease is silicon, than that should be OK. Wrap the joints with several layers of teflon tape to prevent acid
vapors leaking out, and clips aren't needed if your support clamps are properly set up.
Since you'll be using vacuum, be sure all exposed glassware, especially the flasks, are checked for cracks and scratchs, and wrapped with tape and emplaced in a sturdy
container that will contain the glass and acid in case of implosion, which is a common occurance during vacuum work.
PYRO500
Moderator
Posts: 1465
posted 05-31-2001 01:16 AM
--------------------------------------------------------------------------------
what about a commercial vapor drying and netrulizing trap tube avalible from chromatagraphy supply companys
-A-
Frequent Poster
Posts: 100
From:
posted 05-31-2001 01:50 AM
--------------------------------------------------------------------------------
John456, that's almost the same setup I am waiting for...no money yet, you are a lucky guy. A trap bottle is just that, generally a bottle filled with water, a stopper with two
holes and a tube in each hole. I suggest that you put the trap bottle in a mix of ice and salt to keep the water cool and prevent boiling. A good vacuum pump costs a lot, too
much for me. A water aspirator can be used instead. Make sure you are using thick tubing. Oh, and from the picture I can't see what's the volume of the flasks, but I advise
against using anything bigger than 250ml as an implosion can occur.
c0deblue
Frequent Poster
Posts: 229
From:
posted 05-31-2001 03:34 AM
--------------------------------------------------------------------------------
A quite respectable vacuum pump can be improvised from an old refrigerator compressor. Just be sure to get everything with it you need when removing it from the junked
unit, and cut the tubing long enough so you'll have something to work with. These are pretty efficient, and most can draw down to almost 30" Hg - a LOT stronger than needed
for HNO3 distillation.
Does anyone know whether teflon sleeves for rubber stoppers (or rubber-filled teflon stoppers) are available anywhere?
John456
Frequent Poster
Posts: 105
From:
posted 05-31-2001 01:38 PM
--------------------------------------------------------------------------------
I decided to pick up the 23" Hg vacuum, since it was cheap, working, and wont have quite a big risk of implosion. Pyro, i didnt order the kits in parts, i got the whole thing
from one of UGT's ebay auctions for $125 USD. Hmm, thats bad, my flasks are 250mL, 500mL, and 1000mL (i usually use the 500 and 250 for distilling) Guess ill have to order
another 250mL. How common are implosions, and should i wrap every piece in tape?
C0de: i improvised some teflon sleeves with wideteflon tape, but acid vapors got under it and condensed there, eating the rubber.
Also, forgot to mention, its an oil-less pump. I dont know if that would mean i dont have to worry about a trap, because there would be no oil the vapors would contaminate?
no_name_available
New Member
Posts: 25
From: germany (?)
posted 05-31-2001 07:35 PM
--------------------------------------------------------------------------------
if you dont use such strong pumps so that water wouldnt evaporate at room temperature you should think about what will happen if pressure raise at the pumps site of the
water trap...
PYRO500
Moderator
Posts: 1465
posted 05-31-2001 07:43 PM
--------------------------------------------------------------------------------
uh, then you dont havve a vaccume anymore and water gets blown into the still.
John456
Frequent Poster
Posts: 105
From:
posted 05-31-2001 09:38 PM
--------------------------------------------------------------------------------
Oh yeah, one last question to tack on to the huge list Would using flat bottomed flasks instead of round bottomed ones increase the risk of implosion?
10fingers
Frequent Poster
Posts: 411
From: USA
posted 05-31-2001 10:02 PM
--------------------------------------------------------------------------------
Holy Shit! The flasks you have are not going to implode. This system is designed for vacuum distillations. If you don't want to listen to this advice then you can e-mail the
manufacturer and ask them, I already did. Neither do you have to wrap the joints with teflon tape or put grease on them. If you were to rig up some type of vapor trap using
glass then you would have to take precautions against implosions.
Teck
Frequent Poster
Posts: 146
From:
posted 06-01-2001 02:58 AM
--------------------------------------------------------------------------------
John how much did you pay for the setup?
I want to make soe RDX and this is the only thing stopping me from doing it.
wantsomfet
Frequent Poster
Posts: 236
From: EU
posted 06-01-2001 07:47 AM
--------------------------------------------------------------------------------
I learned to NEVER use flat bottomed flasks etc. with reduced pressure. Look in any good chemistry book. The pressure about 1000g/cm2 in a "normal" aspirator vacuum...
------------------
kangaroooo.cjb.net
Bitter
Frequent Poster
Posts: 290
From: 11 Downing Street, London, England
posted 06-01-2001 09:40 AM
--------------------------------------------------------------------------------
Will a really powerful vacuum cleaner be a sufficient alternative ? By how much (%) of one atmosphere does the pressure need to be reduced by ? I have searched for this
information, but nothing had turned up so far. It think it would help everyone if this value was known.
Plus, isn't there any danger of evaporating the nitric acid ? Surely the nitric boils at a higher pressure than water...
frostfire
Frequent Poster
Posts: 266
From:
posted 06-01-2001 09:51 AM
--------------------------------------------------------------------------------
how exactly in the process do you start the vacuu pump; just as the mixture start boiling or throughout the whole process..?
What I mean is if the pressure inside the apparatus goes far below 1 atm then is it possible the glass won't hold anymore and break (implosion) ???
wantsomfet
Frequent Poster
Posts: 236
From: EU
posted 06-01-2001 10:03 AM
--------------------------------------------------------------------------------
First evacuate the apparature, adjust the vacuum and then start heating.
After the distillation is finished, remove the heat source, let the apparature cool down a bit and then slowly release the vacuum.
SEE ATTACHED IMAGE or go to http://internettrash.com/users/altreal/img65.gif
------------------
kangaroooo.cjb.net
frostfire
Frequent Poster
Posts: 266
From:
posted 06-01-2001 02:10 PM
--------------------------------------------------------------------------------
thx a million
I believe d&e are the vacuum parts (what're they?)
and how does it work at e&f (the cold trap; prevent acid vapor get to the pump????)
Anthony
Moderator
Posts: 2306
From: England
posted 06-01-2001 09:31 PM
--------------------------------------------------------------------------------
Just a little add-on, if you switch the vaccum on as the contents of the retort starts to boil then it will flash boil and shoot through your apparatus
Teck
Frequent Poster
Posts: 146
From:
posted 06-01-2001 09:47 PM
--------------------------------------------------------------------------------
Whats the yeild in nitric acid when using a vaccum and when your not using a vaccum?
Lagen
Frequent Poster
Posts: 174
From:
posted 06-01-2001 09:49 PM
--------------------------------------------------------------------------------
IMHO using any type of grease on the joints not only does not help anything but is downright dangerous with high conc. HNO3.
John456
Frequent Poster
Posts: 105
From:
posted 06-01-2001 09:53 PM
--------------------------------------------------------------------------------
I got 62mL nitric acid using 100g H2SO4 and 105g KNO3 yesterday without a vacuum. I think thats a bad yield though. Im hoping to try it under a vacuum tomorrow.
Teck: I payed $125 for the whole set which included: 500mL round-bottom flask, 1000mL round-bottom flask, 3-way distilling adapter, thermometer adapter with o-ring and
bushing, 200mm Liebig condenser, and vacuum adapter.
Lagen: Silicon grease wont react with HNO3 and it does help reduce leaks.

a n d I m provised C hemistry > storage codes - Archive File
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oracal
New Mem ber
Posts: 13
From :
posted 06-02-2001 07:29 PM
--------------------------------------------------------------------------------
No body so far has known ! If you could tell m e for sure n o t g u e s e s , w h a t t h e l a b s t o r a g e c o d e s t h a t y o u s e e o n
m e g a l o m anias chem ical synthesis section mean . I wou ld be very greatfull .
Lagen
Freq uent Poster
Posts: 174
From :
posted 06-03-2001 08:28 AM
--------------------------------------------------------------------------------
There is a number of very different system s for m arking storage, health and transportatio n properties of chemicals
(pictogram s, risk phrases, safety phrases, ADR classification to nam e a few), am ong these two color-coding scheme s a r e u s e d
frequently: the Chem Alert Label and the SAF-T-DATA Label.
Fisher's Chem Alert Label (as used on Mega's site):

Red Flam mable
Blue Health
Yellow Reactivity
W hite Corrosive
Gray General chemical storage
"S top" Exception--reagent incompatible with other reagents of same
color bar. Store separately.
J.T. Baker's SAF-T-DATA Label is slightly different and a b i t m o r e a d v a n c e d :
R e d F l a m mability hazard: store in a flam m a b l e c h e m ical
storage area.
Red stripe Flam mability hazard: do not store in sam e a r e a a s
other flamm a b l e s u b s t a n c e s .
Yellow Reactivity Hazard: store separately from other
chemicals.
Yellow stripe Reactivity Hazard: do not store with other yellow
c o d e d c h e m icals, store separately.
W hite Contact Hazard: store separately in a corrosion-proof
location.
W hite stripe C ontact Hazard: not com patible with chem icals
in solid white category.
Blue Health Hazard: store in a secure poison area.
Orange Not suitably characterized by any of the
foregoing categories.
Also, according to this system, chem icals should be further arranged into compatible (chem ically related) families in storage.
oracal
New Mem ber
Posts: 13
From :
posted 06-03-2001 09:30 AM
--------------------------------------------------------------------------------
Thanks lagen thats all I needed to know .
Lagen
Freq uent Poster
Posts: 174
From :
posted 06-03-2001 10:33 AM
--------------------------------------------------------------------------------
I h a d a l o o k a t t h e c o d e s i n t h e s y n t h e s i s s e c t i o n a n d I f o u n d s o m e g r e e n o n e s t o o . I a m not sure what th ey m ean but it
s e e m s t h a t t h i s c o d e h a s b e e n d i s c o n t i n u e d . I ' v e l o o k e d a t m a n y o f t h e g r e e n c o d e d c h e m icals directly on Fisher's site and
they all have gray codes now - general storage. Maybe green wa s u s e d t o m a r k b ioreagents or biologically active su b s t a n c e s , I
dunno. I guess only Fisher or Mega could tell you for su re.
If you wanted to mak e a bit of research into the subject, here's a couple of links to get yo u started:
http://keats.admin.virginia.edu/lsm/la bel.htm l
http://www.ilo.org/public/english/protection/safework/cis/products/icsc/dtasht /sym b o l s / i n d e x . h t m
http://www.orcbs.msu.edu/che m i c a l / n f p a / n f p a . h t m l
https://www3.fishersci.com/support/hlth/chemicals.jsp
http://www.electrom ark.com /Help_Hints/DOT/different_dot_classes.asp
http://www.electrom ark.com /Help_Hints/RTK/RTK_FAQ_Index.asp
http://www.chm.bris.a c.uk/safety/riskphrs.htm
http://www.chm.bris.a c.uk/safety/safephrs.htm
http://www.hse.gov.uk/pubns/indg186.htm
This carries a load of safety related links:

http://www.anachem.um u.se/cgi-bin/pointer.exe?Safety

I would like to add that I use the "green" storage to indicate a safe or non-toxic chemical that is largely unreactive, and I use
the gray to indivcate an unknown code.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Need help identifying
acid. - Archive File
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Hvoroba
New Member
Posts: 27
From: Israel
posted 06-03-2001 06:52 AM
--------------------------------------------------------------------------------
I found a product in the supermarket recently, used for plumbing purposes. Most of the products I have seen for this purpose use HCl or NaOH, but the label of this one said
:"Sulfur based acid".
I don't know any other sulfur based acids besides Sulfuric and Sulfurous acid. I was wondering, w hich of the two can be possibly used for a purpose like this? How can I identify
which acid is the one I have (I'm not a chemist)?
One more thing : I found another product for cleaning [that thing you boil water in. sorry ] The label said : "CONTAINS 15% SULFAMIC ACID". What can this be?
Also, I found an another source for H202. It is available at supermarkets as a clothing stain-removing agent, which doesn't contain bleach. The concentration is about 15%.
However, the impurities might be a problem, I have't experimented with that yet though (short of cash).
Thanks!
Cricket
Frequent Poster
Posts: 160
From: USA
posted 06-04-2001 06:29 PM
--------------------------------------------------------------------------------
I think the acid you found is Sulfuric Acid. I think I way to see if it is would be to mix it with some H2O2 and maybe some acetone . This might work w ith other Sulfur based
acids too, but at least you'll have some AP. And good luck on your new source of H2O2 also (now you just need acetone and you'll be good). I think it w ill work.
Hvoroba
New Member
Posts: 27
From: Israel
posted 06-05-2001 07:12 AM
--------------------------------------------------------------------------------
Thank you, but...I should have stated that... I don't need the H2SO4 for AP production. I already have plenty of 30% HCl here, for very cheap. Acetone isn't a problem also.
What I want to do is to remove any impurities from the H2SO4 (w ould distilling help?), and make some HNO3, so I'll be able to make some of the good 'ole nitro
So basically, I just need to check if the acid is H2SO4 or H2SO3, if it's the first, I want to concentrate it (will boiling help? What container?), remove the impurities, and make
some HNO3 with it. Then, the same with the HNO3, and viola, i'll go nitrating everything that lies around. So if you'll have the patience required to help a dumbass such as
myself, your help would be very much appreciated, especially about those concentrating and distilling points.
Sorry for all the dumb and unproffesional questions.
Cricket
Frequent Poster
Posts: 160
From: USA
posted 06-05-2001 06:49 PM
--------------------------------------------------------------------------------
Don't feel bad about asking questions, that's w hat The Forum is for. I haven't done any of this, but here we go. You can concentrate H2SO4 by boiling it. Just bring it to a boil
(don't WAY over heat it, just boil it). You should do this in a good, quality, glass pan, bow l, or cup. I would use something made for use on stoves, so it won't break (had some
very bad experiences with this). Also, do it outside or in a barn or something (if your inside, use a acid mask). Only think is that I think you can only get it to about 95% pure
(not anhydrous). Soooo, it wont dry your nitric and wont make any nitroglycerine (although you can make many other very pow erful secondary explosives without 100% nitric
or sulfuric acid, thank god). If you get your sulfuric acid from a battery, you should filter it. I think a coffee filter will work. Do you know how to make your nitric once you get
your sulfuric? And if you need to know about distilling or anything, you can probably find it on The Forum or Mega's site. I don't know about that stuff, sorry . Good luck.
mark
Frequent Poster
Posts: 195
From:
posted 06-05-2001 07:10 PM
--------------------------------------------------------------------------------
What kind of acid can be found in an ace hardware of safeway? I need acid to make Ap, and I need to know where to look.
What w as the name of the cleaning product you found acid in?
Anthony
Moderator
Posts: 2306
From: England
posted 06-05-2001 08:17 PM
--------------------------------------------------------------------------------
I believe you can get H2SO4 to 98% by boiling. If you know the starting conc. of your acid it's w orth marking the level to start w ith and boiling dow n to a level where all w ater
in the acid would have gone.
The resulting acid does work in nitrations (e.g. NG).
BTW, you won't find shit in Safeways!
shooter3
New Member
Posts: 37
From: USA
posted 06-05-2001 09:56 PM
--------------------------------------------------------------------------------
Ace is the place. "RAM OUT" drain cleaner is Sulfuric Acid.
ALENGOSVIG1
Moderator
Posts: 766
posted 06-06-2001 12:08 AM
--------------------------------------------------------------------------------
You can do almost all simple nitrations (NG, NC , EGDN, PA, ETC) Without nitric acid. Theres not too much point ion attempting do distill nitric acid without vacuum and proper
distilation jointed glassware unless you dont need too high of concentration.
------------------
Explosives Archive
Hvoroba
New Member
Posts: 27
From: Israel
posted 06-06-2001 08:07 AM
--------------------------------------------------------------------------------
Thanks!
The brand is named "DRAIN OUT" (how original). However, I doubt you will find this brand at your stores in civilised Europe, since I live in this hell-hole Israel, and I think the
acid is a local brand.
So if the acid isn't anhydrous, does that mean I can't make any HNO3 with it? Or can I?
ALENGOSVIG1, but I thought you must have nitric acid for all nitrations, or have I missed something?
Anthony
Moderator
Posts: 2306
From: England
posted 06-06-2001 04:21 PM
--------------------------------------------------------------------------------
HNO3 can be made in the reaction by mixing H2SO4 and a metal nitrate (e.g. KNO3). So to make NG you just mix KNO3 w ith H2SO4, then add your glycerine to this mix.
mark
Frequent Poster
Posts: 195
From:
posted 06-06-2001 06:51 PM
--------------------------------------------------------------------------------
Thanks shooter! What concentration is it?
shooter3
New Member
Posts: 37
From: USA
posted 06-06-2001 07:43 PM
--------------------------------------------------------------------------------
Mark. I'm not sure. A one quart bottle is pretty heavy though. It boils dow n very quickly. Check the Sp. Gravity w ith a battery checker. Good luck.
mark
Frequent Poster
Posts: 195
From:
posted 06-07-2001 07:12 PM
--------------------------------------------------------------------------------
Have you used it to make AP?
PYRO500
Moderator
Posts: 1465
posted 06-07-2001 07:43 PM
--------------------------------------------------------------------------------
that wont tell him much except it is an acid the acid dosent make ap it is just a catalyst that dosent chamge throughout the reaction
mark
Frequent Poster
Posts: 195
From:
posted 06-07-2001 11:28 PM
--------------------------------------------------------------------------------
I was wondering because if there is impurities in the acid, wont that fuck with the ap?
PYRO500
Moderator
Posts: 1465
posted 06-08-2001 01:16 AM
--------------------------------------------------------------------------------
it might make the ap more sensitive but ap w ill still be produced!
Mr Cool
Frequent Poster
Posts: 991
posted 06-09-2001 05:46 PM
--------------------------------------------------------------------------------
The drain cleaner acid is sulphuric, normally about 90% concentration. Heating to 300*C or so w ill get it to above 98% (H2SO4 boils at 327*C IIRC). Do this with excellent
ventilation, or you'll be coughing like hell.
And check that the container you're pouring the acid into is 100% dry. I left a drop of water last time, and got boiling, concentrated acid on my thumb. VERY FUCKING STUPID
OF ME! Hurts like shit, believe me. Luckily it w as only a splash, and the rest of me was well protected, w ith 3 layers of clothing and a full face shield. I never w ear gloves
though, since it increases the risk of an accident. Lucky I had my bucket of cold NaHCO3 solution next to me That's a very good precaution, just in case. I got my thumb in
there in less than a second, and then ran cold water over it for 20 mins and it still burnt me nastily. Mainly a heat burn though, the H2SO4 didn't have time to get through the
first layer of dead skin.
Sulphamic acid is HSO4NH2, used in one method for making RDX IIRC. If I still have it I'll post it here.
If you're H2SO4 is 100%, and your KNO3 is 100% , then the HNO3 you get will be 100%, even w ithout a vaccuum source. It'll be the fuming red/brown kind. You do need a
good condenser to keep efficiency up and save you from dying of NO2 poisoning, and rubber stoppers w ill dissolve into a crumbly mush. Use quick-fit glass equipment.
mark
Frequent Poster
Posts: 195
From:
posted 06-10-2001 04:16 PM
--------------------------------------------------------------------------------
Container must be cmpetley dry? To make ap, arent you mixing the acid with tw o other liquids?
Does ace sell hydrocloric acid? Any other Acids less scary than sulfuric?
[This message has been edited by mark (edited June 10, 2001).]
blackadder
Frequent Poster
Posts: 313
From: London
posted 06-10-2001 06:27 PM
--------------------------------------------------------------------------------
He's not talking about making AP!!!
He's referring to when you purify H2SO4 and pour it into another container.
yt2095 June 20th, 2003, 08:39 AM

if i were uncertain as w hat the acid w as, i think i`de try and make copper sulphate from it and examine the crystals shape, color, soluability
thought i`m absolutely certain there are mush better ways to find out with simple equipment.
it`s only my 10cents worth :)
it would be worth trying to concentrate it though, then dilute it w ith a known quantity of distiled w ater then do a hydrometer test and a PH test.
thats about the best i can come up with off the top of my head.
if you know someone that works w ith forklift trucks, ask w here they buy their acid from, then go there w ith a 2 litre plastic pop bottle and ask for some. tell then that you`re
working on a Solar pannel arangement and have kept batteries stored w ith just w ater in them, and now you need to re-activate them (that`s how i get mine)
Good luck :)

pH test is useless for identifying a strong acid, as all strong acids w ill produce the same pH at a give concentration because of the nivellation effect. This means that in w ater all
strong acids fully dissociate and thus have effectively the same strength.
If you want to compare them you'll need an acidic medium like CH3COOH and then you can check which acid will most effectively protonate CH3COOH to CH3COOH2 +.
However, you cannot measure pH in other mediums than water....
Sulfamic acid is often use to remove CaCO3 from water boilers, coffeemachines, etc.
I thought it was quite a weak acid but since it can apparently be used to make RDX? Have you got anymore info on this Mr. Cool?
Barium, strontium and calciumsalts will all produce insoluble sulfates with sulfuric acid (and ofcourse w ith any other solution that contains sulfate ions).

Copper will not react with Sulfuric acid to give Copper sulfate (unfortunately). So as Vulture said you would have to react it w ith the the Group II elements if you w anted to try
and make a sulfate to test the acid.

Copper will react w ith concentrated sulfuric acid when slightly heated, after that the reaction becomes selfsustaining and is quite vigorous. It's true that H+ won't attack metals
like copper, unless you are dealing with an oxidizing acid like H2SO4 which is reduced to SO2 by copper. Careful smelling will reveal this.

Thank you Vulture, I didnt know that and I've been w anting some copper sulfate. PH test is useless for distinguishing a strong acid from a different strong acid, but it might be
helpful in determining whether an acid IS a strong acid. IIRC H2SO4 is the only strong sulfur based acid, so if a PH test reveals that it is a strong acid than you have your acid.
Isn't the PH of H2SO4 lower than that of a monoprotic strong acid? When H2SO4 is dissasociated it gives two H+ ions thus doubling the concentration of H+ is that right?

Not really.
The second dissociation of sulfuric acid has a pKa of 1,94 IIRC. This means that HSO4- is a moderatly strong acid. Because the first dissociation step is complete, this w ill hamper
the second dissociation in compliance with Le Chateliers principle.
Thus, the second dissociation will only be substantial in a fairly diluted solution.
The second dissociation becomes noticeable above a pH of 2,4.
This also explains why conc. H2SO4 w ill form HSO4- salts when reacted with other salts like KNO3.
Furthermore, pure sulfuric acid (> 98% ) autoprotonates itself:
2H2SO4 -----> H3SO4+ + HSO4-
EDIT: Actually, adding relatively pure copper to a supposedly H2SO4 solution might be a good w ay to identify H2SO4. You w ill smell SO2 gas and the solution will turn deep blue.
Ofcourse it's also a good way to identify copper metal...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > NH4ClO3 - Archive
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the_wingman
Frequent Poster
Posts: 49
From:
posted 06-03-2001 10:48 AM
--------------------------------------------------------------------------------
I was just wondering if somebody knows whether ammonium chlorate is really that sensitive as everybody says ("neeeever!!!! mix an ammonium salt with a chlorate!!!").
I'm not completely convinced of the danger beause I often mix KClO3 with sulfur and never something happens. And this is also a mixture that "should be avoided at all costs".
Mr Cool
Frequent Poster
Posts: 991
posted 06-03-2001 10:58 AM
--------------------------------------------------------------------------------
If you keep mixing KClO3 with S then eventually it WILL go off. You might get away with it hundreds of times, but eventually you'll have an accident.
The same is true with NH4ClO3. Just because you make it doesn't mean it'll explode, but there is a chance. And that chance isn't worth taking.
the freshmaker
Frequent Poster
Posts: 175
From: Heaven
posted 06-03-2001 02:26 PM
--------------------------------------------------------------------------------
pretty much like CTAP, would I say!
------------------
good boy with bad ideas
kingspaz
Frequent Poster
Posts: 347
From: UK
posted 06-03-2001 05:09 PM
--------------------------------------------------------------------------------
Has anybody here actually made ammonium chlorate?
If so how good would it be for a primary explosive?
Fallout85
Frequent Poster
Posts: 55
From: U.S.
posted 06-05-2001 10:43 PM
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Look at www.boomershoot.org

Ammoniumchlorate can be isolated in very small amounts when handled very carefully and spread out in a very thin layer. The product will decompose explosively eventually,
seemingly without reason.
I have a way of preparating it, which I will not post here. There's a reason why...
Ollie Snowie September 11th, 2003, 03:36 PM

I'm not sure about it being sooooo sensitive. I once tried a very small amount of NH4Cl mixed with NaClO3 weedkiller. Nothing happened. I moistened it. Nothing happened. I
heated it with a blowtorch. Nothing happened (not even NH4Cl smoke forming(the wood around it was glowing red so it definitely was hot)). Do you think that whatever is in
the other 50% of the weedkiller was stopping it forming NH4ClO3. I thought the fire depressant was just NaCl and I don't see how this would interfere. I also tried electrolysing
NH4Cl solution at a moderate temperature and still nothing happened. Maybe it isn't so sensitive as people make out, but from what i've concluded, it's not much use either,
and it emits nasty fumes when it explodes (IF it does).
On the other hand, I might not have made it at all. I'm not encouraging anyone to blow a hand off, and from what vulture says it is pretty sensitive, and he's probably right.
vulture September 11th, 2003, 03:47 PM

I've got this information from a German book, sixties. I can't remember the name right now, but it came from the uni library.
I think your reaction didn't form anything nasty because there was alot of inert NaCl in it and the solubility of the products and reactants doesn't differ very much, resulting in
poor yield.
Sparky September 11th, 2003, 06:04 PM

Ammonium chloride is the one salt that is considered 'safe' to use with chlorates, though I'm not sure why this is. It is used in smokes a lot.
Vulture, it surprised me when you said you would not post how to make it. I considered the issue I think you're overreacting. Certainly people here understand (or they will ;))
that it is of no practical use and wouldn't try to actually use it for anything except to make it as an experiment. Anyways I decided to post part of Shimizu's Fireworks: The Art,
Science and Technique. It's quite simple so it's not like anyone couldn't figure it out anyways. The information about it that comes after the synthesis is interesting too.
"
Ammonium perchlorate and pottasium chlorate can cause a double decomposition to produce ammonium chlorate and potassium perchlorate when they are mixed in a wet
state:
NH4ClO4 + KClO4 --> NH4ClO3 + KClO4
Ammonium chlorate decomposes gradually at room temperature. Needless to say compositions which contain ammonium perchlorate and potassium chlorate must be avoided.
An experiment for producing ammonium chlorate by above reaction can be carried out as follows: add 35 grams of potassium chlorate, KClO4, to 100 ml. water and dissolve it
with heat. Add 36 grams of ammonium perchlorate, NH4ClO4, to the solution and stir it well when a large quantity of white crystals will appear; these are almost all potassium
perchlorate. Leave it to cool to room temperature. Remove the crystals by filtration. The remaining liquid is mainly ammonium chlorate. Evaporate the mother liquor to about
30 ml. on a water bath. Cool it to room temperature and the ammonium chlorate will crystalize out as a crude product. Remove the crystals from the mother liquor. Dry the
crystals leaving them at room temperature. The amount of ammonimu chlorate thus obtained is about 19 grams. The yield is about 55~63% of the theoretical value.
This substance, NH4ClO3, decomposes gradually, generating a yellow-brown gas which smells strongly of chlorine. The degree of decomposition is about 50% of the original
amount at an average temperature of abotu 26oC over 35 days. A quantity of ammonimu chlorate thus prepared nwas stored in a glass bottle which had a loose filling (sic)
rubber stopper and left at room temperature during the summer; in 48 hours it decomposed explosively, breaking the bottle.
Ammonium chlorate, NH4ClO3, alone explodes on strong impact, but it is not so sensitive to shock and friction in the absence of other combustible substances. A mixture of
ammonium chlorate and shellac in the right ratio 10:2 burns with a rate of 1.2~1.3 mm per second, producing a slight yellowish flame. This burning rate resembles that of
potassium chlorate composition.
tmp November 25th, 2003, 04:08 AM

I don't know how unstable NH4ClO3 is. But from the description of the last reply
I won't mess with this one. The Code Of Federal Regulations lists this, among
many other substances, as FORBIDDEN to transport by any means. If I were to
synthesize this, I would probably use my favorite metathesis reaction that yields
a relatively insoluble compound. I like to mix a hydroxide or sulphate of one
compound with a calcium compound. The precipitate is either calcium hydroxide
or calcium sulphate which filters out easily. In this case I would mix ammonium
sulphate and calcium chlorate. The calcium sulphate should precipitate out leaving
the ammonium chlorate in the solution.

NH4ClO4 + KClO4 --> NH4ClO3 + KClO4
That equation's not balanced...
fire vs. water November 25th, 2003, 05:22 PM

I think he meant KClO3 in the left side of the equation...
he said
ammonium perchlorate + pottasium chlorate => ammonium chlorate + pottasium perchlorate

Ah, ofcourse, how silly of me. So the driving force is the insolubility of KClO4.
This seems a rather dangerous method however. If it detonates when still reacting you have NH4ClO4 which could explode too.

a n d I m provised C hemistry > potassium to potassium nitrate - Archive File
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m yo u n g b h s 0 3
New Mem ber
Posts: 4
From : W est Virginia, US
posted 06-11-2001 12:58 AM
--------------------------------------------------------------------------------
i am having trouble finding potassium nitrate b ut i found potassium is th ere anyway to convert it?
i h o p e n o o n e h a s a s k t h i s b e fore because i se arched a nd i fear the criticism
-A-
Freq uent Poster
Posts: 100
From :
posted 06-11-2001 01:57 AM
--------------------------------------------------------------------------------
Y o u f o u n d p o t a s s i u m b u t n o t p o t a s s i u m nitrate???. I must say that, at least for me, is the exact o pposite.
W ell, potassium nitrate is formed by the reaction of potassium with nitric acid.
K + HNO3 --> KNO3 + H (as H2)
But this reaction is far too dangerous and costly to make potassium nitrate in apreciable amounts.
ALENGOSVIG1
Moderator
Posts: 766
From : V a n c o u v e r , C a n a d a
posted 06-11-2001 04:10 AM
--------------------------------------------------------------------------------
I find that a good source for potassium nitrate is a hydroponics store. U nderwater plant growing. Its very pure and it like
$15.00 for 2.5 kg's.
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How much power will you lose if you do not know what they already know?
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J
Moderator
Posts: 602
posted 06-11-2001 06:42 AM
--------------------------------------------------------------------------------
If you search the forum, you'll find ways to convert NH4NO3 to KNO 3, as well as m any other sources (garden centers etc) for it.
I personally wouldn't waste the K (and HNO3 for that m atter) on this.
------------------
Download the forum archive from m y y a h o o b r i e f c a s e
Anthony
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Posts: 2306
From : England
posted 06-11-2001 06:11 PM
--------------------------------------------------------------------------------
Mixing potassium with a very strong oxidiser like HNO 3 has got to be asking for a very large explosion...
You could ha ve only gotten K from a lab supplier and all lab sup pliers carry KNO3, so are you sure its pure K and not a K
compound?
CodeMason
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Posts: 383
posted 06-11-2001 06:22 PM
--------------------------------------------------------------------------------
Dude, I don't think he actually found K, I just think he found a bag of fertilizer that said "16% potassium " o r t h e r e a b o u t s a n d
he thought it m e a n t e l e m e n t a l .
m yo u n g b h s 0 3
New Mem ber
Posts: 4
From : W est Virginia, US
posted 06-13-2001 12:08 AM
--------------------------------------------------------------------------------
well i called walm a r t a n d i a s k e d i f t h e y h a d p o t a s s i u m nitrate
they said that they only had p otassium
is hydroponics the sam e a s h y d r o s e e d i n g ?
Anthony
Moderator
Posts: 2306
From : England
posted 06-13-2001 08:29 PM
--------------------------------------------------------------------------------
They meant they have a fertiliser that contains a large num b e r o f p o t a s s i u m a t o m s , t h e s e a t o m s are howe ver com p o u n d e d ,
s o i t c o u l d o n e o f m a n y p o t a s s i u m c o m p o u n d s . A l t h o u g h KNO3 is said to be the fertiliser with the highest a m o u n t s o f
potassium, so it *cou ld* be KNO 3 but it probably isn't b e c a u s e p l a c e s l i k e W al*Mart usually sell useless shit.
yt2095 June 20th, 2003, 10:03 AM

d i s s o l v e s o m e and te st with litmus, if it goes blue, it could also contain P otassium carbonate.
all`s not lost tho as i use K2CO 3 for sodium conversion in Chlorates and Nitrates.
the litmus test however isn`t a YES if it`s blue, it`ll only be a NO if stays sam e or goes red )unless countered in solution by
s o m ething equaly acidic) but that would cause a reaction anyway, and so no.
i`de lay wager that wal-m art d oes not stock Potassium (if it did, i`ll consider im migrating) :)
see if you can get hold off "nitrate of potash"

at a push "nitrate of soda" but you`ll need to convert the soda nitrate later (time consum ing but worth it if you have no other
way)
a good thing to look for on these bags in the fertiliser dept, is som ething called the N-P-K ratios
Nirogen Phosphorous Potassium
try and keep the m iddle num ber as low as possible 0 would be ideal!
if the N and K numbers are both sim ilar then that will be a good source o f your potassium nitrate :)
if the N is m uch m uch higher or even 99-0-0 than you`ve got AN :) worth buying just to keep till you need it (just in case they
decide to ban that too)
if yo u do a search on here, the NPK is m u c h b e t t e r e x p l a i n e d t h a n i c a n p o s s i b l e h o p e t o i n o n e p o s t !
all the best :)

a n d I m provised C hemistry > R efluxing - Archive File
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10fingers
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Posts: 411
From : U SA
posted 06-18-2001 03:24 PM
--------------------------------------------------------------------------------
I s r e f l u x i n g t h e s a m e as fractional distillation? Would you use a vigreux column for this process?
I was just reading a process for m a k i n g e t h a n o l fuel from corn. They describe how to make a reflux distillation colum n which
can give you a high p urity of alcohol,(95%) on one pass through. That's starting with a m ixture of 90% water and 10% ethanol.
I t s e e m s t h i s s a m e s y s t e m c o u l d a l s o b e u s e d f o r s e p a rating nitrom ethane from hobby fuel. It also m ight work for distilling
acetic acid to get all the water out. I have som e app. 80% acetic acid and I have distilled from sulfuric acid three tim e s u n d e r
vacuum and it still ha s water in it.
John456
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Posts: 105
From :
posted 06-18-2001 03:45 PM
--------------------------------------------------------------------------------
Refluxing is when you boil a liquid and condense it back into the sam e f l a s k . I t s u s e d i n m o s t o r g a n i c s y n t h e s e s t h a t t a k e
hours or days to perform. All you have to do is put a condenser in the top joint of a flask and run cold wate r through the
condensor th roughout the procedure. If you want to protect your reaction from water you p ut a drying tube filled with som e
drying agent (Calcium chloride is a popular one) at the top of the condensor.

I just install m y liebig cooler vertically without the destillation bend. However, I did once operate it vertically using the 2 bends
to create a 180C turn which went into the distilling flask.
This way you can achieve a higher separation b etween closely boiling liquids.
It should not be used this way for distilling acid s like HNO3 that decom p o s e b e c a u s e y o u ' l l n e e d t o h e a t m uch m o r e t h a n
during a norm al destillation. That's also why a vigreux colum n shouldn't be used for distilling HNO3.
I've got pics (B&W ) if anybody is interested.
BTW , the spot where the condensing starts should m aximally reach 1/3 of the total length of your cooler if you leave it open
on the topside! Certainly with flam m able or harmful com p o u n d s !
Refluxing is not the same as fractional destillation. Fractional destillation separates several boiling fractions by rotating a
special piece of glass with multiple flasks connected to it.
The fractions are collected by boiling point.

a n d I m provised C hemistry > C hlorine by HCl an d MnO 2 - Archive File
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Rhadon
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From : Germ a n y
posted 06-29-2001 06:32 PM
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Does anybody know which reaction takes place when HC l and Mn O2 react to chlorine? There are three possibilites:
1) MnO2 + 2 HCl -> Cl2 + MnO + H2O
2) 2 MnO 2 + 2 HCl -> C l2 + Mn2O3 + H2O
3) 3 MnO 2 + 4 HCl -> 2 Cl2 + Mn3O 4 + 2 H2O
I need to know that because I want to get the m a x i m um yield.
T h a n k s i n a d v a n c e f o r your help.
jin
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Posts: 111
From : u k
posted 06-29-2001 08:52 PM
--------------------------------------------------------------------------------
i got this from a old chemistry book
M n O 2+4HCL=MnCL2+H2O+C L 2
[This message has been edited by jin (edited June 29, 2001).]
Rhadon
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Posts: 95
From : Germ a n y
posted 06-30-2001 05:03 AM
--------------------------------------------------------------------------------
Thanks for your help.
Y e s , y o u r o n e s h o u l d a l s o b e p o s s i b l e . P r o b a b l y s e v e r a l d i f f e r e n t reactions take place.
Hm m, this m akes it hard for me to calculate the am o u n t s o d c h e m i c a l s n e e d e d .

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Microtek
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posted 06-28-2001 05:05 AM
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First, let m e a p o l o g i z e f o r w h a t s o m e m ay see as repetitious, but I think that this deserves specific attention.
In an old chemistry book that I have, it is stated that when acetylene gas is bubbled through acetic acid you get acetic
anhydride and acetaldehyde.
This would be a m uch easier way to ge t acetic anhydride from 99% acetic acid, an d i f r e a s o n a b l e a m o u n t s o f a c e t a l d e h y d e i s
produced and could b e distilled off....
So the question is: Can you simply bubble acetylene gas through the acetic acid at perhaps 25 degrees and condense the
acetaldehyde, or do you need katalysts or certain temps, etc.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
posted 06-28-2001 07:58 AM
--------------------------------------------------------------------------------
Let's figure that out...
H-C#C-H + CH3-C(=O)-OH --> H2C=C HOH + C H2=C=O
Basicaly you have a dehydration of acetic acid into ketene and in the same time hydratation of acetylen in vinylic alcohol.
Ketene can react further with an exces molecule of acetic acid to give ace tic anhydride.
C H 2 = C = O + H O C O - C H 3 - - > C H3-C O - O - C O - C H 3
Vinylic alcohol or ethenol/ethylenol is in equilibrium with the m o r e s t a b l e i s o m er (due to enol-ceton equilibrium ).
CH2=CHOH <-===> CH3-CH=O (acetaldehyde or ethan al)
Now you can also have some other pro d u c t s d e p e n d i n g o n t h e e x p e r i m ental cond itions like vinyl acetate CH2=CH-O -C O - C H 3
and polyvinylacetate, and ...
M y g u e s s i s t h a t p r e s s u r e h a s t o b e a p p l i e d , s o m e h e a t , s o m e c a t a l y s t , a n d p o l y m erisation inhibitors. I can't tell you

m ore...you'll have to find it out (a little tial?).
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Microtek
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From :
posted 06-28-2001 05:00 PM
--------------------------------------------------------------------------------
I tried simply bubbling the acetylene through the 99% acetic acid. No cooling, no heating, no catalyst and no success...
After having passed the acetylene thro ugh for 30 min, I tried cooling the liquid down to se e if it fro ze, since glacial acetic acid
freezes at ca . 15 C and the anhydride at ca. -70.
At first, I thought that it had worked as I got to ca. 5 C and it was still liquid, but when I decreased the tem p to -18 C it froze
solid.
Is it concievable that there was some anhydride in it, or does the two ( acetic acid /anhydride ) not coexist?
Mr C ool
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Posts: 991
posted 06-29-2001 04:52 PM
--------------------------------------------------------------------------------
T h e y m u s t b e a b l e t o coexist, otherwise you couldn't m ake acetic anhydride by bubbling k etane or whateve r it is through acetic
acid, since it can't all be converted at once so at some point there m u s t b e a m ixture of the two.
I ' d g u e s s t h a t y o u ' d n e e d h e a t t o m ake the reaction proceed (or at least at a rea sonable rate), pressure to stop an ything
boiling away, m aybe polymerisation inhibitors since thin gs tend to polymerise faster at higher temperatures (like all reactions),
and maybe a few catalysts to help it along.
But if you got the mixture down to -18*C, then it can't be just acetic acid anymore...
How does it smell? Does it burn? If so, how well? Does it heat up on contact with water? How acidic is it?
O h , a n d I ' d b e c a r e f u l about bubbling acetylene into you house for 30 minutes! (I'm a s s u m ing you did it outside, right?)
c0deblue
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Posts: 229
From :
posted 06-29-2001 05:45 PM
--------------------------------------------------------------------------------
I'd also be careful about using too much pressure with acetylene - from what I un derstand, the m a x i m u m p r e s s u r e p e r m issible
with the dry gas is about 30 psi; any higher and it self-combusts. I don't know, but applying heat m ight lower this point. The
300 psi acetylene in tanks is achieved by drivin g it into solution in acetone (that's why ace tylene tanks are so heavy), but I
think any attem pt to pressurize acetylene directly is asking for trouble. This would almost certainly be the case in a sealed
reaction vessel.
Very interesting possibilities though, and I agree that the depressed freezing point is evid ence tha t * s o m e * c h a n g e h a s t a k e n
place. I wonder if (instead of bubbling) one could calculate the amount o f acetylene needed to completely react with a given
a m ount of acid, seal those qu antities in a cham b e r a n d s h a k e h ell out of it for a few hours (for exam ple with a paint shaker).
A process like that would certainly encourage m ore complete rea ction, assum ing reaction pressures rem ained within safe limits.
Another possibility m ight be to use an ultrasonic atomizer (hum idifier type) to spew a m icrofine acetic acid m ist into an
atmosphere of acetylene (in a closed chamber). Not exactly a vapor phase reaction, I kno w, but ought to provide am ple
opportunity for the reactants to come into intim ate contact.
John456
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Posts: 105
From :
posted 06-29-2001 10:01 PM
--------------------------------------------------------------------------------
Heres what i did: I took one o f those vacuum trap jars (the kind with the vacuum connector at the bottom of the jar and the
stop per with 2 connections, one for a vacuum a n d o n e f o r a b u b b l e r ) a n d c o n n e c t e d a n a c e t y l e n e g e n e r a t o r ( a n e h r l e n m e y e r
flask with calcium carbonate and water) and left the vacuum connector one open. The idea was for the aquarium pum p to
create a sort of acetic acid mist so the acetylene gas wo uld touch more of the acid. After h alf an hour of bubbling the acetylene
i took it off the generator and poured the product into a beaker. First i tested the flam mability (apparently none at all) and
then i took 1 0ml of it and added it to 5m l of water and it got a little warm but not m uch warmer than it was. W hen i was
bubbling the gas in it did get notibly warmer though. Th en i tried freezing it and it froze at about 5 *C. PURE acetic acid and
acetic anhydride can coexist but the presence of any water will convert the anhydride back into acid . W h a t i t h i n k i s h a p p e n i n g
is some vaporized wa ter is com ing ove r with the acetylene gas and thats causing any anhydride converted to convert back to
acetic acid. P erhaps drying the acetylene will so lve this problem ? Does anyone know how to dry it? C alcium chloride m ight react
with the gas to form calcium carbide again so i dont think that would work. Possibly calcium oxide?
PHILOU Zrea lone

Freq uent Poster
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posted 07-04-2001 08:45 AM
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Microtek:
Two liquids m ixed together have a lower m eltin g point than the original products...that's cald cryoscopic lowering of the MP...an
im pure product has a lower MP than the origina l pur product even if the im purity has a higher MP.
So with a MP of 18 instead of 15, I would say it is only your glacial H-AC being in overmelting!
------------------
deezs
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Posts: 113
From : Hungary
posted 07-04-2001 02:23 PM
--------------------------------------------------------------------------------
I h a v e r e a d s o m ewhere, that clear acetic acid, containing just ab out 1% water, fre ezes at 5 deg. (it m e l t s a g a i n a t 1 6 d e g . )

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > more concentrated
H2SO4 from car batteries - Archive File
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kingspaz
Frequent Poster
Posts: 360
From: UK
posted 06-21-2001 05:33 PM
--------------------------------------------------------------------------------
well i was reading through something about car batteries on my computer on the comptons encylopedia and i found this:
The 12-volt battery commonly used in automobiles has six 2-volt cells connected in series. The electrolyte is dilute sulfuric acid. Each electrode is made of connected plates.
Between the two sets of plates are thin separators made of wood, glass, or plastic that do not enter into the chemical reaction. The separators are porous so that electrolyte
can flow around the plates.
Each plate has a framework, or grid, made of a hard alloy of lead and antimony. The grid of a new positive plate is filled with lead dioxide (PbO2). The negative plate contains
spongy metallic lead.
Lead dioxide attracts electrons more strongly than metallic lead and starts drawing current when the external circuit is closed. This leaves lead ions (Pb++) in the negative
plate. Each of these ions draws a sulfate ion (SO4=) from the solution, making lead sulfate (PbSO4) in the negative plate.
This leaves free in the solution two hydrogen (2H+) ions for each sulfate ion withdrawn. Oxygen ions released by the lead dioxide join the hydrogen ions, forming molecules of
water (H2O). This action keeps the positive plate clear to draw current. Since there is no polarization, the battery works as long as any acid is left to furnish sulfate ions and
until each plate contains lead sulfate only. Once this condition is reached, the battery can be recharged by sending current through it in reverse. This changes lead sulfate in the
plates back to lead dioxide and spongy lead and restores acid to the solution.
So this means that if you charge the car battery before you extract the acid then you'll get acid of a higher concentration and purity
mongo blongo
Frequent Poster
Posts: 175
From: I live in a Creosote Bush!
posted 06-21-2001 08:36 PM
--------------------------------------------------------------------------------
i think that sounds right the battery should be charged and is not much use after the battery has been used.but i think u can buy it from gararges for electrolite topp ups (u
know then just boil it)
10fingers
Frequent Poster
Posts: 415
From: USA
posted 06-21-2001 09:54 PM
--------------------------------------------------------------------------------
This is a good point to bring up. If you try to get sulfuric acid from a dead battery you will not get much. Car batteries that have been discarded usually have little sulfuric acid
in them. Plus it will have lead contaminants in it.
It is much better to go buy battery electrolyte from an auto parts supplier. From 5 gallons you can get 1.6 gallons of conc. acid.
kingspaz
Frequent Poster
Posts: 360
From: UK
posted 06-22-2001 04:45 PM
--------------------------------------------------------------------------------
thanks guys. my biggest problem however at the moment is not a matter of chemicals but equipment. i've been searching second-hand shops and car boot sales for a glass
pan to boil acids in. i can't find anywhere in the uk that will send things to individual.
10fingers
Frequent Poster
Posts: 415
From: USA
posted 06-22-2001 06:46 PM
--------------------------------------------------------------------------------
Go to a 2nd hand store and buy a glass coffee pot. These work well but to be safe only place a small quantity in the pot the first time in case it breaks. Heat the acid until it is
giving off dense white smoke, continue this for about 15 minutes. DO NOT touch or move the pot until the acid has cooled down. One the worst things you could possibly get
on yourself is hot sulfuric acid.
Always check the pot for small cracks after each use and discard it if you find any.
jin
Frequent Poster
Posts: 113
From: uk
posted 06-22-2001 07:51 PM
--------------------------------------------------------------------------------
you can get large pyrex pans from index or argos.you can boil sulphuric acid to a high concentration in them.
[This message has been edited by jin (edited June 22, 2001).]
Anthony
Moderator
Posts: 2383
From: England
posted 06-22-2001 08:06 PM
--------------------------------------------------------------------------------
Kingspaz last time I concentrated some H2SO4 I used a 1L Pyrex measuring jug. It's got a scale on the side, a pouring sout and will take any heat you can give it. Cost was a
few quid from a supermarket. You can get pyrex in shapes and sizes from jugs to dishs, bowls, cylindrical doodads that are like beakers etc etc. It's all over the place I can't
beleive you can't find something suitable.
kingspaz
Frequent Poster
Posts: 360
From: UK
posted 06-23-2001 04:04 PM
--------------------------------------------------------------------------------
thanks guys. i've looke in index but i couldn't find anything. i'll keep looking though.
anthony, on another post i asked if stainless steel would work. anyways you said it should work and i tried it today and it didn't. however it did make alot of what i guess to be
chromium sulphate. well whatever it was it was very dark green. when i emptied the container it was severly corroded. oh well i'll have to keep searching for somthing glass.
Donutty
Frequent Poster
Posts: 228
From: UK
posted 06-23-2001 04:37 PM
--------------------------------------------------------------------------------
I got mine from Wilkinsons. Even though it is Pyrex, make sure you don't 'shock' it. I placed mine on a cold tile and guess what?
D'oh!
Anthony
Moderator
Posts: 2383
From: England
posted 06-24-2001 09:36 PM
--------------------------------------------------------------------------------
Hmm, I *thought* stainless was acid resistant, although I may have been thinking of aluminium which is *apparently* HNO3 resistant. A good example of why you should
check things people say and not trust my dodgy memory In theory a cheap teflon coated saucepan should be able to handle just about anything (as long as none runs down
the side) although I managed to strip the teflon off a pan with a sodium bicarbonate solution!
Argos sell a glass "chopping board" for less than 5, I think it's worth having as it's stopped me burning holes in my workbench with acid/hot pyrex.
10fingers
Frequent Poster
Posts: 415
From: USA
posted 06-24-2001 11:45 PM
--------------------------------------------------------------------------------
There are different types of stainless steel, magnetic and nonmagnetic. I think the latter is resistant to nitric acid. In KIPE 2 it describes how to make a nitric acid still, in this he
uses type 316 stainless steel tubing.
Aluminum is resistant to nitric acid at lower temps but not at temps required for distillation.
[This message has been edited by 10fingers (edited June 25, 2001).]
Tony Montana
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Posts: 145
From: Australia
posted 06-25-2001 03:56 AM
--------------------------------------------------------------------------------
I have concentrated battery acid numerous times, since its one of the only practical ways I have of obtaining H2SO4. You do not need exotic glassware for this one, I like the
suggestion about the coffe pot though. In the past I used a large pasta sauce jar, it had an approximate measure down the side, and was made from thick glass.
I filled a frying pan with oil and put a home made stand in it so the jar did no rest on the bottom of the pan. Out of a new battery expect to yeild 1/4 of what you started with,
canning jars can also be purchased very cheaply. And they are heavy duty glass, they hold boiling acids no worries(or none yet).
kingspaz
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Posts: 360
From: UK
posted 06-25-2001 05:43 PM
--------------------------------------------------------------------------------
well i think the stainless holds it at lower temperature because it started to foam and bubble once the temperature increased. does the non-stick coating on pans get eaten by
acid. these pans are available everywhere...i could use a big coffe jar i have but i want something that i can trust not to shatter everywhere because i don't want to take the
risk of getting concentrated, 100* H2SO4 on me. thats got to be the one of the worst things you could spill on your self.
Anthony
Moderator
Posts: 2383
From: England
posted 06-25-2001 08:38 PM
--------------------------------------------------------------------------------
From my experience jars don't explode if over heated (only to that if badly "shocked") but just crack. Having an even heat source, not like a flame directly on the base of the
jar (that does crack it) but like an oil bath or something it should be ok.
Tony Montana
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Posts: 145
From: Australia
posted 06-26-2001 01:27 AM
--------------------------------------------------------------------------------
The only way to crack your jar is to put some icy-cold acid in it and quickly submerge it in some intensly hot oil.When heating oil have jar in it from the start.Or drop it, as I
said most canning, pasta jars are thick hence; it takes a very big accident like dropping it on cement to break it. I cant see why a 5 or 6 buck jar would not be the logical
answer for someone in your position. Concentrating sulfuric acid would NOT be logical in ANY bare metal(uncoated or untreated)recepticle.
Kingspaz: In short use your head, not your keyboard!!!
kingspaz
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Posts: 360
From: UK
posted 06-26-2001 05:28 PM
--------------------------------------------------------------------------------
tony, i didn't think stainless would hold it but i wasn't 100% sure since it is quite unreactive. on another topic anthony thought it should work so that kind of persuaded me to
try it. i think i'll make an oil bath and use a coffee jar as you said i have a deep pan so it should be ok if i suspend the jar with wires so as to avoid direct conduction from the
pan base.
Anthony
Moderator
Posts: 2383
From: England
posted 06-26-2001 08:34 PM
--------------------------------------------------------------------------------
Years ago I cracked many jars boiling liquids directly over and alcohol burner.
The base of the pan should spread the heat so it should be ok resting on the bottom, although being suspended would be more even heating. Depends what's practical really, it
mgiht be a bit unstable dangling from wires?
10fingers
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Posts: 415
From: USA
posted 06-26-2001 08:55 PM
--------------------------------------------------------------------------------
To get high concentration sulfuric acid you have to heat it until it begins to decompose. This about 330 C, or 626 F. Not too many canning jars etc. can take that temp. The
Pyrex type glass bowls or coffee pots are so plentiful in second hand stores etc. that anyone could find a truckload of them in half a day.
kingspaz
Frequent Poster
Posts: 360
From: UK
posted 07-02-2001 04:27 PM
--------------------------------------------------------------------------------
well i tried the oil bath thing. what i did was suspend a cup in a deep pan with copper tube. the cup won't move and does not touch the pans surface. then i filled the pan half
way with oil and put dilute H2SO4 in the cup. i heated it and the water began to boil off. everything worked fine until my stove ran out of petrol ehich really pissed me off. but
the main part is that it worked fine and i'll finish it tomorrow. thanks alot for all the info guys
10fingers
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Posts: 415
From: USA
posted 07-02-2001 05:37 PM
--------------------------------------------------------------------------------
It just amazes me how long some of you guys will stick to a bad idea. What you are trying to do is so fucking simple and yet you persist in trying to do it in the most
complicated way you can come up with.
Oil will begin to smoke heavily and may even catch fire long before you reach the temperature sufficient to drive off all the moisture from the sulfuric acid.
[This message has been edited by 10fingers (edited July 02, 2001).]
kingspaz
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Posts: 360
From: UK
posted 07-02-2001 05:56 PM
--------------------------------------------------------------------------------
sorry 10fingers, i used cooking oil. i know its simple to do but i want to do it safely.

Had my fun when boiling down some battery acid, my first time. From 300 ml 20-30% I got 63 ml 93-96% clear as water H2SO4!! :D My methods of measuring conc is a bit
crappy, first I titrated with NaOH solution taking my borrowed 96% H2SO4 as reference, then I measured by dencity. First method gave 96%, while second gave 93%. Second
is probably the right one..
In my experience, while boiling, acid gave off acidic fumes in all concentrations, from 20-30% and up. And smell of SOx was detected all the way too, first, bearable to breath
and then increasing. The white fumes appeared at about 50% (taking dencity change in account) and become more dence with time. So, IMO apperance of white fumes cann't
be used as indicator to stop heating.
Procidure was following. Charged/drained standard car battery, got 2l. Leaved this for 3 days and decanted clear liquid. Acid was then heated in a baker on an iron plate with a
gas burner. It took 3-4 h, damn long, so I'm planning to go another way remembering the other thread on dessicants. Maby rising the concentration to 70-80% by drying
above CaCl2, this may take several month per liter but I don't have to bike for half an hour and watch the baker for half a day.. The rest will be done with a burner, 1 hour or
so per liter.
Hihi, and then I had this evul laugh inside my head when I sealed my product in a little flask.. It's so dence and oily.. (I have a certain drag to sulfuric acid almost like love to
gold.. but that deserves another thread) :rolleyes:
Gonna tell how the dessication will proceed..

Well, heres some results from dessication of dilute H2SO4.
50 ml battery acid was standing in airtight container together with 50 g CaCl2. After 1 month, 20 ml dissapeared, wee. Thats slow.
Now I want to speed up the evaporation by increasing the liquids area. Idea came to use capillary force of glass-wool sheet (like textile of glass, sold in paint section). By
dipping a large piece of glass-wool in a liquid, one can basically increase evaporating area of liquid to anywhere you like.. and glass wouldn't react in any way.
In one experiment I dipped a 10X20 cm glass-wool sheet in beaker with water. In 24 h, 20 ml evaporated :)
This may be a crap method with limited use but I'm sure one can find many applications. I sure will have fun with battery acid.
grandyOse September 26th, 2003, 01:23 AM

suitable glassware should be easy to aquire even in UK. Anchor Hocking glass company produced a line of glass kitchen ware called "FireKing" from 1942 to 1976. It is very
sturdy and heat resistant. It is both kitchen usable and collectilbe. There are no restrictions nor suspicions regarding this kitchen ware. It is all over ebay. I have used the clear
and dull/milk white varieties for acids, bases, boiling and freezing. My fireking has survived drops and bumps that probably would have shattered pyrex labware.
kinetic October 15th, 2004, 11:17 AM

Go to Walmart and buy an enameled steel pot. They work great, are very cheap, and come in gallon-plus sizes. If you don't know what they look like, they are usually blue
(but can be any color) and have white specs all over them. The enamel is a plastic like coating on the steel but will resist the boiling acid very well.
Now for a question. I noticed that car batteries have warnings on them saying that they potentially contain "explosive vapors." Is it dangerous to boil the acid on a coleman
propane stove? I also usually boil with the lid on. The vapors get very dense!!
cyclonite4 October 15th, 2004, 11:49 AM

I noticed that car batteries have warnings on them saying that they potentially contain "explosive vapors." Is it dangerous to boil the acid on a coleman propane stove?
I believe these vapours are hydrogen gas from the lead reacting with the acid in the battery, you shouldnt have a problem boiling them on the stove as these explosive
vapours will only form in the presence of a reactive metal which ofcourse you wouldnt have in the solution your boiling.
Anthony October 15th, 2004, 01:59 PM

The warning does not relate to H2SO4 vapour, but to hydrogen gas which is generated by the chemical reaction within the battery when it is charged or discharged.
QuartzRox October 15th, 2004, 06:58 PM

Why the hell do you boil it with the lid on ? Isn't the water vapor supposed to go away ?
Oil baths are messy and slow. I made good conc. H2SO4 boiling it directly in teflonware.
FinnBell October 21st, 2004, 04:48 PM

He boils with the lid on due to the dangerous vapors, as he explained like three posts ago.
meselfs October 21st, 2004, 06:34 PM

So he boils it inside?
:-S

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > chemicially
destroying explosives
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frostfire
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Posts: 267
From:
posted 06-28-2001 03:53 PM
--------------------------------------------------------------------------------
I had always wanted to start this topic,a counter explosive preparation...I believe decomposition isn't the right word but basically how is it to turn HE into scrap/ non explosive
anymore.....I read long ago the procedure for NG, but it's gone somewhere..
ahh,Nitroglycerin can be destroyed by boiling in a solution of potassium or sodium hydroxide and ethyl alcohol. (the great MEGA)
Does anyone has the database of lists of methods to change HE chemical properties to a non-explosive substance?
ps, interesting link for NI3 (is it me? can't tell)

http://boyles.sdsmt.edu/triiodide/explosive_decomposition.htm
[This message has been edited by frostfire (edited June 28, 2001).]
mongo blongo
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Posts: 175
From: I live in a Creosote Bush!
posted 06-28-2001 05:03 PM
--------------------------------------------------------------------------------
is this just out of interest?
do you mean to safely dispose of an explosive?
i remember reading something about a strain of bacteria has been produced by the army or bomb squad or something to eat away and decompose explosives safely and
environmently friendly.( not practical)
i suppose its possible to, as you say, to deompose or safely dispose any explosive.
obveously there would be different procedures for each exolosive.
one that i know of is to dispose of lead azide. you mix celic ammonium nitrate to it(im not sure about the "celic" bit but it's something like that)
do a search on the net for safety cards. It should give disposal procedures for what ever explosive you seek.
hope this is usefull?
frostfire
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Posts: 267
From:
posted 06-28-2001 07:34 PM
--------------------------------------------------------------------------------
hey thanks alot,
I've never heard some of them so it is in fact useful, although I haven't found anything particular with the keyword
cutefix
Frequent Poster
Posts: 330
From: california
posted 06-30-2001 04:06 AM
--------------------------------------------------------------------------------
During nuclear disarmament,conventional explosive boosters found in Russian missile warheads were recycled to commercial explosives.This is indeed a worthwhile way than
allowing it to biodegrade, or make it inert in some form of chemical decomposition.This latter procedure will create difficult to dispose residues ,and pose health hazards.Just
think of the fact that most of older military explosives contain aromatic derivatives which are carcinogenic and slow to degrade.Even RDX and HMX are potential health
hazards.The energy locked in surplus and waste energetic materials are enormous and should not be wasted by throwing in a dump an letting microbes decompose it; why not
dispose it by blowing it up in a safe place in front of safely located audience and film the explosion.Hollywood could well authenticate their special effects,by using real
explosives and not fuels!Majority of humanity are impressed by explosions.But many are afraid of it because of ignorance!
The state should amply educate its citizens and remove the mystique of explosives by doing that. It can be a good souce of tourist entertainment creating additional income for
a certain locality that practices it.
PYRO500
Moderator
Posts: 1513
posted 06-30-2001 12:14 PM
--------------------------------------------------------------------------------
Well, what if you did something you shouldnt have and need a way to get rid of your chems safely, this is what I think FF had in mind.
frostfire
Frequent Poster
Posts: 267
From:
posted 07-01-2001 09:05 PM
--------------------------------------------------------------------------------
VERY TRUE!!
and I need access to destroy AP fasttt (not by decomposition!)
PYRO500
Moderator
Posts: 1513
posted 07-02-2001 12:26 AM
--------------------------------------------------------------------------------
ap you could just flush, although if it got caught in a clog and you drained your pipes someday and it was still there you could have a sewage pipe explosion, needless to say
this is not pretty and it dosent smell pretty either, so I wouldn't recomend that unless they were knocking at your door. I think ap is semi soulable in acetone so you could take
a large amount of acetone pour your ap in there and dump it on some land, it would then soak in the soil and evaporate and leave the ap behind, although this could cause a
problem for smokers that like to throw their cigarettes on the ground you can deflagrate it fairly safely when wet although this does leave some behind.
Mick
Frequent Poster
Posts: 240
From:
posted 07-02-2001 03:51 AM
--------------------------------------------------------------------------------
simply disolve the AP in some acetone, and then poor the acetone on the ground and burn it.
simple and effective.
frostfire
Frequent Poster
Posts: 267
From:
posted 07-02-2001 11:42 AM
--------------------------------------------------------------------------------
aye, why didn't I think of that, thanks Mick
only, I'm kinda environmentalist and seek for the "best" way...
anyway, we got nitro and AP, anyone can add other exp method to the list?
I'm also still searching in libraries and searchengines....to whom who has the complete Urbanski series, does the book cover such exposive conversion process?
John456
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Posts: 105
From:
posted 07-02-2001 12:15 PM
--------------------------------------------------------------------------------
The approved method of destroying TNT is by burning it.
Mr Cool
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Posts: 1013
posted 07-02-2001 04:21 PM
--------------------------------------------------------------------------------
I bet many could be oxidised by HNO3 or dehydrated by H2SO4 at high temps., but then you have the waste to get rid of...
I'd say burn them in small amounts.
PYRO500
Moderator
Posts: 1513
posted 07-02-2001 09:46 PM
--------------------------------------------------------------------------------
I for one would not add ap TO H2SO4
Lagen
Frequent Poster
Posts: 178
From:
posted 07-02-2001 11:30 PM
--------------------------------------------------------------------------------
All that the Urbanski books have to say about explosives disposal deals with MF, lead azide, DDNP and tetryl. But maybe I've missed something, I don't have Vol.4... Anyways,
now for vols. 1-3:
Tetryl reacts with excess of sodium sulfiDE (in the form of a 13% solution). Even at normal temperature the nitro groups are reduced to yield a nonexplosive compound. This
reaction can be used to dispose of tetryl containing wastes.
A 10% solution of sodium sulfiTE is capable of reducing tetryl to a nonexplosive compound at a temperature of 80-90C. A similar reaction proceeds with sodium thiosulfate,
which yields a residue, yellow in colour, of uncertain composition.
Mercury fulminate is decomposed by means of a sodium thiosulfate solution:

(CNO)2Hg + 2 Na2S2O3 + 2 H2O = HgS4O6 + (CN)2 + 4 NaOH
This process is suitable for quantitative assay of MF by titration of the resulting sodium hydroxide solution. It can also be used for disposing of MF containing waste and
residues. The usual impurities contained in the MF (oxalate and nitrate) are insoluble in thiosulfate.
Lead azide is destroyed by a dilute solution of sodium nitrite in weak nitric or acetic acid, the decomposition products being soluble therein. To dispose of residual and waste
lead azide, an 8% solution of sodium nitrite in 15% nitric acid is used.
An aqueous suspension of lead azide can be oxidised by cerium(IV) sulfate, which is accompanied by liberation of nitrogen:
Pb(N3)2 + 2 Ce(SO4)2 = PbSO4 + Ce2(SO4)3 + 3 N2
This reaction is also suitable for quantitative assay of lead azide.
Diazodinitrophenol (DDNP) cannot be decomposed by concentrated acids at normal temperature. However, a dilute solution of NaOH (e.g. 0.5%) causes its decomposition even
at normal temperature, with liberation of nitrogen. This can be used to dispose of it.
frostfire
Frequent Poster
Posts: 267
From:
posted 07-03-2001 04:02 PM
--------------------------------------------------------------------------------
hey Lagen,
I owe you man!
THANXSSS
anything else?
'n thanks for the other too!!!
[This message has been edited by frostfire (edited July 03, 2001).]
Lagen
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Posts: 178
From:
posted 07-05-2001 04:51 AM
--------------------------------------------------------------------------------
One more I could remember - according to Gerald L. Hurst, this is the
"Picatinny Arsenal standard method for the destruction
of picric acid:
Dissolve the material in 25x its weight of a solution

made of 1 part NaOH and 21 parts Na2S.9H2O (Na sulfide)
in 200 parts water. The reaction gives off some ammonia
and hydrogen sulfide.
The recipe is somewhat generic in nature. With some

modifications, the general chemistry can be used to
dispose of certain other R-(NO2)x and R-(ONO2)x compounds,
but a specific, tested standard procedure should be used
for each material."
And he recommends lighting a bonfire from a safe distance as the most convenient method for "most" explosives.
I'm aware that in the Urbanski books they give a lot of other destructive reactions for almost every material, but I couldn't find any more that would be specifically designated
as disposal methods. I guess usually either the process, or the products are not benign enough (e.g. picric acid -> picramic acid, chlorpicrine, HCN etc.)
Lagen
Frequent Poster
Posts: 178
From:
posted 07-05-2001 06:27 AM
--------------------------------------------------------------------------------
Now I noticed that the procedure I gave for lead azide might well be what mongo blongo had in mind - cerium(IV) sulfate is also called ceric sulphate (celic-ceric???)

a n d I m provised C hemistry > chlorate or perchlorate? - Archive File
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king s p a z
Freq uent Poster
Posts: 360
From : U K
posted 07-02-2001 04:38 PM
--------------------------------------------------------------------------------
well i electrolised som e NaC lO3 for about 4 days. today i boiled alot of the water away so the NaClO4 could crystalise. the
p r o b l e m is i'm not sure if i boiled enough water off or i electrolised it long enough so i could be left with the chlorate or
perchlorate in the pan. i was wondering if there is a way to tell which is NaClO 3 and which is NaClO 4. i was thinking a long the
lines of crystal structure. does anybody have any inform ation or know anything about how i can tell the difference?
Mr C ool
Freq uent Poster
Posts: 1013
posted 07-02-2001 04:44 PM
--------------------------------------------------------------------------------
NaClO3 is in the form of two square-based pyramids on top of each other. KClO4 is norm ally needle-like crystals, I don't know
about NaClO4.
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
posted 07-07-2001 06:38 PM
--------------------------------------------------------------------------------
This will prob ably help you:
http://huizen.dds.nl/~wfvisser/EN/analysis_EN.htm l
king s p a z
Freq uent Poster
Posts: 360
From : U K
posted 07-08-2001 09:02 AM
--------------------------------------------------------------------------------
thanks guys. i think i have impure NaClO 4 so i'll have to recrystalise it and convert it to the potassium salt. i don't really need
it for anything i just m ade it to see if i could.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > DDNP: Mega's
procedure: Production of Picramic Acid? - Archive File
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Dhzugasvili
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Posts: 64
From:
posted 07-03-2001 06:40 PM
--------------------------------------------------------------------------------
I have made some DDNP, it detonated lovely when confined very well in a tube of notecard jammed at both ends with tissue paper and cellotape. otherwise, it would not
detonate, only burn. This DDNP was produced by the masterj method where sulfur, lye, potassium nitRITE, Picric Acid, and sulfuric acid are used etc etc im sure some of you
are familiar with it.
I was just wondering do any of you know how to PREPARE PICRAMIC ACID for use in Mega's procedure? he says he included it in synth section but it is not there.
10fingers
Frequent Poster
Posts: 415
From: USA
posted 07-03-2001 07:05 PM
--------------------------------------------------------------------------------
In the first part of the procedure you used, where you mix picric acid with the sulfur/lye solution, that's making picramic acid.
Tony Montana
Frequent Poster
Posts: 145
From: Australia
posted 07-03-2001 07:13 PM
--------------------------------------------------------------------------------
The chemistry of powder and explosives "Picramic Acid, red needles, may be prepared by evaporating ammonium picrate in alcohol solution with ammonium sulfide."
[This message has been edited by Tony Montana (edited July 03, 2001).]
Mr Cool
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Posts: 1013
posted 07-04-2001 07:38 AM
--------------------------------------------------------------------------------
Yes, it is formed by the reduction of one of the nitro groups on TNP, to form C6H2(NO2)2NH2OH.
The most common substance used to reduce it is a sulphide of an alkali metal or ammonium.
Dhzugasvili
Frequent Poster
Posts: 64
From:
posted 07-04-2001 07:23 PM
--------------------------------------------------------------------------------
Ah! So! then shit, PA has to be made first and sacrifice some of it to produce DDNP. I was looking for a way around to produce picramic acid with phenol, or otherwise without
using sacrificial TNP, but I guess that was just a stupid querry.
megalomania June 22nd, 2003, 04:01 PM

stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-21-2001 05:37 AM
--------------------------------------------------------------------------------
I did a search but I didn't found precis things ...
so, is there a way to make picramic acid (for DDNP) ? Megalomania forgot to post them on his site
tahnx !
cutefix
Frequent Poster
Posts: 330
From: california
posted 07-21-2001 06:38 AM
--------------------------------------------------------------------------------
Stanfield,there is an simpler way to make DDNP found in KIBC(by Tim Lewis).
MANUFACTURE:
In a pint glass jar place 90 ml warm water and 1.5 grams of lye
(sodium hydroxide). Mix these with a "teflon" stirrer until all the lye had
dissolved. Dissolve 9 grams of picric acid crystals in the lye-water
solution by stirring. Label this jar solution #1. In a 500 ml beaker 3 ml
of water is placed. Dissolve 7.5 grams of sulfur and 7.5 grams of lye (sodium
hydroxide) by stirring the solution. Boil this solution over a heat source.
When the solution turns dark red remove and allow the liquid to cool. Label
this solution #2. Add this cooled solution #2 in three portions, to
solution #1. Stir with a teflon rod while the liquid is being added. Again
allow the solution mixture cool. Filter this mixture through filter papers
(coffee filter, paper towels). Small red particles will gather on the
paper. Discard the liquid. Dissolve these red particle in 180 ml of boiling
water. Remove and filter this hot liquid through a filter paper (coffee
filter, paper towels). Discard the particles left on the paper and label
the liquid left #3. To Solution t#3 with an eyedropper slowly add sulfuric
acid (Janitor supply, boiled battery acid) to the filtered solution until
it turns orange brown. Add an additional 7.5 grams of acid to the liquid.
In a separate pintjar, dissolve 5.4 grams of potassium or sodium nitrite in
240 ml of water. Label this solution #4. In one portion solution #4 is
added with stirring to solution #3. Allow the solution to stand for 10
minutes. The mixture will turn light brown.
Filter the light brown solution through a filter paper (paper towel, coffee
filter). Wash the particles left on the paper with 60 ml of water. Allow to
completely dry for 24 hours. Drying time can be reduced to 2 hours if
crystals are placed in a shallow pyrex dish and this placed in a hot (not
boiling) water bath.
This powder should be stored in small quantities in stoppered glass
containers. More safety in storage leave 25% water in the powder and dry
immediately prior to use.
Good Luck to your experiments,and be careful,this is a sensitive primary explosive.
Lagen
Frequent Poster
Posts: 178
From:
posted 07-21-2001 07:01 AM
--------------------------------------------------------------------------------
I believe there should be 300ml, not 3ml of water in the preparation of soln. #2.
quote:
--------------------------------------------------------------------------------
... Add this cooled solution #2 in three portions, to solution #1. Stir with a teflon rod while the liquid is being added. Again allow the solution mixture cool. Filter this mixture
through filter papers (coffee filter, paper towels). Small red particles will gather on the paper. Discard the liquid. ...
--------------------------------------------------------------------------------
They then use these "red particles" to proceed to DDNP. This is picramic acid. You can plug it into Mega's recipe. Picramic acid is soluble in benzene and acetic acid, but not in
other organic solvents. It's not explosive, yet more dangerous than PA, this is the stuff that forms in small amounts in your body from picric acid and accounts for most of its
toxicity. Also have a look at "DDNP: Mega's procedure: Production of Picramic Acid?" in this section.
[This message has been edited by Lagen (edited July 21, 2001).]
stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-21-2001 12:27 PM
--------------------------------------------------------------------------------
"I believe there should be 300ml, not 3ml of water in the preparation of soln. #2"
so, is there 300 or 3 mL ??
thanx !
stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-21-2001 01:38 PM
--------------------------------------------------------------------------------
another question :
"Add an additional 7.5 grams of acid to the liquid"
ok but what's the concentration ?
thanx
Lagen
Frequent Poster
Posts: 178
From:
posted 07-21-2001 02:31 PM
--------------------------------------------------------------------------------
Obviously, the author meant 300ml. Dirk Goldmann in his Improvised Primary Explosives noticed that typo, so in IPE you'll find a similar procedure, but with 300ml. Why would
they put 3ml and a few grams of other stuff into a 500ml beaker? And how on earth could the sodium sulfide that's produced dissolve in 3ml solvent? Only a fraction of a gram
would dissolve.
Anyways, you could just as well get away with as little as 100ml water, and as much as 10gr sulfur and NaOH each.
Tonight (maybe in 1-2 hours) I will try the experiment with 3ml, 100ml and 300ml and will post the results here immediately.
The acid is just a catalyst, the amount is not that important, but if yours is real dilute increase the amount accordingly. They probably meant concentrated. HCl can be used
also. When I post the results of the sulfide experiment I will give the exact procedure for HCl as well. Please excuse me I'm in a hurry now...
stanfield
Frequent Poster
Posts: 176
From: FRANCE
posted 07-21-2001 04:32 PM
--------------------------------------------------------------------------------
yeah, post your exact recipe plz !
it will be very nice
see ya !
Lagen
Frequent Poster
Posts: 178
From:
posted 07-21-2001 04:43 PM
--------------------------------------------------------------------------------
Ok guys I'm back, I just had to get a few explosives precursors from the local grocery before they closed up shop at 9pm. Will append the results to this post...
OK I wiped the beaker completely dry... At first with an ordinary towel, then with a soft paper towel. Then I placed it in the oven for 10 minutes to drive off the remaining
moisture, the usual procedure in every recipe Then 3ml of water were carefully measured out into the beaker... I added 7.5g sulphur and 7.5g NaOH. There was no reaction. I
put it on the hotplate. Soon I realised that there is no way this is gonna work. All of the NaOH dissolved, and some sulphur too, the solution indeed turned yellow-red (which I
assume to be Na2S and Na2S4), some yellow-green oily liquid formed on the top of the mixture, which I assume to be molten sulphur. But, on cooling (which they suggest)
the sulphur solidifies, so it's neither dissolved nor reacted. Some S remains unreacted. The red solution started boiling and smelling like hell, I fear it's decomposing. OK so tell
me (with a straight face) how many of you guys have actually attempted DDNP according to the Tim Lewis' recipe...
Now adding 297ml H2O. At first solution turned yellow-green. After a while the red stuff started dissolving. I stirred it, solution turned orange. Small bubbles formed on the
sulphur. Now I am cracking up the solidified sulphur, it still takes ages to dissolve it... After some time solution is about the color of tea. Now there are huge bubbles on the
sulphur pieces, and I can't crack them up, because they're flying around, funny... The volume of the solution was reduced to 270ml by boiling! Reduced the heat, now it's at
lowest heat. The 3ml experiment was a fuckup in that it turned the sulphur to big pieces, which don't dissolve. So when you do this, start with a fine sulphur powder. Solution is
brown, 250ml. After some more ages it starts turning red. Refilled to 320ml. Finally, it all dissolved, by the time it was boiled down to 120ml. Solution is reddish brown, but
stains paper in yellow-green. Some fine insoluble residue appears in the liquid, but I assume this to be an impurity from the sulphur.
The 100ml batch took a lot of time too, I haven't crushed it properly, but finally it dissolved, some residue appears - the amount is negligible, but it's a bit coarser than in the
previous batch. After cooling nothing precipitates, so 100ml should be OK.
10fingers suggested the Lewis formula is correct so I tried the controversial stuff again... Trying with 1ml, 2x 2.5g. Upon addition of the NaOH to the 1ml water there is a
violent reaction and heating, some of the NaOH cakes. Put it on the hotplate. The 1ml water is quickly boiled away, it's difficult to keep replacing it so that the volume is
constant. When heated, the mixture is brick red. Then it starts to fizzle, decompose and gives off some irritant gas (feels kinda like tear gas). After cooling it forms the sulphur
lumps same as before, color is reddish brown. I cycled through this 3 times, and allowed to cool. It definitely doesn't form a solution, but rather a thick mass. So my conclusion
is: This way it is difficult to moderate the reaction, it gives off nasty fumes, cannot be poured out the reaction vessel, and does not behave the way it's described in the books
(I cannot imagine how this could be poured in three portions). I can't help it but I keep thinking the 3ml or 1ml formulas, must be wrong. And why would they use a 500ml
beaker? (The next day I inspected the "solution", it was a tough cake, difficult to remove from the beaker even with a wire, smelled like rotten eggs...)
The recipe: Crush 10g of sulphur to a fine powder. Into a 250ml beaker or jar place 100ml distilled water. Dissolve 10g NaOH in the water, stir to prevent caking. Pour in the
sulphur powder and heat the mixture so that it gently boils. Stir occasionally and keep replacing what is being boiled away, until everything had dissolved. Solution should be a
reddish brown color. This is a mixture of sodium sulfides in water. Let it cool down. If an insoluble residue remains in the solution, do not filter, it will be removed later in the
process. Into another 500ml beaker or jar put 90ml distilled water and 1.5g NaOH and stir until the lye had dissolved. Dissolve 12g of PA in the solution with stirring. Add the
cooled sodium sulfide solution in five portions, to the PA solution. Stir with a teflon rod while the liquid is being added. Again allow the solution mixture cool. Filter this mixture
through filter papers (coffee filter, paper towels). Small red particles will gather on the paper. Discard the liquid. Dissolve these red particles in 180 ml of boiling water. Remove
and filter this hot liquid through a filter paper (coffee filter, paper towels). Discard the particles left on the paper and save the liquid.
Now if you just wanted to make %SUBJ% (why??? Silly idea! It's toxic!) just evaporate the liquid to dryness (do not overheat, dry in an oven with precise regulation at 150C,
or on an oil bath, do NOT exceed this temperature) and you should get red crystals of pure picramic acid. You should evaporate this and weigh it out anyway, at least for the
first time, to ascertain the yield of picramic acid. Theoretical yield is 11,26g.
10g of picramic acid is dissolved with strong stirring (or magnetic stirrer) in 120ml of 5% HCl in a 250ml beaker placed in an ice bath. 3.6g of NaNO2 is dissolved separately in
10ml water and added in one portion to the picramic acid solution, with stirring. Let the mixture stand for 20 minutes. The mixture will turn a brown color. Filter the brown
solution through a filter paper (paper towel, coffee filter). Wash the particles left on the paper with 60 ml of ice cold water. The DDNP is then purified by dissolving in the
smallest amount of acetone possible. The acetone should be preheated to 40-45C. With stirring this solution is slowly dumped into ice cold water, the precipitate is filtered and
allowed to dry. Leave a small amount of water for safety.
I will keep updating this recipe and will write a note here if anything changes. Recently I adjusted amounts so that amount of picramic acid matches second step. Now I found
out that the "second step" is virtually identical to Megalomania's procedure. Any input is welcome.
[This message has been edited by Lagen (edited July 22, 2001).]
10fingers
Frequent Poster
Posts: 415
From: USA
posted 07-21-2001 07:28 PM
--------------------------------------------------------------------------------
In the Improvised Munitions Handbook the formula says, "place 1 milliter water in a glass container, add 2.5 gms. sulfur and 2.5 gms. sodium hydroxide. Boil over heat source
until solution turns dark red".
The ratios of chemicals in this book are all 1/3 of the formula in the Tim Lewis formula.
so if this formula is correct then the correct amount would be 3 milliters.
Lagen
Frequent Poster
Posts: 178
From:
posted 07-21-2001 11:27 PM
--------------------------------------------------------------------------------
There is an issue regarding DDNP which any of the *IPE books don't tell you. The crystal density of DDNP seems to be high, but when made with the usual process above, the
density of the material is only 0.27 g/cm3... When pressed mildly, this can be pushed to 0.86, resulting in a VOD of only 4400... The crystals are also long and thin, difficult to
load in the detonator, and very sensitive. These disadvantages can be overcome by modifying the reaction conditions, which results in a smaller, grainlike material of
somewhat higher density (0.82 unpressed). Similar results are obtained when using a different process, you start from the sodium salt of picramic acid.
I will post the details sometime, now it's morning here and I'm exhausted...
Lagen
Frequent Poster
Posts: 178
From:
posted 07-22-2001 12:02 PM
--------------------------------------------------------------------------------
I found out about three possible ways of increasing the density of DDNP. When using these methods, the DDNP purification step must be omitted, as that would change the
crystal shape and size.
Carrying out the diazotization step (the second part of the process) at a higher temperature (25-45C). This way a higher density (0.82) should be obtained, but it looks kinda
dangerous.
Adding a small amount (perhaps 0.5-1%) of a triphenylmethane dye to the diazotization mixture. An example of such a compound would be 2-amino-5-[(4-amino-3-
sulfophenyl)(4-imino-3-sulfo-2,5-cyclohexadien-1-ylidene)methyl]-3-methyl-benzenesulfonic acid, disodium salt, otherwise known under the following trade names: Acid
Magenta, Acid Violet 19, Acid Fuchsin-sodium salt, CI 42685. Don't let the name fool you, it is a quite common organic dye. The molecular formula is C20H17N3Na2O9S3, CAS#
3244-88-0, Aldrich cat.# 33,270-4. Edit: The formula from the CRC book was wrong!
The best method IMO: starting from the sodium salt of picramic acid. I have found no info on its synthesis, but I assume one could prepare a solution of picramic acid in
absolute alcohol, and neutralize by stirring in some NaOH (in the ratio 1.9g NaOH to 10g picramic acid). The salt would then be precipitated in the form of a very fine powder
by adding a large excess of cold water, filtered out and dried. 10 grams of this powder would be stirred into 80ml water (20C). To this suspension a solution of 3.6g NaNO2 in
20ml water is added slowly. Then 60ml of a 5% HCl solution is added dropwise over a period of two hours (with stirring, eg. a magnetic stirrer). The temperature rises from
20C to 25C, if necessary, moderate the temperature. The DDNP is then filtered out, washed with cold water and dried at 35-40C. Yield approx. 84% theory, or 7.44g.
tom haggen September 1st, 2004, 01:17 AM

I read about the synthesis of picramic acid in The Chemistry of Powder and Explosives. It says to evaporate ammonium picrate in an alcohol solution with ammonium sulfide.
Anyone have any ideas on what ratios should be used for this? When it says evaporate ammonium picrate in an alcohol solution, I assume they mean mix ammonium picrate in
with a solution of ammonium sulfide and ethonal, and let the ethonal evaporate. I noticed that the chemlab is under construction. Hopefully this synthesis will be covered along
with many others. I'm ripe with anticipation, It's like Christmas in August. Ya I have rep power, I guess all that studying and kissing ass is paying off.
bobo September 1st, 2004, 04:51 AM

I think the molar ratio should be like 120% of sulfide. I think i will try this one out soon, my old procedure (sulfur to sulfide in water) works somewhat well but the downside is
birds drop dead over the roof from the godawful stench that is produced.
EDIT: found some info on ammonium sulfide. Somehow, I think this compound has more hooks than sodium sulfide or others. Why would the ammonium compound be
preferred (since it is the sulfide or rather HS- ion that seems to act).
Also, the ammonium sulfide that seems mostly available is in aquous solution, should you purchase it. I think that using ethanol is a bit roundabout however, the ammonium
picramate would crystallize out
http://www.fact-index.com/a/am/ammonia.html
Ammonium sulfide, (NH4)2S, is obtained, in the form of micaceous crystals, by passing sulfuretted hydrogen mixed with a slight excess of ammonia through a well-cooled
vessel; the hydrosulfide NH4.HS is formed at the same time. It dissolves readily in water, but is probably partially dissociated in solution. The hydrosulfide NH4.HS can be
obtained as a white solid, by mixing well-cooled ammonia with a slight excess of sulfuretted hydrogen. According to W. P. Bloxam (Jour. of Chem. Soc., 1895, lxvii. p. 283), if
sulfuretted hydrogen is passed into strong aqueous ammonia at ordinary temperature, the compound (NH4)2S.2NH4HS is obtained, which, on cooling to 0C and passing more
sulfuretted hydrogen, forms the compound (NH4)2S.12NH4HS. An ice-cold solution of this substance kept at 0C and having sulfuretted hydrogen continually passed through it
gives the hydrosulfide. Several complex polysulfides of ammonium have been isolated, for details of which see Bloxam's paper quoted above. Compounds are known which
may be looked upon as derived from ammonia by the replacement of its hydrogen by the sulfo-group (HSO3); thus potassium ammon-trisulfonate, N(SO3K)3.2H2O, is
obtained as a crystalline precipitate on the addition of excess of potassium sulfite to a solution of potassium nitrite, KNO2 + 3K2SO3 + 2H2O = N(SO3K)3 + 4KHO. It can be
recrystallized by solution in alkalies. On boiling with water, it is converted, first into the disulfonate NH(SO3K)2 thus, N(SO3K)3 + H2O = NH(SO3K)2 + KHSO4, and ultimately
into the monosulfonate NH2.SO3K. The disulfonate is more readily obtained by moistening the nitrilosulfonate with dilute sulfuric acid and letting it stand for twenty-four hours,
after which it is recrystallized from dilute ammonia. It forms monosymmetric crystals which by boiling with water yield amidosulfonic acid. (See also E. Divers, Jour. of Chem.
Soc., 1892, lxi. p. 943.) Amidosulfonic acid crystallizes in prisms, slightly soluble in water, and is a stable compound.
K9 September 1st, 2004, 09:46 AM

Well I went with the procedure of dissolving NaOH and S in water and then boiling to make a mixture of sulfides and polysulfides. When I mixed that with sodium picrate I got
a reddish powder (I'm assuming picramic acid) which was then reacted with KNO2. Seemed to work for me.
bobo September 1st, 2004, 12:37 PM

I suppose you mean you mix sodium picrate with the sulfide bath, then toss that mixture in the vessel for diazotization with nitrite.
The problem with this is that the intermediate contains sulfur compounds and in general is just a mess. Try burning your product just to smell sulfur oxides, and of course, if it
shows primary properties.
K9 September 1st, 2004, 04:36 PM

Well what I did was mix the the sodium picrate and sulfides together and then filtered the reddish precipitate. That filter paper was later burned and definitely gave off a strong
smell of sulfur oxides. That precipitate was then dissolved in water and filtered getting rid of something - I assume impurities. The solution was then acidified with H2SO4 and
KNO2 was added. The yield wasn't great, but I suppose the experiment could have gone more smoothly at some points. The product was burned in the open but didn't det -
and apparently it's not supposed to det in open air except for larger amounts. Is there anyway to be certain of the product?
EDIT:
At this point, I think something was screwed up in the synth. Apparently others have had the same problem as what seems to have happened in my synth. I guess all that's
left is trying again.
Ok here's the new question - was that picramic acid that was created from the addition of the sulfides to the sodium picrate? It was a reddish coloured solid that precipitated
and was filtered. If up to that point is right, then I can deal with the next step as a new point.
But everyone seems to have a different idea about this synthesis.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Polyvynyl alcohol
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zeocrash June 22nd, 2003, 11:29 AM

i was up at manchester uni open day and i was watching them do a polymer demonstartion with polyvynyl alcohol and borax.
now i saw the lable on the bottle and thought, "hey i can use that to make PVN". anyway the demonstrator refered to it as PVA. this got me thinking that PVA glue was
polyvynyl alcohol, anyway after looking it up i found out that pva glue really was poly vynyl acrylate, like i orininally thought. anyway, i researched more and found out that
PVA glue could be hydrolised into PValcohol.
i came up with a method of refluxing it with NaOH to hydrolise it
doing this leaves me with sodium acetate, polyvynyl alcohol, water, and excess NaOH
i was wondering if anyone knew how i could separate the PValcohol from the unwanted crap.
or if anyone knew a beter method of producing PValcohol
yt2095 June 22nd, 2003, 11:58 AM

Difficult, but not imposible, the PVA being macro covalent and the remainder being ionic and covalent with ionic properties.
i sugest a 2 step procedure, 1`stly the NaOH when dry will crystalise, as will the sodium acetate (same stuff they use in the pocket warmer pack)
there`s 2 ways i THINK you may be able to get away with making your product a little purer, 1`stly, can you distil the PVA out, it may indeed make an azeotrpe with the
water, but you`ll be a step closer and have less crap to deal with.
secondly try and find a reaction that will make sodium salts less soluable (tho most sodium salts are quite soluable) maybe a sulphate or a carbonate perhaps?
the other idea would be a reagent that "fixed" the PVA into a solid but ignored the ionic chems in your mish mash, so that you could extract the reacted PVA and then start with
a less complex and mixed molecule, and merely remove it with a simple solvent.
an EXACT answer i DON`T have, ideas plenty! and if any of this helps you think of further ideas as a thought provoker, glad to have helped, if not, sorry to have wasted a post
guys.
Good luck anyway :)
zeocrash June 22nd, 2003, 12:28 PM

i just had a thought,
how about i use calcuim hydroxide to hydrolise the PVA glue
this way when hydrolosys is complete i can blow carbon dioxide through the mix, converting the Ca(OH)2 into CaCO3, like limewater. i then filter the mixture to remove the
CaCO3. then i boil the water off, and continue to heat the mixture to 160-170C this causes the breakdown of the calcium acetate into calcium carbonate and acetone. the
acetone evapourates off.
the calcium carbonate and the PValcohol stay in the flask.
the mixture is then mixed with water to disolve the PValcohol. the solution is then filtered to remove the CaCO3, and crystalised to obtain the PValcohol
this is all i have come up with and i thint it'd probably be horribly inneficient give a terribly low yield and would take hours, any ideas
yt2095 June 22nd, 2003, 12:38 PM

not a bad call actualy! tho the CO2 bit would be painfully slow, but a sulphate of calcium would be equaly as insoluable, as long as you could garauntee the sulphuric acid
didn`t reverese your hydrolysis.
remember tho, as i`ve no experience with this procedure your embarking on, and only chatting basic chemistry 101 (no organic stuff) that all my posts on this particular link
are meant as Thought provoking ideas only! :)
Calcium at face value seems like a good option tho, certainly easier to clear up than sodium salts. tho i stongly suspect you`ll need more refluxing time, as CaOH isn`t as PK
base as NaOH.
tho it was good enought to strip the flesh off people in shallow graves during WW2!
besides, there`s no such thing as a failed experiment, only more data :)
frogfot June 22nd, 2003, 01:15 PM

It could be extracted by Et2O but maby acetone could do it too.. Since all byproducts are salts, there will form a layer of acetone with PVOH.
yt2095 June 22nd, 2003, 01:35 PM

frogfot,
i`m not sure what Et2O is, but based on that thought it just made me think, perhaps it`s possible to lockup the sodium with EDTA. tho i`m sure that`s what you meant frogfot.
Ethylene diamime tetra acetic acid?
either way, if it IS seperate things, you`ve now got some more data to work with :)
altough i`ve only ever known EDTA used to lock up heavy or toxic metals, so maybe it won`t work with sodium? i have no data to either confirm or deny this.
frogfot June 22nd, 2003, 05:15 PM

Soz, i meant diethyl ether (Et2O), but this may be hard to get by anyway.. btw, hydroxide is preferrably neutrolised before extraction.
EDTA with metal would be still soluble..
Mr Cool June 23rd, 2003, 08:03 AM

I'm wondering about an acid-catalysed hydrolysis, where the acid is simply your nitrating acid. This would be nice, as it makes it into a one-pot reaction, with fewer impurities.
After the reaction, neutralise any remaining acid with NaOH. So you'd have sodium nitrate, sulphate and acrylate in solution, and insoluble PVN which could be filtered and
purified as usual.
It just depends on where the equilibrium lies between PVA + HNO3 <=> PVNO3 + HA...
Edit: Tetrasodium EDTA exists, but EDTA will not form a complex/chelate with sodium because it isn't a d-block element - it has no unfilled d-orbitals to accept electrons from
the EDTA in order to form the complex. Thus you can only get the sodium salt of EDTA.
Marvin June 23rd, 2003, 04:18 PM

PVA glue is mostly polyvinyl acetate together with some unreacted alcohol, so it would indeed hydrolyse to to the alcohol and sodium acetate. Extraction with ether could work,
but I dont know how soluable it is. I think its virtually insoluable in something like hexane, and probably in anything thats completely insoluable in water. I have the funny
feeling salting out would work well though, say with pot carbonate. Youd have to remove anything that crystalised, which should be everything after neutralisation. I have the
feeling the sodium carbonate wouldnt work. Driving out the water by heating then decanting from the insoluable solids might also work.
What would bother me, is half way through the reaction, how can you tell if its totally hydrolysed or not?
kingspaz June 23rd, 2003, 05:57 PM

i guess you wouldn't and work on the assumption that after a given time it MUST be hydrolised. like keep the heat on for 2 hours or something as that would hydrolise most if
not all.

PVAcetate? I thought it was PVAcrylate :confused:.
I've spread some out in a thin layer to dry out, then I'll mince it up in a coffee grinder and try a direct nitration, to see if I can swap a nitrate for the acetate/acrylate/whatever.
One problem might be that it is very possible that the generic "PVA Glue" is not pure PVA and water. Other things might be present to improve its guiness.
Edit (typo): "guiness" should be "gluiness." Guiness doesn't need improving :).
kingspaz June 24th, 2003, 11:42 AM

i thought the A in PVA was acetate also. i'm pretty sure it is.
http://www.export911.com/ref/plasApp4.htm
in the middle of the page somewhere.
Marvin June 25th, 2003, 09:56 PM

Acrylate glues are of the 'superglue' class activly polymerise (and usually crosslink) when hardening.
The 'wait 2 hours and assume its all gone' would require an act of faith I wouldnt have. For example, if you have a secondary alkyl chloride and refluxed it with plain water I'd
expect it to be gone pretty rapidly. The secondary chloride equivalent in this case though is polyvinyl chloride! If I refluxed that with water, or even with strong alkali I'm not
convinced Id have a significant conversion after a year, though I confess I dont have the slightest real idea how long it would take. (Yes it would be a different phase than the
water which slows things down, but then so is the alkyl chloride)
What bothers me slightly more is that with polymers the reaction is never actually 'done' done. Instead of a molecule with 1 OH, that goes directly to the product you have a
molecule with thousands (probably) or more and its a question of getting a polyalcohol that is 50% aceylated or 10% or 5% or 0.5%.... How can you check how far along
hydrolysis has progressed without purifying the product out of the reaction mixture and then measureing its density or boiling point....
Edit, Yes there will be small amounts of plasticisers too.
zeocrash June 26th, 2003, 03:51 PM

mr cool: i dont think that a direct nitration/hydrolosis of PVA would be a sensible idea, according to meglomania's synth while making PVn you should cool the mixture to -8 C
during the nitration. but the hydrolosis requires refluxing and therefore heat. now i have 2 queries, firstly what would happen if i were to heat this mixture as it was hydrolising
/ nitrating
secondly do i need to hydrolise the pva at all or would it be possible to do a direct nitration, substituting PVA for PValcohol.
also i believe industrial hydrolosis to form PValcohol uses alcohols, which would definatly be worth a try

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Acetic Acid - Archive
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Tony Montana
Frequent Poster
Posts: 145
From: Australia
posted 07-06-2001 08:06 PM
--------------------------------------------------------------------------------
I was reading a patent, to be precise:
PATENT NO.5,250,687
Process For Preparation Of RDX.
In which they say; "Waste acetic acid formed during the reaction is re-condensed and subjected to an energy intensive ketone process being thereby, converted back to useful
acetic anhydride."
Does anybody know what an energy intensive ketone process involves?
If they have to re-condense the acetic acid, this would mean vinegar would be a good substitute that could be condensed. And condensed vinegar could then be subjected to
the energy intensive ketone process, yielding acetic anhydride. Is this possible without too much hassle??????
Anthony
Moderator
Posts: 2383
From: England
posted 07-06-2001 08:09 PM
--------------------------------------------------------------------------------
Yes that is how acetic anhydride is made, try a search as the process has been covered in detail before.
10fingers
Frequent Poster
Posts: 415
From: USA
posted 07-13-2001 10:24 PM
--------------------------------------------------------------------------------
Ketene is made by passing acetone vapors through a chrome/iron pipe at high temperatures and then leading the ketene into a container of glacial acetic acid to form acetic
anhydride.
I've seen the exact procedure posted here before and it can be found in one of the Kitchen Improvised Plastic Explosives manuals.
I have never heard of anyone trying this process and I am curious if it works.
[This message has been edited by 10fingers (edited July 13, 2001).]
cutefix
Frequent Poster
Posts: 330
From: california
posted 07-14-2001 02:57 AM
--------------------------------------------------------------------------------
That procedure is feasible in an industrial setting , but for laboratory scale I doubt if anybody will exert effort to recycle his spent acetic acid,when he has more important things
to do.
The acetic acid waste is more stronger than normal home vinegar(5-10 % acid),other food processingl vinegars reach to 20%. But still lesser than about 40% or more
concentration found in that spent acids.It may be theoretically feasible to convert household or food grade vinegars to acetic anhydride but not a practical,or economical idea.
10fingers
Frequent Poster
Posts: 415
From: USA
posted 07-14-2001 09:09 AM
--------------------------------------------------------------------------------
The process may be practical for someone has access to glacial acetic acid but not acetic anhydride.
I once tried to make glacial acetic acid from vinegar. I neutralized the vinegar with sodium bicarbonate to make sodium acetate, dried it in the oven to remove all water and
distilled the sodium acetate from sulfuric acid. I obtained some strong acetic acid (80%), but it was not glacial because it would not freeze. I distilled it again under vacuum but
it was still not pure. Don't know why.
The whole process was a lot of work and I don't recommend it.

a n d I m provised C hemistry > formaldehyde toxicity - Archive File
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king s p a z
Freq uent Poster
Posts: 360
From : U K
posted 07-07-2001 06:34 AM
--------------------------------------------------------------------------------
i read on a site that was linked from here that a by product of RDX m anufacture (can't rem e m ber the proce ss letter...think it
was E, it used nitric anyways) is form aldehyde. i've read from various sources that form ald ehyde is carcinog enic. i've searche d
on altavista and found out that its bee n linked to leuchem ia, nasal cancer, lung cancer and some others ca ncers i can't
r e m e m ber. is formaldehyde a strong carcinogen or would you need decades of co ntact with it to de velop cancer?
[ T h i s m e s s a g e h a s b e e n e d i t e d b y k i n gspaz (edited July 07, 2001).]
jin
Freq uent Poster
Posts: 113
From : u k
posted 07-07-2001 07:05 AM
--------------------------------------------------------------------------------
i think its long term contact th at causes cancer.i read somewhere it was slightly m ore toxic than hydrazine when taken by
m outh not sure about vapours breathed in.
John456
Freq uent Poster
Posts: 105
From :
posted 07-07-2001 12:21 PM
--------------------------------------------------------------------------------
I think its the other way around, vapors are m ore toxic than taking it by m outh. I knew a kid when i was in high school that
swallowed a sm all pie ce of a clam they were dissecting because som e other kid was paying him . He had to go to the hospita l
b u t n o t h i n g h a p p e n e d l o n g t e r m , and he doesnt have cancer as far as i know, although hes likely to get it som eday. Also, ive
heard on the news once that some rap ist was g etting his victims by holding a rag of form a l d e h y d e t o t h e i r nose, and
supposedly they would im m ediately fall unconcious.
king s p a z
Freq uent Poster
Posts: 360
From : U K
posted 07-07-2001 04:56 PM
--------------------------------------------------------------------------------
so would it be kind of like sm o k i n g ? s m oking causes ca ncer but only if you do it for years. does anybody have any information
on its toxicity in relation to other chem icals? i k now som e people here use it for m aking RDX so what precautions do you
people take when using it?
hardliner
New Mem ber
Posts: 9
From : Austra lia
posted 07-07-2001 06:10 PM
--------------------------------------------------------------------------------
This is from pm jb 1
"A m uch better irritant is formaldehyde.Better known as embalm ing fluid,it sm e l l s h o r r i b l e , h u r t s t h e e y e s a n d n o s e , a n d o n
expososure to the air it vaporirizes,m a k i n g a r o o m uninhabitable for hours."
nitroglycast
New Mem ber
Posts: 4
From : french
Registered: JUL 2001
posted 07-09-2001 12:25 PM
--------------------------------------------------------------------------------
SCUSE-ME FOR MY ENGLISH
I h a v e m a k e o n e m e l a n g e o f f o r m a l d e h y d e a n d am moniac for m a n u f a c t u r e o f h e x a m i n e a n d i h a v e b o i l t h e m e l a n g e . T h e
vapors of this melange are it toxic ?
king s p a z
Freq uent Poster
Posts: 360
From : U K
posted 07-09-2001 05:05 PM
--------------------------------------------------------------------------------
it probably will be toxic as it contains formaldehyde so will give off formaldehyde vapour before the reaction is com p l e t e d . d o e s
a n y b o d y k n o w how safe it is to handle and if i would be risking cancer handling it?
jin
Freq uent Poster
Posts: 113
From : u k
posted 07-09-2001 05:39 PM
--------------------------------------------------------------------------------
heres som e health information on formaldehyde
www.mednets.com /toxicology-Formaldehyde.htm
s m a ll am ounts of form a l d e h y d e a n d h y d r a z i n e a r e f o u n d i n t o b a c c o s m o k e .
[This message has been edited by jin (edited July 09, 2001).]
cutefix
Freq uent Poster
Posts: 330
From : california
posted 07-09-2001 10:36 PM
--------------------------------------------------------------------------------
A lot of thing s are carcinogenic,due to the presence of pollutants the air we breath can be carcinogenic also, yet we are not
worried m uch about it.These cancer paranoia is a deterrent to progress .If we just take good care that we do our chemical
e x p e r i m ents seriously,and observe proper safe ty in our work- we can outlive cancer worries and at the sam e t i m e a c h i e v e t h e
fruits of our labors.

a n d I m provised C hemistry > peroxysulfuric acid - Archive File
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- (V)Z -
New Mem ber
Posts: 2
From :
posted 07-09-2001 04:31 AM
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Hello all! I know that you frown on having new m e m b e r s p o s t n e w topics, but I feel this is interesting enough to merit it, and I
wasn't able to find an y m entions of this compound earlier.
Do any of you here have any knowledge relatin g to peroxysulfuric acid, a lso known as caro's acid or pirahna fluid? I originally
came across this in the explosives newsgroups. It was described as being one of the very strongest acids that you can get, and
'it can rem ove skin as fast as a knife' according to the m ember posting information on it. In addition to that, it can also
d i s s o l v e g l a s s a n d d i a m ond [!]. This sounds very fascin ating, as you cou l d w r e a k s o m e s e r i o u s d a m age with a chem this
dangerous. However, very little info can be found out there on it via google. Abou t all i could find is that it is used in etching
m etals and glass as a dilute agent. Basically, what it is is H2SO 5, form ed by adding conce ntrated H2O2 to H2SO 4.
H2SO 4 + H2O2 -->H2SO5 + H2O
So in that regards it would be very easy to m ake, but I have no idea if you could concentrate it by boiling, if that wo uld even
be possible as it will dissolve glass. I couldn't find any info saying whether or not it could dissolve ceram ic or teflon tho. If
anyone out there cares to try to m ake it, go rig ht ahead. Or even better, if you have som e info on caro's acid, any help would
be appreciated!
deezs
Freq uent Poster
Posts: 113
From : Hungary
posted 07-09-2001 01:05 PM
--------------------------------------------------------------------------------
As far as I know, the strongest acid is a m ixture of HF and Sb(F)x. A well known hungarian chem ist kills his tim e playing with
this stuff. It dissolves wax too !
Caro's acid is a very strong oxidizing a gent. Perhaps too strong. I belive, that it reacts wit diam ond. Diamond is just carbon, it
can be lighte d with a special m irror. I think caro's acid is so strong, that it has no practical use. You can not m ix it with any
reducting agent.
Dissollving glass? I think glass can not be oxidized.
I h a v e f o u n d a few words about it's m anufacture:
- H2 O2 + ccH2SO4
- H2 O2 + HSO 3Cl
- hydrolisis o f H2S2O6 with H2SO4
Before you try to m ake it, sea rch for detailed recipe.
------------------
"Don't belive anything, just because th ere is a good pro verb for it."
a_bab
Freq uent Poster
Posts: 55
From : d o e s n ' t m atter
posted 07-09-2001 03:46 PM
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I r e a d e d o n c e a b o u t t h i s s t r a n g e a c i d , a n d a l l I r e m e m ber is that it is a VERY corosive substance, obtained from 98% sulfuric
acid and 30 % (m inim u m ) hydrogen peroxide, and a little experim ent with it : if you drop a m atch (wood type), or a piece of
wood (a splinter) in it, it will vanish is seconds !
The pyranha solution is obtained from
K2Cr2O7 and sulfuric acid, and is used for cleaning the lab vessels (glass). It is werred off when th e colour is changed from
orange to green (the Cr ions are reduced)
Your H2O 2/H2SO4 mix won't corrode g lass (at normal tem perature only HF, som e F c o m p o u n d s a n d s o m e hydroxid es can).
P.S. For God sake, ch a n g e y o u r u s e r n a m e !

________________________
http://m ove.to/pyrom a n i a
sim ply RED

Freq uent Poster
Posts: 242
From : HELL
posted 07-09-2001 08:26 PM
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Is its formula : H-O-O-(SO2)-O -H?
I read aboutthe existance of HClO5...which is a lso a peroxyacid. I don't have info on these acids...
- (V)Z -
New Mem ber
Posts: 2
From :
posted 07-10-2001 03:45 AM
--------------------------------------------------------------------------------
Next off, thx for your info about caro's acid. I was not able to locate any decent info on it anywhere, so wha t I know only com e s
s e c o n d h a n d f r o m a c h e m ist on the alt.engr.explosives newsgroup, so I do trust h is imput. I'm g o i n g t o g e t s o m e h 2 o 2
tomorrow, so I'll boil that down and try to m a k e s o m e caro's acid, and i'll report b ack the results.
BTW , d o e s a n y o n e k n o w t h e t e m perature that h2o2 decomposes? the best that I could find last nite was the heat o f
decomposition, how much energy it releases. But it appears that you can at least heat it to the boiling tem p at 1atm before it
will decompose. And lastly, if anyone knows what concentration you can reach by boiling h2o2, that would be very appreciated.
I was under the impression it was arou nd 60ish , but I couldn't tell you the source of this info.
Thx all!
------------------
-----
oh shit, you m ean it's lit?
Rhadon
Freq uent Poster
Posts: 95
From : Germ a n y
posted 07-13-2001 07:39 PM
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Deezs: As far as I know HClO4 is the strongest acid that exists.
- (V)Z -: To mention a way how to synthesize Caro's acid: KHSO 5 u n d K 2 S O 4 a r e a d d e d t o H2SO 4 . A n o t h e r m e t h o d :
Adding H2O 2 to chlorosulfuric acid. I doubt that adding H2O2 to H2SO4 will work, but just try it out and tell us what you found
out. If you're well-equipped you can try if the resulting acid oxidizes aniline to nitrobenzene (H2SO 5 d o e s s o ) .
Though, boiling down hydroge n peroxide will not work, most of it will just decom p o s e .
Marvin June 23rd, 2003, 02:29 PM

Deezs was describing a 'super acid' far superior to perchloric in terms of [H+], tho ugh I do nt know if they have any uses.
Adding sulph uric acid to barium p e r o x i d e t o p r o d u c e d i l u t e h y d r o g e n p e r o x i d e , a n d t h e n b oilng gently in a scratch free

container until it starts to decompose is supposed to produce ap prox a 40% solution. The stabilise rs in com m ertial stuff m a y
or m ay not h elp. Ive produced som eth ing over 30% by heating 9% to a little below boiling and directing a fan onto the surface.
T h e f u m es were more than a little unpleasent but I got what I wanted som ewhere between a 3:1 a nd a 4:1 reductio n in
volum e .
Pure 40% can be furthur concentrated up to 99+% as is needed by leaving the solution over sulphuric acid in a vacuum
dessicator at RT. More peroxide will be lost per amount of water as the concentration rises, and all im purities rem ain to
contam inate the prod uct. Much more o f a problem with stabilised dilute solutions. There is aparently no eutectic for this
m ethod.
drednort June 24th, 2003, 08:28 PM

Caro's acid (H2SO 5) is pretty aggressive and is a better oxidiser than H2 SO4 from which it is derived. Not e n o u g h t o d i s s o l v e
g l a s s , b u t m a y b e t o d a m age the surfa ce upon long exposure (HF although not a strong acid corrodes glass very easily). I use
it so metim e s ( i n s m a ll am ounts) for cleaning u p particu larly dirty glassware. Eithe r use Caro or fum ing nitric. I've never heard
or read of anyone concentrating it. I would guess that it is not so stable in pure form so concentration would probably give
degradation.
K2Cr2O7 and sulfuric acid (i.e. "Chrom ic Acid") is also a good oxidising a cid. This acid is stable but I've seen an accident with
this, in which it was being stored in a sealed container. It developed pressure (som ehow) and the guy who tried to open it to o k
a hit from the shattering vessel.

a n d I m provised C hemistry > Di-(2-ethylhexy)sebacate - Archive File
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m ongo blongo
Freq uent Poster
Posts: 175
From : I live in a Creo sote Bush!
posted 07-13-2001 11:17 PM
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Is Di-(2-ethylhexy)se becate u s e d i n C 4 ?
i have never seen this stuff!
I cant find a single post on it. Not even anythin g on the NET!
W hat the hell is this stuff?
W here can this be obtained/or how can it be made?
W hat is it's purpose in C4?
Any help will be great!!!
------------------
i like blowing shit up
cutefix
Freq uent Poster
Posts: 330
From : california
posted 07-14-2001 01:14 AM
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I think the reason why you cannot find it in the net is you m isspelled it.It should be Di(2-ethyl hex yl) sebacate ,synonym o u s t o
Diiso-octyl sebacate.This material is a plasticizer,like polyisobutylene.Better checkTim Lewis Kitchen im provised plastic
e x p l o s i v e s 2 s o t h a t y o u c a n l e a r n m ore about its purpose in C-4.
For MSDS check:
http://www.redox.com .au/m sd s/m sds.data/ETHESE.HTM
[This message has been edited by cutefix (edited July 14, 2001).]
m ongo blongo
Freq uent Poster
Posts: 175
posted 07-14-2001 08:49 AM
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Nice one dud e!!
Shit I don't know how this got posted twice!
m ongo blongo
Freq uent Poster
Posts: 175
posted 07-16-2001 04:30 PM
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Right just looked at Kitchen im provised plastic explosives2 from http://www.sectio n1.f2s.com /files.html
It doesn't say much dude.
I still do not know m uch about it's purpose in C 4 or whe re to get it/make it.
cutefix
Freq uent Poster
Posts: 330
From : california
posted 07-16-2001 08:03 PM
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Ethyl hexyl sebacate is one of the plasticizers for m a k i n g plastic explosives like C -4.Regarding sources,i think you have to find
that from chem ical supplies,anyway there is already a specs listed in that website I listed before.
Dave Angel Decem ber 22nd, 2003, 01:20 PM

I have been scouring the web for inform ation on this substance and came across a pdf detailing th e c o m p o sition of oils, in
which it state d that th e sebacic acid used in the m anufacture of sebacates is from castor o il. This g ot me th inking that it can't
b e t o o h a r d t o s y n t h e s i s e a s e b a c a t e f r o m widely availa ble OTC products by way of a transesterification: The conversion of an
este r of one alcohol into the ester of a nother.
In the case of di-(2-ethylhexy)sebacate the alcohol use d would be 2-ethylhexanol. Unfortunately, AFAIK, 2-ethylhexanol is not
a v a i l a b l e O T C s o a n o ther alco hol will h ave to be used in its place. In my synthesis below, I used IPA as it is readily available in
relatively high purity as a cleaner for electronics. If my nom enclature is correct, it should g ive the product di-
(methyethyl)sebacate, which will probably have a lower viscosity than di-(2-ethylhexy)sebacate owing to the sorter chained
alcohol. This may or m ay not be a problem in using it a s a subtitute for the latter, and will require further investigation.
Also, one would ideally use KOH as the catalyst due to its higher solubility in the alcohol, but NaOH is m uch easier to get hold
of.
The only difficulty I can see with this hom e synthesis is the refluxing step. I have the luxury of a reflux con denser, but I
thought that if I didn't, I might try using a pressure cooker to keep the liquids from boiling away whilst they were heated.
Having said that, I wouldn't want the over pressure valve venting alcohol vapor everywhere, especially if I was using gas...
In m y synthesis, I used:
5 0 0 m L IPA
4 0 0 m L Castor Oil
17g NaOH (d ried as best as possible, water mu st be kept to a m inimum )
Procedure:
D i s s o l v e 1 7 g o f N a O H i n t o 5 0 0 m L of IPA, (not all of this dissolved in m y case, but it was the amou nt I calculated was
appropriate.)
Stir the solution into 400m L of C astor O il. I continued stirring for about a n hour before realising that on a cold winte rs night at
3 degrees above zero, the reaction would need some heating to get anywhere.
Once thoroughly mixed, pour into a rb flask with a condenser an d reflux it to boiling for 9 hours. This was perhaps a bit
excessive, but the ex cess NaOH only started to dissolve after about 3 ho urs indicating tha t only then was significant product
bein g form e d .
Leave to cool only until it stop s boiling and then pour in to a suitably sized pyrex bowl. A tall jar would probably be better, but
at this stage was not large enough to accomodate the product and the first lot of washing water. In fact a separating funnel
would be ideal if available.
Now all that it left is to wash the product. Pour plenty of hot wate r into the mix and stir it well. Leave it to settle and the layers
should separate until the lowe r water layer will be milky - full of impurities such as glycerol, soap, NaOH, ex c e s s I P A , a n d t h e
upper layer will be an off-yellow oil, the sebacate.
Pipe tte the top layer off (turkey baster?) and into another jar into which hot water is again poured and stirred in. Repeat the
process so that sebacate is thoroughly washed and the water layer is clear. It's a good ide a to pipette the product into a
container for storage whilst it is still hot and easier to handle due to its lower viscosity.
I obtained about 260g of product with this method.

a n d I m provised C hemistry > W eird nitration pro cess - Archive File
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HMT D Factory
Freq uent Poster
Posts: 220
From :
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W ithout using HNO3 and H2SO4? This process is m o r e l i k e a n e x t r a m e t h o d f o r k nowledge since HNO3 and H2SO 4 m u s t h a v e
flooded in you people's room .
C a m e across this patent that use NO2 and Fe(NO3)3.H2O--"wet" ferric nitrate, to nitrate aromatic compound, like to l u e n e .
T h e p r o c e s s t a k e s p l a c e a t r o o m t e m p erature and under norm al pressure. Produces no waste

acid and m ild tem perature. By product is washed away with water. Funny huh?
nbk2000
Moderator
Posts: 1135
From : G u e s s
--------------------------------------------------------------------------------
Rather than teasing us, why not give u s the patent num ber?
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HMT D Factory
Freq uent Poster
Posts: 220
From :
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Not listed, I think it is a JP patent num ber,
not US.
nbk2000
Moderator
Posts: 1135
From : G u e s s
--------------------------------------------------------------------------------
Than type the details or scan it in. Hell, even a screen shot would be OK.
------------------
HMT D Factory
Freq uent Poster
Posts: 220
From :
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Details are just like that. Things are all done in room condition, solid liquid mixing, gas blowing.... No liquid is involved except
the benzene derivatives.
I think both ferric nitrate hydrate and NO2 involves in the nitration, neither of them is
a catalyst.
ezekiel
Freq uent Poster
Posts: 110
From :
--------------------------------------------------------------------------------
Shall I let you in on the secret?
Here we go:
The NO2 gas dissolves into the hydrated iron oxide,

Now you have a curious little particle that essetially contains HNO 3.
The iron oxide will not nitrate itself, pa rtly because is is unreactive, and partly becasue of the local charge configuration in th e
particle.
Now, the NO 2 (kinda part of a HNO3) is being ionised and pushed into an electrostaic filed created by the iron oxide. This
m a k e s i t e v e n m ore of a nucleophile than norm al.
W hen a tluen (or wha tever) atom com es along the NO2 can't wait to jum p o f f a n d react with it.
Thus you are still left with your iron oxide; which acts as a catalyst.
------------------
Ezekiel
HMT D Factory
Freq uent Poster
Posts: 220
From :
--------------------------------------------------------------------------------
It's not even iron oxide.
It's Fe(NO3)3 . H2O
Just because you have a general idea of catalyst m e c h e n i s m d o e s n ' t m e an you have to let out a lot of "educated guess".
Plus, hydrated iron oxide will react with NO2 in the instant they com e in contact. "partially because it is not reactive"?
W achatalkinbout?
ezekiel
Freq uent Poster
Posts: 110
From :
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Sorry Im u s t h a v e m i s r e d t h e q u e s t i o n .
I said "partly" beacsu e it is a com plex electrostatic mechanism that is no t easy to explain to anybody witho ut alot of time and
a basic knowlege of chem istry.
The reason i assumed it was iron oxide is that a sim ilar reaction occurs b e t w e e n s o m e g a s e s i n t h e p r e s e n c e o f i r o n o x i d e .
I'm really ever so sorry for assum ing something like that, really I am .
A "BASIC KNOW LEGE O F C A T A Y L T I C P R O C E S S " e h ?

W hy do you have to try and imply that I do not fully understand it?
I accept that I am not an expert, and catalytic chem istry is a subject in itself that is im possibly com plex in nature.
W ell, having been so rightiously corrected by the m an who m a k e t h h e x a m ethylenetriperoxidediam ide...

I will conlcude that in fact the reaction is still catalytic (it m u s t b e a s N O 2 a n d t o l u e n e d o n o t r e a c t n o m ally).
It could be basically what I said before but wiht the NO2 anion form ed differntly. In the en d there m ust be a NO2 nucleophile
ion to bond into the benzene ring.
Sorry guys for misreading that...
I m ean I was sjut so out of place!
------------------
Ezekiel
HMT D Factory
Freq uent Poster
Posts: 220
From :
--------------------------------------------------------------------------------
Now our venerable gu e s t s p e a ker who jumped in, didn't read careful enough, acted like an know-it-all, condescende d , a n d t h e n
backfired, apologized !
If it is a reaction catalyzed by ferric nitrate hydrate.
Then try explain this : (HA!)
R-H + NO 2 ---> R-NO 2
without any byproduct or involvem ent of ferric nitrate hydrate...
Now where'd "thine" H atom go? Shake-a-spear?
Mr C ool
Freq uent Poster
Posts: 991
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Ezekiel: just checking , but you didn't really m e a n t o s a y a t o l u e n e a t o m , did you? An ATOM of tolu e n e ?
N o ? O h g o o d , that's OK then.
PHILOU Zrea lone

Freq uent Poster
Posts: 479
--------------------------------------------------------------------------------
If you knew m ore about organic chem istry, you would know the chlorination process of arom atics to involve a Cl(+) ion m a d e
from C l2 with a catalyst; this one is AlCl3 (dry) or Fe(Cl3)....They act as Lewis acid by complexing the Cl(-) anion...
FeCl3 + Cl-Cl--> (FeCl4)(-) + Cl(+)
W hitout this C l2 is inert or attacks but outside the arom atic ring.
C6H6 +Cl(+) ---> (C6H6Cl)(+)---> C6H5Cl +H(+)
Then
H(+) + FeCl4(-) gives HC l (dry gas) and FeCl3.
As a conclusion when all term s in com m o n h a v e b e e n t a k e n a w a y (catalyst):
C6H6 + Cl2--> C6H5Cl + HCl
W hy to tell this? Think a bit....
Fe(NO3)3 + O2N-NO2 ---> NO2(+) + O 2N-Fe(NO3)3(-)
NO2(+) + C6 H6 --> (C6H6NO2)(+)--> C6H5NO2 +H(+)
H(+) +O2N-Fe(NO 3)3(-)---> HNO2 + Fe(NO3)3
2HNO 2--> H2O + N2O3--> H2O + NO + NO2
2NO + O2 -->2NO 2
Thus after sim plification:
C6H6 + N2O4 --> C6H5NO 2 + 1/2H2O + 1/2NO +1/2NO 2
ASAT: As sim p l e a s t h a t

a n d I m provised C hemistry > Hydogen Iodine - Archive File
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C h e m Boy
A new voice
Posts: 7
From : s d f a s
--------------------------------------------------------------------------------
Has anyone m ake Hydrogen Iodine? If you havnt heard of it its hydrogen gas and iodine gas combined to make a explosive.
Or h ydrogen gas driped into iodine (liquid) to making a gas. If you have heard it or m a d e i t p o s t a m e s s a g e .
m egalom ania
Adm inistrator
Posts: 653
From : U SA
--------------------------------------------------------------------------------
Do you m ean hydrogen iodide gas? If so, it is not explosive, nor flam m able. It is just anhydrous hydroiodic acid, like HC l. The
only way a m ixture of iodine and hydrogen is explosive is because hydrogen is explosive. And you can't drip hydrog e n o n t o
l i q u i d i o d i n e t o m a k e a n y t h i n g , h y d r o g e n i s a g a s a n d i o d i n e e x ists as a solid, jeez. Maybe this guy is thinking of n itrogen
triiodide.
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For the m o s t c o m p r e h e n s i v e a n d i n f o r m a t i v e w e b s i t e o n e x p l o s i v e s a n d r e l a t e d t o p i c s , g o t o M e g a l o m a n i a ' s E x p l o s i v e s a n d
Stuff at http://surf.to/m e g a l o m a n i a
nbk2000
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Posts: 1135
From : G u e s s
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Hydriodic acid (HI gas in water) is used in clandestine chem istry for m a k i n g m e t h a m pheta mine by reduction of ephedrine.
It has no explosive use.
T o m a k e i t , p l a c e a q uantity of iodine crystals in distilled water. Bubble a stream of hydrogen sulfide gas through th e solutio n
till n o crystals are visible at the bottom of the flask.
Then filter th rough glass wool to rem o v e t h e e l e m ental sulfur that precipitates out. Concentration is determ ined by specific
gravity.
Distillation yields the 1.54 needed for reduction.
Hydrogen sulfide is easily m a d e b y m ixing sulfur and paraffin wax (or ke r o s e n e ) a n d h e a t i n g t o j u s t h i g h e n o u g h t o m e l t t h e

sulfur. Pass the gas through a long, wide tube loosely filled with cotton wool to filter out sulfur particles.
I f n o n e o f t h e a b o v e i n f o r m ation has any m eaning to you, you obviously didn't need to ask the question in the first place.
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Jhonbus
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From :
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Be careful... Hydrogen sulphid e is a *mite* tox ic
PYRO 500
Moderator
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Hydrogen Sulfide is VERY TOXIC!
HMT D Factory
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H y d r o g e n s u l f i d e s m ells like fart
hodehum
A new voice
Posts: 21
From : New Zealand
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Hydrogen Iodine is used as an inhibitor in liquid rocket fuel that contains red fum ing nitric acid/kerosene m ixtures to stop it
e a t i n g t h e m etal fuel tanks.
see for yourself
http://www.gulflink.osd.m il/irfna/irfna_sec01.htm
PHILOU Zrea lone

Freq uent Poster
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2HI<==>H2 + I2
The reaction is easily reversible reason why HI is a good mild reducer...

a n d I m provised C hemistry > m annitol = sorbitol? - Archive File
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Mr C ool
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--------------------------------------------------------------------------------
I'm posting this, since for a lo ng tim e I've been wanting som e m annitol, for mannitol hexanitrate. Also, for a long time I've
been buying sorbitol by the pound for use in ro ckets. I knew tha t both were poly-hydric alcohols, but I've never tried to nitrate
sorb itol in case it was hyper-sensitive. Just now, I was reading Mega's site, and lo oked at the structure for MHN. Then, a little
later, I was looking at R ichard Nakka's m odel rocketry page, and noticed that if you replace the nitro groups on the MHN
m olecule, the formula and structure is the same as sorbitol!!!
Is it true that m annitol and sorbitol are synonym s for the sam e chem ical? Please reply if you have any info on this. I don't
want to nitrate som e sorbitol without m aking sure that there hasn't been a typo, or m a y b e o n e o f t h e m g o t c o n f u s e d.
10fingers
Freq uent Poster
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From : U SA
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Mannitol and Sorbitol are two separate things. Hydrogenation of fructose with catalyst will yield a 50/50 m ixture of these two
sugar alcohols.
Sorbitol can be nitrated to Sorbitol Hexanitrate but I can find no info on its properties.
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
I just found a site on sugar substitutes which m e n t i o n e d t h e m b o t h s e p e ratley. O h well, never m ind.
If I dare to nitrate som e sorbitol I'll post my re sults.
Oh, and if you want to buy som e sorbitol then I've found a place that's e a s i e r a n d c h e a p e r than Skyilghter (I didn't actually
search for it m yself, Richard Nakka did , but tha t's not important). It is: www.sugarlessshop.com /20 00/sugarsubstitutes.htm It's
$3.79/lb, rather than $5.15/lb , and you don't h ave to give ID or be on file with them . They don't have pure m annitol though .
Mr C ool
Freq uent Poster
Posts: 991
--------------------------------------------------------------------------------
W e l l , d o e s a n y o n e h a v e a n y i n f o r m ation on hexanitrosorbitol? It'd be very similar to MHN, but I'd like to m a k e s u r e b e f o r e I
m ake any, for obviou s reason s.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > making K2CO3 -
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the_wingman
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Posts: 48
From:
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I read in a former topic that it's possible to make potassium carbonate from KNO3 and C.
blackadder
Frequent Poster
Posts: 313
From: London
--------------------------------------------------------------------------------
Just wondering why you want potassium carbonate, when you can have kno3?
hehe
[This message has been edited by blackadder (edited February 14, 2001).]
firebreether
Frequent Poster
Posts: 109
From:
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Probably wants to make fulminating powder.
right?
jin
Frequent Poster
Posts: 111
From: uk
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its been a few years since i have done it,but i think its the same as normal gunpowder without the sulphur 2kno3+3c=k2co3+3co
try 3 parts kno3 and 1c if that will not work try 2 parts c.
[This message has been edited by jin (edited February 14, 2001).]
Mammut
A new voice
Posts: 39
--------------------------------------------------------------------------------
quote:
--------------------------------------------------------------------------------
Originally posted by the_wingman:
I read in a former topic that it's possible to make potassium carbonate from KNO3 and C.
--------------------------------------------------------------------------------
U have KNO3 and u will make K2CO3 oh oh oh

I can tell u a easier way to make K2CO3, if u give me the KNO3
J
Moderator
Posts: 605
--------------------------------------------------------------------------------
Why not tell us all?
J
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'Lofty' Wiseman
SMAG 12B/E5
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You can obtain potassium carbonate from some pool suppliers for akaline Ph adjustment of water or leach it from wood ashes.
[This message has been edited by SMAG 12B/E5 (edited March 16, 2001).]
Agent Blak
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From: Sk. Canada
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Can't you also get K2CO3 as Baking Powder? I will check the Pool thing today.
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Anthony
Moderator
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From: England
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Baking soda is sodium bicarbonate
washing crystals are sodium carbonate

In my estimation the best source of potassium carbonate is from wood ash. As a frequent fireplace user I have access to large volumes of the stuff. It is quite readily soluable
from the ash, from which it can be filtered. I can't vouch for the purity, but after a few recrystillizations one can get fairly ash free crystals. There may be some other soluable
components, but the vast majority is potassium carbonate. I recommend using cheap shop towls for the initial filtration to remove the bulk of the ash after steeping the ash in
hot water. This filtered water can then be subjected to more vigerous filtration methods.
jeffchem2000 July 24th, 2003, 05:35 PM

if you are going to collect the potash from ashes make sure that the wood wasn't treated because they leave some nasties in the ash. I don't know what exactly but they could
be copper and arsenic salts. They also make the solution a yellowy green colour.
frogfot July 24th, 2003, 05:52 PM

Some year ago I burned a mix of 100 g KNO3 and 50 g coarse C to ubtain K2CO3 also. I wrote down yield of extracted solid to 49 g (91%).
matjaz December 12th, 2003, 05:52 AM

megalomania:
In my estimation the best source of potassium carbonate is from wood ash. ...
... This filtered water can then be subjected to more vigerous filtration methods.Any recall of the yield you've got?
I just washed some 100g of ash (mixture with lots of charcoal pieces :rolleyes: ) last night. Used a nylon sock to filter off the charcoal and got some 1/2 l of darkgrey slurry.
This morning, I noticed that the slurry settled to the bottom 1/3 of the cup and I could decant crystal clear colourless solution from the top. I figure, I'd get at least 66% of all
K2CO3 this way since it's so soluble. Will post the results when I get the crystals and weigh them.
matjaz December 13th, 2003, 06:54 AM

(couldn't EDIT, 1440 min limit... please join this msg with the previous one if you see fit)
The dirty bottom third settled again to 1/2 mud, 1/2 clear solution so i could decant another 70ml. This makes 300ml of the solution, pH=10-11. 15ml of this were dried in a
petri dish on the room heating radiator. I got 200mg of dry crystals of potash, probably not a very pure one,
tiny fragile dirty-white crystals. My 300ml solution should thus contain 4g of K2CO3. Since my ash had a LOT of charcoal pieces mixed in, I'd say 4g of potash from 40g-60g of
pure ashes.
This makes around 10% by weight of K2CO3 in wood ash (beech-wood I believe). The only pain is to get rid of all the water. If less water is used, the fraction you can pour
off is smaller, reducing yield.

a n d I m provised C hemistry > m e t h e n a m i n e / h e x a m i n e m anufacture? - Archive File
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BaDSeeD
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From : buffalo, ny
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Sorry to ask a question that has proba bly been answered already... but I cant seem to search up any results. Yes I checked
the forum , and yes I checked the synthesis section on m e g a l o m ania's site.
I know I have read this som ewhere, and probably had it saved on m y ha rd drive (before it crapped out on m e ) . C a n s o m e o n e
d e s c r i b e t h e m e t h o d f o r h e x a m ine/m e t h e n a m ine m anufacture? I've never m ade HMTD before, and would like to try it, as I am
a little fed up with cra ppy AP yields. I can't seem to find a source to buy it from locally, so that leaves m e with the a lternative
of m aking it.
To all m oderators:
T h i s m ay not be the best place to ask this question, but as it is FO R H M T D ( a n e x p l o s i v e p e r o x i d e ) it seem e d l i k e t h e b e s t
choice. I have a sugg estion though. If you revamp the forum again... ho w about adding a n "im pro vised chem icals" section, or
"che mical synthesis" section.
Might be a good idea.
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BaDSeeD
Knowledge is the true power, ignorrance will bring your demise.
vehem t
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You could try surplus stores north of the border.
Cricket
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I know KIPE (I think one, but m aybe two) has it in there. I believe I have posted that chapter (Hexam ine Manufacture) befo re,
but you said you couldn't find it. If you need, I will post it again. Also, if you live in the US (check even if you don't), look in an
Army Surplus store. I bought three bottles a couple days ago. The bottle is white and says:
"HEXAMINE TABLETS
(Com pressed Fuel)
Stock No. T908
Contains 6 Tablets
KEEP DRY".
It costs (m e) $1.75 U SD. The tube is about 1" in diame ter by 3" in length. Also it said you get a 20% disco unt if you can
provide a m ilitary ID or a couple other things.
[This message has been edited by Cricket (edited March 02, 2001).]
SofaKing
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4 0 0 g a m m onia water (5%)
54g formaldehyde (37%)
Mix in shallow pyrex dish, let evaporate. C ollect crystals.
green beret
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From : Austra lia
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D o e s a n y o n e k n o w a w a y o f r e m o v i n g t h e w a x c o a t i n g o n H e x a m ine fuel tablets? Mine are coated in wax and I want to get it
o f f b e c a u s e I a m going to ate mpt to m a k e R D X .
blackadder
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green beret, try putting the tablets on a radiator, or maybe putting the tablets in front of one of th ose electric heaters (on the
high e s t h e a t ) .
10fingers
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T o p u r i f y h e x a m i n e g et some methanol, put it in a jar and place in hot water. Dissolve as much hexamine as will go into
solution, The impurities will settle to the bottom , take o ff of hea t and let settle for a m inu te, pour off liquid and place this in
the freezer. In a few hours the hexamine will crystallize out.
[This message has been edited by 10fingers (edited March 04, 2001).]
BaDSeeD
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From : buffalo, ny
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I h a v e h o n e s t l y n e v e r s e e n a n A r m y surplus store in O ntario, m ight be worth a look thoug h. But th a n k s f o r t h e i n f o o n t h e
synthyesis. I'll use that as a last resort if I can't find a supply.
As for the hydrogen peroxide, I read in one of the posts that som eone found 30% as a "chlorine free pool oxidizer". Has
a n y o n e s e e n this? Got a brand name? Or a chain store that carries it? I'm sick of 3%.
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BaDSeeD
Knowledge is the true power, ignorrance will bring your demise.
BaDSeeD
Freq uent Poster
Posts: 80
From : buffalo, ny
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Nevermind, did a little searching and a nswered my own question.
I found a very helpfull site that is not only a so urce for it, but also told m e that it was 27% hydrogen peroxide.
http://stores.yahoo.com / s p a s t o r e / b a q u a c i l s h o c k . h t m l
$13.75 per g allon isn't that bad, and it shouldn't be hard to find locally a nyhow.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Easy O2 - Archive
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ChemBoy
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Posts: 7
From: sdfas
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I found out how to make cheap and easy O2. Now this might sound funny and stupid but I know for a fact that this works. 2 things you need is some Hydrogen Peroxide and
some potatoes. First you put the potatoes into a blender to make a potato extract. Add water to make a soup like extract. Take the extract and put it into a container. Add
some H2O2 to the potato extract. Now what happens is the enzymes in the potatoes speeds up the brake down of the H2O2 and brakes it down into H2O and O2 . Now I know
this works because I did this in Biology a while back in school.
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What comes up must go down.
Anthony
Moderator
Posts: 2321
From: England
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Even easier O2! - buy a compressed oxygen bottle...
I know the reaction you mean though, the enzyme (catalyse?) in the potato (lots more of it in liver) breaks down the peroxide etc
ChemBoy
A new voice
Posts: 7
From: sdfas
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Ahh liver I didnt think of that. I posted the message for the underaged people out there who cant get compressed O2 tanks. Im guessing your talking about the ones welders
use?
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What comes up must go down.
pyromaniac_guy
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Posts: 33
From: us
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if you want compressed o2.. go and buy it... here int he states kmart, walmart, sears (at least by me) all carry compressed o2 in low pressur tanks similar to the ones propane
used in household blow torches comes it...
Nitro
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Blood has the same results on peroxid.But i think its better you use an very small amount of KMNO4.
Digital-Demon
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All metal oxides will come up with the same result.
H2O2 will decompose slowly into H2O + O2 at room temp, but then at least you know it's pure.
Anthony
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Posts: 2321
From: England
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Yeah, they're sued for small welding outfits (DIY level) the bottles are dispossable (contain about 60litres of 02 IIRC) and are a few quid each.
BoB-
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I've been working on an o2 making regulator, it will use Manganese Dioxide and H2o2.
ChemBoy
A new voice
Posts: 7
From: sdfas
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I posted my message for the poeple who are underage and cant get a hold of welding o2.
Anthony
Moderator
Posts: 2321
From: England
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There is no age restrcition on oxygen. Just walk into Halfords/a "hardware store" pick one up and pay for it.
blackadder
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From: London
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What legitimate reason could a 14 year old like me possess, to buy oxygen.
Jhonbus
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You don't need a reason; they won't ask.
blackadder
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From: London
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I guess I could say it was for a science projekt, just in case there's a really suspicious sales clerk there.
Anthony
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From: England
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They won't ask, but if it made you feel better then just say your dad asked you to pick one up.
ChemBoy
A new voice
Posts: 7
From: sdfas
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The thing is where I live you have to by 18 up to buy things like welding gas (propain) welding suplies and O2. What I can but is solidox rods and make cool shit out of that.
Anthony
Moderator
Posts: 2321
From: England
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I can understand them restricting propane because some idiots inhale it, but they won't let you have 02 but they will let you have KCl03?!
firebreether
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wtf is a solidox rod?
PYRO500
Moderator
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why not go to a medical supply outlet (they are everywhere, just follow the cars filled with the old people. you could probably steal or buy an o2 tank from them they may be
a bit pricy though. if they ask just tell them that you need it for your grampa who has athsma real bad and sent you to bring him some O2
blackadder
Frequent Poster
Posts: 313
From: London
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"solidox" is short for "solid oxygen". It's used in welding applications to provide a source of O2.
It consists of KClO3 and some other binder to hold it together into a "rod".
Basically, solidox rods are sticks of KCLO3.
Mendeleev November 7th, 2003, 05:42 PM

I can't believe they will not let you buy oxygen tanks, from a freakin' hardware store, that sounds like a load of shit to me. Damn, I hate those suspicious asses, when I tried
to buy an oxygen tank the guy asked me if I was making a bomb, but here in South Carolina, there are no laws agaist buying O2 tanks at age 16. As far as I know there are
four methods of getting oxygen. One is most likely not possible in house conditions, which involves freezing air, and since the different gases in air have different boiling and
freezing point, you could drain of all the gases but oxygen, or drain of oxygen from all the other gases. This method is how oxygen is industrially extracted, but it is not very
atainable, unless you can somehow rig your fridge into overdirive (good luck). The other three methods are much more attainable. One is, as was mentioned, adding liver to
hydrogen peroxide. This works because the liver is a detoxifying center and thus its cells contain more organelles known as peroxisomes which contain contain the enzyme
catalase which catalyzes the following reaction: 2 H2O2 ---> 2 H2O + 1O2. The second method is buying it at Lowes or Home Depot, but that method was unavailable to
Chemboy. Chemboy however mentioned he could get solidox rods. To generate oxygen just mix potassium chlorate (the solidox rods) with manganese oxide, which is the
gooey, gritty stuff inside batteries. Put the two ingredients into a container and heat them. This will yield oxygen. You can do the reaction with just KClO3 and heat, but MnO2
makes the reaction faster. I personally think it is really gay that you can't buy oxygen tanks wherever it is Chemboy lives, I don't know what I would do without my oxy-MAPP
blow torch.
Cyclonite November 8th, 2003, 11:27 AM

You just posted a bunch of info that was stated above you in one post.......anyways O2 production with h2o2 is a waste of time. Im sure you can find a way to obtain an O2
tank. You put 1/2 the effort into that that you put into making it and it should be no problem. Look at the time vs. product amount. Think how much h2o2 you would go
through and time to simply get the same amount from a small O2 tank.
klassasin November 8th, 2003, 12:01 PM

That is interesting, Solidox Rods. Does anyone know what brand name they are sold under? and maybe where? They sound like an interesting investment.
Thank you for help in advance.
Mendeleev November 8th, 2003, 03:49 PM

Solidox used to be sold at K-Mart, but not anymore. Try some hardware stores like ACE or Lowes. Also I think the anarchist cookbook (I know I shouldn't mention it, but that
thing has occasionally useful information) says you might be able to get it at Sears or a heating and plumbing supply store. You could just make potassium chlorate by distilling
a mixture of houshold bleach and potassium chloride.
Edit: I forgot to mention you can mix solidox with sugar and use a fuse to make a decent explosive. Be careful though, its sensitive to friction.
klassasin November 8th, 2003, 07:10 PM

Friction... curse friction. Thanks for the tips, now I must go look.
Ropik April 23rd, 2004, 08:22 AM

I prepare my oxygen with H2O2 and manganese dioxide from bateries. I just went to my school class(yes I am still student) and ask: "Has anybody an old batteries? I need
some. Thanks" and next day I leave the school with one pound bag full of batteries. Cheap ;) (maybe even cheaper than potatoes). I rip batteries out, place the black stuff to
bucket, rinse with tap water(manganese dioxide is acid-polluted) and let dry. Then I place it in my gas-making apparatus(really complicated:flask, drilled stopper, tube through
this hole and syringe needle for adding H2O2 stick in the stopper) and slowly add the peroxide. I used this mainly for speed up melting of candles. Stupid but funny: you light
the candle and run a stream of oxygen through the flame.
Jome skanish April 24th, 2004, 09:37 PM

One method for obtaining a steady flow of O2 gas is electrolyzing a solution of copper sulphate. The H2 formed is absorbed in the liquid to form H2SO4 as the copper is "plated"
onto the cathode. But I guess this method is useless if you can obtain O2-flasks, MnO2, KMnO4 or H2O2...
vulture April 25th, 2004, 08:41 AM

You could just make potassium chlorate by distilling a mixture of houshold bleach and potassium chloride.
<nitpick> It's not exactly distilling...</nitpick>
kingspaz April 25th, 2004, 12:49 PM

Mendeleev, please re-read your posts before posting. Posting of inaccurate information will give you a bad rep, and consistently bad information WILL lead to banning.

a n d I m provised C hemistry > Potassium picrate - Archive File
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FadeToBlackened
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O n m e g a l o m ania's, it is described how this Glauber guy m ade it by disso lving wood in nitric acid and neutralizing it w/
p o t a s s i u m c a r b o n a t e . W hat is in wood that takes place in this re action? Is there something resem bling picric acid or what. And
where can I get m ore info about this Glauber guy, a website, book, or wh atnot? -thanks
jin
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if yo u purified wood b y boiling and bleching and then nitrated it you would get a im pure nitrocellulose m ixture.
there must h a v e b e e n a m istake in wh at you read.
Mr C ool
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I read that TNP was first m ade by nitra ting wood, so ma y b e t h e r e i s s o m e t h i n g i n s o m e k i n d s o f w o o d t h a t r e s e m b l e s p h e n o l ?
Many natural resins a re smelly, so they might contain arom a t i c c o m p o u n d s s o m e t i m e s .
But I don't think it wo uld be a useful way of m aking it.
jin
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in 1645 glauber disco vered that heatin g saltpetre with sulphuric acid was better m e t h o d o f m aking nitric than the old way of
heating green virtiol with alum and saltpetre.
btw som e tre e barks contain acetylsalicylic acid but in very small amounts.
[This message has been edited by jin (edited March 16, 2001).]
Mr C ool
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W illow, conta ins salicylic acid.
c0deblue
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Just a thought, but could this have anything to do with the reason willow charcoal is widely regarded as a su perior ch arcoal?
blackadder
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I think willow charcoal still has lots of Hydrogen and Oxygen in it.
Jhonbus
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W illow charcoal is very porous.
m egalom ania
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That info on my site comes straight from a book, I forget which one, and it was an older reference, but still quite accurate.
C e l l u l o s e m a k e s u p o n l y 4 0 - 5 0% of th e conten t of wood. Then there is h emicellulose, lignin, and a varity o f cresols and saps.
Don't forget that plan ts are a veritable factory of chemical substances, and rich in aromatic molecules.
And plants do not have acetylsalicylic acid, the acetyl part is added by m a n b e c a u se salicylic acid straight up has som e b a d
side effects.

Furthermore, acetylsalicylicacid wouldn't exist in a plant, as it imm ediatly hydrolyzes into salicylic acid and acetic acid.

a n d I m provised C hemistry > Nitrating mixtures - Archive File
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FadeToBlackened
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Forg ive m e for asking, but why is sulfu ric acid used in nitrating things so much? Like T.N.T . nitic An d sulfuric acids are used.
W hy is this?
CragHack
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i believe it is used to isolate water m olecules so as to get a "dryer" m ixture.
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c0deblue
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CragHack is correct. By binding water m olecules H2SO 4 effectively "concentrates" the Nitric Acid to a level suitable fo r nitration
purposes. I believe it's accurate to say that in m ost cases no Sulphuric Acid would be nece ssary if 99% Nitric Acid could be
obtained.
Machiavelli
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W hen nitrating som ething you normally have an equilibrium reaction like
Nitric + Shit <=> Nitra ted Shit + W ater
This reaction has a certain reaction constant de pending on concentrations and temperature and pressure etc and it will try to
stay in a state of equ ilibrium.
L e t ' s a s s u m e for our exam ple that it's 1:1, the same concentrations of p roducts and educts.
Now when I use concentrated sulfuric acid, it will form a hydrate complex with the water and we'll get a proportion of eg 2:1
because it re moves the water from the reaction and we have eg twice as m uch nitric + shit as we have nitrated shit.
But the reaction wants 1:1 so it'll produce m ore Nitrated Shit and m ore water to get 1:1 again. The water gets absorbed again ,
2:1, etc, ...
D e m olition
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Shit!!!
Sorry but I just couldn't resist.
D e m olition
Bitter
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Oh......Shit.
Roughly how much sulphuric a cid (99%) would be needed to isolate the water from 70% Nitric acid ? I can't seem to find this
information anywhere (I wonder why...).
c0deblue
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I'm not a chem ist, but Machiavelli's ex p l a n a t i o n s u m m ed things up and certainly increased my own understanding of nitration
d y n a m ics. Given the variables in equilibrium reactions it would seem the H2SO4 requirem ent could be different not only for
each substance but for each set of nitration conditions as well. If this is so then perhaps the amount of H2SO4 needed to
"con centrate" 70% Nitric Acid to 99% is irrelevant since m ore or less water would be produced during the reaction itself and thus
require m ore or less H2SO 4. Mach, could you elaborate further on this point?
Bitter
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I don't think it's all that im portant to take the water produced as a reaction by-product into consideration. After all, using 99%
nitric acid doesn't need anything extra putting in for it to produce, say RDX or PETN.
DF90 June 11th, 2007, 04:57 PM

From my understanding the sulphuric acid is used with the nitric acid in a nitrating m ixture to generate the nitronium ion, which
can then electrophilically substitute onto the arom atic ring
HNO 3 + H2SO4 -> H2NO3(+) + HSO4(-)

H2NO 3(+) -> NO 2(+) + H2O
W here a +/- in brackets indicates an ion.
The nitronium ion (NO2+) then substitutes into the aromatic ring producing a H(+) ion tha t regenerates the sulphuric acid.
H(+) + HSO 4(-) -> H2SO4
The sulphuric acid can then react with m ore nitric acid to produce even more nitronium ions, and is therefore a catalyst to the
reaction.
As for the R DX, I am unsure because it is a non-arom atic heterocycle (all the atom s h a v e m a d e a l l t h e b o n d s t h e y c a n ,
therefore there are no electrons that can delocalise, and so it is not arom atic?) and so probably doesnt follow the sam e
m e c h a n i s m , a n d t h e r e f o r e d o e s n o t r e quire the sulphuric acid present. Also with RDX it is the N atoms being nitrated, not the C
atoms like in the synthesis of TNT.
It m ight also be possible to substitute other acids in the place of sulphuric for nitration m ixtures as the acid is just a source of
H+ ions. The general nitration reaction should also require som e water present at the start to allow the acids to dissociate into
ions, although the reaction do es produce its own water. Again the presence of water does not seem to affect the RDX reaction,
a s M e g a l o m ania's synthesis u ses 100% nitric a cid and m e t h a n a m i n e ( h e x a m i n e ) .

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FadeToBlackened
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I v e l o n g h e l d s o m e fascination with electrochemistry (since 3rd grade probably), but age restrictions apply to m e so i cant get
a lot of chem icals. Th e following is just som e thinking i've been doing. I ask of you to read it,to (try) to understand it, and to
critique, verify, or con tradict m y ideas, and to fill m e in on what im missing out on.
Beware, and judge not, for what lies below is the ramblings of a 15 yr. old (yes, thats right). I may not have used correct
term inology, or said somethin g incorre ctly, but I know what I am talking about. I try to explain myself as best as possible, but
it is partly up to the reader to try to interpret m y words.
-------------------------------------------
Today I was thinking about something.
I n a N a C l s o m ewhat concentrated solution @12v
In doing various things with NaCl solution and a 12v power supply, I have noticed that if I didn't use an iron nail for one of my
electrodes, cathode i think, my copper wire wou ld erode away, leaving som e green com pound in the electrolyte. If I just put in
it for a few m inutes, then took m y soldering torch to it (the green stuff on the wire) it m a d e a n i c e g r e e n f l a m e. I'm a s s u m i n g
this was copper chloride, in fact im pretty convinced it is. If so, one could produce reasonable am ounts by using, say, a copp er
pipe /tube for the electrode. The coppe r pipe would provide the copper, and the Cl- in solution would be the Cl for th e
compound.
I was thinking today, if am m o nium sulfate, which I hear is available as fertilizer, was used as an electrolyte, couldn't you
produce (with an iron electrode), iron sulfate and a high concentration of amm onium hydroxide?
Assuming this is true, the Fe2SO 4 (i think thats right) could be used to p roduce sulfuric acid, and amm oniu m h y d r o x i d e c o u l d
b e u s e d i n m any applications, hydrazine, m aking AN if you cant get it, and other things.
On the chlorate/perchlorate cell pages, it is said that iro n can be 'cathodically protected', which, as I understand, is when there
is enough power flowing through an electrode for it's given surface area. This protects the iron from corrosion, but corrosion is
actually what I want. Im thinking increasing the surface area (or decreasing current flow) o f the electrode would negate this
effect, leading to the corrosion (desired) of the electrode. I think about this kind of stuff a lot and i com e up with different
idea s s o m e t i m e s .
I r e a d o n M e g a l o m ania's site ((gotta love that site) under 'Am m onium Nitrate), that am m onium sulfate is not very soluble in
water, so if you could substitute in am m onium nitrate, you would not get a sulfate com pound but rather a nitrate com p o u n d .
Usin g a copp er electrode you could get copper nitrate, possibly for TACN or whatnot. Im guessing you m ight also be able to
use iron, to get iron nitrate for use in HMTD Factory's (i think) "Weird Nitration Process". All this is based on m y observation of
corrosion of the copper cathode by chlorine. W h e n a n o r m a l l a r g e i r o n n a i l i s u s e d t h i s d o e s n t h a p p e n ( i t d o e s o n t h e a n o d e
though! Rust! Lots of it! So I use carbon!).
I would try this out, but I dont have any AN or AS.
I think I am ( s o m ewhat) safe in saying, that if this process work s, high concentrations of am m o n i u m h y d r o x i d e c o u l d b e
attained until the amount of electrolyte becam e quite low, where the process would slow down and would eventually not be
worth the tim e/effort.
I can't try any of this right now, though. I don't have a power source at the m o m ent, because once I left an electrolysing
s o l u t i o n u n a t t e n d e d , a n d w h e n I c a m e back the fuse was blown, and the glass part was a nice black color (it's one of those
t u b e s h a p e d f u s e s a b o u t 1 " l o n g ) . I c a n ' t c o n t i n u e m y ' e x p e r i m ents' without one of those, so until I get on e I am stuck.
M y i d e a o f a m m o n i u m h y d r o x ide being produced com es from a website call From Cavem an to C hemist. W hen I was searching
for ways of producing sulfuric acid (I have given up the search, and decid ed to just wait for Megalom ania to put it in his
synthesis section ), I stum bled across
this page and it is actually quite interesting. I think it is actually some class. One of the projects described is electrolytic
production of NaO H. I believe this is produced because chlorates are produced at higher tem peratures (around 80c if i recall).
The only thing I am unsure about is the production of NaOCl (undesired). If you read the procedures for making hyrdazine, it
describes dissolving chlorine in cold sodium hydroxide solution. Chlorine is obviously one of the chem icals produced by
electrolysing NaCl solution, an d since it does produce hydroxide, you would think it would eventually begin to change to
hypochlorite. W hile it could be useful, electrolytic production of sodium hypochlorite is not som e t h i n g I a m terribly interested in
at the m o m ent. It m a y b e s o m ething I could do as a future project (when I get m o r e f u s e s ) .
Returning to the topic of electrolytic production of amm onium hydroxide, something you would NOT want to do is to use
a m monium chloride. I say this because in Improvised Primary Explosives, it gives electrolysing a NH3Cl solution as a m e t h o d
of producing NCl3 (nitrogen trichloride), a sensitive, unstable, explosive oily substance.) I actually want to try this som etime. At
high er tem peratures (anything not ice cold im guessing) there is a chance of am monium chlorate form ing, which I have read is
q u i t e u n s t a b l e , a n d s h o u l d n o t be used for anything. I am not sure, but I highly doubt that any danger could com e f r o m u s i n g
the other am m o n i u m c o m p o u n d s I h a v e b e e n t a l k i n g a bout.
S o m ething I also want to try is to melt NaCl (or any alkali Cl for that m atter) and electrolyse the m olten com p o u n d t o g e t
m etals that i can thro w in a bucket of water on a boring day or som e t h i n g h e h e . I i n t e n d t o d o t h i s ( s o m e d a y ) b y m elting a
compound such as NaCl (i hear CO3 and OH also work) in an iron 'trough' that I will have som eone weld for m e from flat iron
that is something like 3/16" thick, and electrolyse it (with iron electrodes, and m aybe steel cables for wires hehe.) A propane
torch ought to be enough, dont you think?
Okay now im done talking for the time being. Please inform m e o n i f m y thinking is right, wrong, genius, or incredibly stupid,
and tell me how I could im prove my comprehension of the subject.
I could use some references on what com pounds will/will not ionize or dissociate in water. Som eone care to fill m e in on this?
Is it just nonpolar substances?
...damn thats a lot o' typin...
(did that link come out right?)
the_wingm a n
Freq uent Poster
Posts: 48
From :
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I once tried to produce Sodium by m elting NaCl. But it didn't work.I assum e it was because of my poor equipment. I would
advice you to use NaOH; it m elts m uch earlier than NaC l.
I think producing all chemicals at home isn't a good choice. It is inneffective and needs a lot of tim e. I'd rather search in
different shops where you can find many chem icals.
You can get "Sulfate of Iron" in garden shops as fertilizer. And you get other useful stuff there. Look at pet, photog r a p h y a n d
electronic shops ( the ones that sell etching eqipment), too.
PS: iron sulfate will never be Fe2SO4. The only possibilities are FeSO4 or Fe2(SO4)3.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
--------------------------------------------------------------------------------
T h a n k s , I ' l l k e e p t h a t i n m ind. But would this idea work at all (for iron/copper/whatever com p o u n d s , a n d f o r N H 4 O H ) ?
jin
Freq uent Poster
Posts: 111
From : u k
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i just heard on the news today som eone in jail tryed to eat through the b ars of his cell with electro chem istry.he used vinegar
from b r o w n s a u c e o n t h e b a r s o f h i s c e l l a n d m a d e s o m e al foil leads from the lights.he only m ade it half way throu gh the bar
before being caught.
FadeToBlackened
Freq uent Poster
Posts: 201
From : Hell
--------------------------------------------------------------------------------
Cool. That's what I call improvising hehe. I wonder how he connected his Al leads though...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Toluene to Benzene? -
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Alchemist
Frequent Poster
Posts: 211
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Hello all,
Is there a way to remove the methyl group in Toluene? That is, is there a way to convert Toluene back into Benzene? A friend found, a cheap source for Toluene, but he really
needs some Benzene and also Aniline!
Keep up the great work.......
------------------
FadeToBlackened
Frequent Poster
Posts: 201
From: Hell
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Well Ive read that benzene is really nasty stuff. Carcinogen and all, and the OSHA limit is like.. im not sure but extremely small.. i mean really really really small seeing how it is
a pow erful carcinogen and all.
Hermes
A new voice
Posts: 4
From:
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This info bomb comes courtesy of another board:
Many benzene derivatives occur in nature, e.g. oil of bitter almonds, benzoic acid, salicylic acid, and hippuric acid, while others are obtained from the destructive distillation of
organic substances, especially of coal.
The destructive distillation of coal yields (a) gases (illuminating gas); (b) an aqueous distillate containing ammonia and its salts, (c) coal-tar; and (d) coke. Coal-tar is the chief
source of benzene derivatives, and is formed in the manufacture of coal-gas for illuminating, purposes, and in "coke ovens" used for the production of high-grade coke for
metallurgical purposes. In both cases coal is distilled from closed retorts at relatively high temperatures, about 1000' C, and the main difference betw een the two processes is
the nature of the coal used. For gas, making a bituminous coal containing 32-40 per cent of volatile matter is used, and in order to obtain the maximum yield of hard coke
bituminous coals containing from 18-32 per cent of volatile matter are employed.
The tar from the tw o processes is much the same. At the present time numerous low-grade coals, e.g. cannel coal, lignite or brown coal, and even bituminous shales, are
distilled at comparatively low temperatures (500-600' C.) in order to obtain oils, and, in the case of cannel coals, smokeless fuel for household purposes, coalite. The tar
produced in all these cases is essentially different from the coal-tar obtained from gasworks and coke ovens. It consists largely of paraffin hydrocarbons, and is valueless for the
manufacture of dyestuffs, explosives, etc., but yields valuable illuminating and fuel oils.
When coal-gas was first generally used for illuminating purposes (1813) the tar w as regarded as a waste product, and could only be used as fuel, and its value as the source
from w hich important synthetic dyes, perfumes, explosives, medicinal drugs, and photographic developers could be manufactured was only gradually recognized. For many
years after the introduction of coke ovens for the manufacture of metallurgical coke, the ammonia and tar formed at the same time were not collected (so-called bee-hive
ovens), but at the present time the great majority of the ovens are of the closed type, and are provided with by-product recovery plant. Still more recently, as the demand for
benzene and toluene has increased, it has become customary to recover the benzene and toluene contained in the gas from the coke ovens, and even from the gas from
gasworks, although this removal appreciably diminishes the illuminating power of the gas. The benzene hydrocarbons are usually removed by passing the gas through scrubbers
containing creosote oil, which absorbs the hydrocarbons, and these can be afterwards isolated by heating the creosote oil or subjecting it to steam distillation. The amount of
benzene and toluene in coal-gas is, roughly, About 15 times as much as that contained in the tar formed at the same time. In coke-oven gases the amount is only about half
this. By this method of extracting benzene and toluene from the gases the amounts of these materials for the manufacture of explosives etc. has been increased enormously.
The follow ing figures will give some idea of the importance of the coal-tar industry: In 1914, in Great Britain, about 14.5 million tons of coal were coked in by-product coking plants and
in the USA about 20 million tons w ere treated in recovery coke ovens, and about 20 million tons in gasworks. In the USA the output of crude benzol was about 14.5 million gallons in
1914 and this was increased to 40 million gallons in 1917. Coal-tar contains as many as 200 different chemical substances these are not present in the coal itself, but are formed during
the distillation. During the past thirty years Investigators have attempted to isolate compounds from coal itself by extraction with solvents, such as chloroform (Keinsch, 1910), pyridine
(Bedson, 1908), benzene (Pictel and Ram, 1911), but so far few relationships have been established between the, different materials present in coal and the chemical compounds
present in tar (cf. Tideswell and Wheeler, J. C. S. 1919, 115, 619). The most important compounds present in coal-tar are benzene, toluene, xylenes, phenol, cresols, naphthalene, and
anthracene. Among the other compounds present are homologues of benzene, especially the methyl homologues; complex hydrocarbons, such as diphenyl, phenanthrene, fluorene,
acenaphthene, chrysene and retene, indene and its homologues, and homologues of naphthalene; thiophene, aniline, pyridine and its homologues; quinoline, euorene, quinoline,
pyrrole, indole, carbazole, and acridine. Most these are of little commercial importance, as the amounts present are small and their isolation from the tar is difficult. Many of the
hydrocarbons present in the tar are probably formed by the pyrogenic polymerization of acetylene, as this hydrocarbon w hen heated yields many of the products present coal-tar (R.
Meyer and H. Frieke, B. 1914, 47, 2765). The crude tar contains appreciable amounts of water, and as to be dehydrated before it can be distilled. Numerous methods are adopted, e.g.
centrifuging the warm tar; heating the tar, allowing the water to rise to the surface, and removing it by a draw-off cock, or allow ing the wet tar to come in contact with the hot vapour
from another lot of boiling dehydrated tar. The actual distillation is carried out in iron stills directly fire-heated. In many tar distilleries continuous stills are employed; in others intermittent
distillation is used, the pitch being removed from time to time and a fresh charge of tar introduced. The fractions collected vary in different distilleries, but, as a rule, in the first distillation
the following are collected: (1) First runnings up to 105 or 110'; this contains water, ammonia, and some light oil (2) Light oils up to 210' (3) Middle oil or carbolic oil up to 240' (4)
Creosote oil up to 270' (5) Anthracene oil above 270' (6) Residue in the still=pitch. The relative amounts of the different fractions vary considerably in different countries and
different districts, but the following are fairly typical values for 1 ton of tar -Light oils, 12 gall; carbolic oil, 20 gal; creosote oil, 17 gal; anthracene oil, 38 gal; and pitch, 11 cwt.
Calculated on 1 ton of tar, the yields of important products are:-Benzene and toluene, 25 lb., or 1.1 per cent; phenol, 11 lb., or 0.5 per cent; cresols, 50 lb., or 2.2 per cent;
naphthalene, 180 lb., or 8 per cent; creosote, 200 lb., or 8.8 per cent; and anthracene, 6 lb., or 0.27 per cent.
The light oils, including those from the first runnings, give rise to 60-65 per cent of benzene hydrocarbons, 12-15 per cent of naphthalene, 8-10 per cent of phenols, and 1-3 per
cent of pyridine bases. The phenols are readily removed by treatment with caustic soda solution, and bv treatment with dilute mineral acids.the pyridine bases The neutral
substances, on further fractionation under varying conditions, yield 90 per cent benzol, 50 per cent benzol, 30 per cent benzol, and solvent naphtha. The numbers 90, 50, and 30
denote the percentage of the oil which passes over below 100' C., and not the actual benzene content of the oil. 90 per cent benzol contains 81 per cent of benzene, 15 per cent
of toluene, 2 per cent of xylenes, and 2 per cent of impurities; and 30 per cent benzol contains respectively 13.5, 73.4, 11.7, and 11.7 per cent. From these crude benzols, by
careful fractionation, pure benzene, toluene, and xylenes can be isolated.
In addition to the compounds, such as benzene, toluene, naphthalene, phenol, and anthrace, which are actually isolated and form important articles of commerce, a number of
products consisting of complex mixtures are also manufactured. The most important of these are (1) solvent naphtha, which is used as a solvent for rubber in preparing
waterproof fabrics and also for burning purposes, and (2) creosote oil, which is used in enormous quantities for pickling timber for use as railway sleepers, posts, and other
purposes. For hydrogenation of coal cf. Bergius, Chem. Age, 1927, 134.
Many methane derivatives, e.g. alcohol, yield a mixture containing a large number of the derivatives of benzene when their vapours are led through red-hot tubes. Acetylene,
C2H2, polymerizes at a low red heat to benzene, C6H6, (Berthelot)
Benzene is formed when benzoic acid is distilled w ith soda-lime: C6H5COOH = C6H6 + CO2
Industrial Chemistry is Cool, isn't it?
Alchemist
Frequent Poster
Posts: 211
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Thanks guys, good info!
Mr Cool
Frequent Poster
Posts: 991
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This is how to make benzoic acid from toluene, from an e-mail sent to me from a guy called Robert. Thanks Robert. It's pretty simple to do.
"By the w ay, if you do get your hands on some toluene, you should know that it can be easily
oxidized to benzoic acid. I did it once, using sodium dichromate. I don't have the correct
amounts method for you, but I'm sure you can figure one out yourself. What I do know: you have to
put toluene in a flask, together w ith the dichromate dissolved in w ater. Stir that w ith an
electric stirrer, then add 98% H2SO4 from a dripping funnel.
It w ill get hot, so put a reflux-condenser on the flask. After all H2SO4 has been added, boil
the solution for half an hour. Cool the solution and mix with the same amount of cold water,
then filter.
The residue is crude benzoic acid. Dissolve in warm (max. 100 deg.) 0.5M sulphuric acid, to get
the chromium salts out, and filter again. Then dissolve in 2M NaOH until the solution reacts
basic. Unreacted toluene w ill separate, chromium salts will be transformed into hydroxides.
Decant the toluene, add active carbon, and filter the solution. Slow ly drip the filtrate into 2M
H2SO4. Benzoic acid will precipitate. Filter with a vacuumfunnel, and dry the benzoic acid.
Sincerely,
Robert
Alchemist
Frequent Poster
Posts: 211
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Thanks Mr. Cool,
and thank you too Robert............
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Rhadon
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Posts: 95
From: Germany
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I have read that benzoic acid and toluene will react to phenole. Though, I have to admit that I'm not able to find a chemical reaction for this at once.
Mr Cool
Frequent Poster
Posts: 991
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Do you mean if you mix them together, or do you mean that both of them will decompose to it seperatley? (did you mean phenol, not phenole?)
Maybe C6H5CH3 + C6H5COOH -> 2(C6H5OH) + C2H2
That could be quite a useful reaction, although I'm not sure if it's correct. I just made it up, but it balances. How ever, I think it's unlikely that it'd react like that.
Alchemist
Frequent Poster
Posts: 211
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Hello all,
Yes this would be cool! Any other chemists out there w ho would like to respond?
Thanks.....................................
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Rhadon
Frequent Poster
Posts: 95
From: Germany
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Yes I wanted to say phenol, excuse my misspelling. I found the reaction in a book in a library, but don't have the time to look for it again right now. As soon as I get to it
(probably in 2 weeks or so) I'll tell you w hat I have found.
Mr Cool
Frequent Poster
Posts: 991
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OK, let us know what you find out.
Maybe if you bubbled C2H2 through a cold nitrating mixture you'd get an addition reaction, forming C2H2(NO2)4 ? Tetranitroethane? Very oxygen rich, probably a volatile,
unstable liquid.
Rhadon
Frequent Poster
Posts: 95
From: Germany
--------------------------------------------------------------------------------
Today I found some time to search for the benzoic acid / toluene reaction in the library, unfortunately I couldn't find it. The only thing that could be from interest w as a reaction
between benzoic acid and NaOH which will yield benzene and water when distilled off, but I don't know if this is new to you. Perhaps I have a bit more time next week so I can
search again.

Toluene ---> Benzoic acid
2Benzoic acid ----> terephtalic acid + benzene
IIRC, the second procedure is simply strongly heating anhydrous benzoic acid. Benzene w ill distill over.
DF90 June 13th, 2007, 12:48 AM

If you're mad enough to make benzene, then here are a few routes from some fairly common benzene derivatives:
Benzoic acid: Neutralize w ith Sodium carbonate to produce Sodium benzoate, Carbon dioxide and water. The benzoate salt is then reacted w ith Sodium hydroxide to yield
Benzene and Sodium carbonate.
Toluene: Oxidize w ith alkaline Potassium manganate (VII) under reflux. The reaction mixture is then acidified by addition of dilute acid, precipitating the Benzoic acid out. The
above procedure can then be followed to produce Benzene.
Benzaldehyde: This too is oxidized under the same conditions as the toluene to produce benzoic acid, and again this is then treated with Sodium carbonate then Sodium
hydroxide to give Benzene.
It is possible to substitute other oxidizing agents such as dichromate (VI) salts for the Potassium manganate (VII). I am unsure w hether or not the oxidizing agent has to be
alkaline or not but i assume it is just to prevent precipitation until the reaction is finished and acidified.
If anyone successfully produces some Benzene, please can they give some feedback :)
++ ++++ +++ ++++ +
'oxidising' is spelt 'oxidizing'. I corrected it for you. NBK

Oxidizing the likes of toluene is a seemingly a good route to benzene, I should know as I have been doing this for several years now . The problem I have, not me personally,
but in my research on this I limit myself to oxidizers that ordinary people can actually get ahold of. Permanganates (not manganates) are getting rather hard to find, and, unless
you recycle the w aste manganese dioxide, can be very expensive to produce decent quantities of benzene. Chromates are fine as oxidizers, but these are quite toxic, and
where do you expect to get them outside of a laboratory?
The chemistry is quite well established, the procedure is not at all difficult, but getting all easy OTC materials that are inexpensive and sustainable is the real challenge. I have
looked a little into alternative oxidizers. Last year I did find an interesting article in Catalysis Letters for oxidizing toluene to benzene using manganese dioxide and oxygen gas.
The reaction does require some pressurization (145 psi), but that is at least doable on the OCT side. The manganese dioxide is only a catalyst, so all you need is toluene and air.
I would try air instead of oxygen to make the reaction cheaper, but one could buy an oxygen tank. The oxygen is added as a make up gas to sustain the pressure, not just
bubbled through and lost, so if you went the expensive oxygen gas route none w ould be wasted.
I found another article in Applied Catalysis that described using a vanadium and titanium oxide catalyst to oxidize toluene to benzoic acid with even greater yield than the above
reaction by using a microwave as the heating source. This reaction still uses oxygen and a catalyst, but no pressure is required. In fact yields are increased, at the expense of
rate of reaction, by using diluted oxygen (they used an oxygen nitrogen mixture), so I would think air w ould be good for this especially since this is a continuous flow situation
where the gas is continuously bubbled into the reaction.
There is another process I have become aware of to convert toluene to benzene called transalkylation and disproportionation. There is a catalytic reaction w here the alkane
attachment can be shifted onto other aromatic molecules. With pure toluene it w ould be possible to form a mixture of benzene and xylene (disproportionation). This reaction
could also use xylene to form a more complicated mixture of benzene, xylenes, and mesetylene (transalkylation). I only mention using xylene because it seems even toluene is
getting harder and harder to find.
Next up? Better methods of decarboxylating aromatics using microwaves to do the job better, cleaner, with higher yield, and few er chemicals to use.
Beyond toluene I have found a few more tidbits for dehalogenating dichlorobenzene (good ol urinal cakes and mothballs) using microwave, photochemical, and even
sonochemical means (that I have to try). I even found a catalytic method of directly forming benzene is decent yields using natural gas, why they pump that right into my home
almost begging me to try it.
Here is a take home lesson for the astute in the audience Manganese dioxide can be a good oxidation catalyst, microw aves can be a good heating medium, w hat if we used
manganese in the microwave? I love the possibility of microw ave chemistry because its about as OTC as you can get.
Enkidu June 15th, 2007, 11:21 PM

Good info about the use of microwaves in chemistry, mega. IIRC, quite a few people have had good success with microw aves in... erm, the chemistry of psychotropic
substances. Anyw ay, home chemistry involving microwaves is a little researched subject, at least as far as I have seen. This topic would make for an interesting thread, i.e.,
Microwaves as Applied to Home Hobbyist Chemistry.
The most economical means for most people to make benzene is by refluxing Sodium Benzoate (much cheaper than Benzoic Acid) w ith a hydroxide, preferably sodium
hydroxide. SM has a member publication about X compound goes to Benzene, although I've not more than glanced at it in a long time.

They do have a very nice compilation of methods including some experimental results. The procedures are derived from 19th century publications, but the old stuff makes it
seem easy. The SM experimenters did have some difficulty w ith the method. It is not that they did anything wrong, it is just that the method is not as desirable or effective as
the literature made it seem.
I am not sure if I would consider the method "economical," but it is at least the most doable by citizen chemist standards.

a n d I m provised C hemistry > NH3 gas
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View Full Version : NH3 gas
frogfot July 6th, 200 3, 06:38 AM

W hat appara tus would be best to produce NH3 gas from NaO H and NH4Cl (or NH4 NO3)?
Asking this b e c a u s e i g o t s o m e problem s. Synth of acetamide required that you pass am m o n i a g a s through liquid (no need to
dry the gas) As gasgenerator I used a filtering flask with a corc (a syrigne with water was placed through the corc). A m ix of
m entioned salts was placed in flask and pipe was im m e rced into solution .. Flask was in cold water-bath At first reaction went
fine and steady without water, then, when it slowed down i started to add some drops of water. This resulted in vigorous
evolution of gas which stopped quite fast. Further addition of water resulted in underpressure in fla sk.. as result some liquid
from m y a c e t a m i d e e xperiment was sucked into flask.. :(
How to preve nt this? I don't wanna place any safety vessel between gas generator and experim ent vessel cause this would be
only temporary solution... Maby there are som e s t a n d a r d e q u i p e m e n t o n e h a v e t o u s e ?
Thanx for inputs
yt2095 July 6th, 200 3, 06:52 AM

in your am monia receptical, m ake it a shallow dish (a few mm d e e p o n l y )
then on your gas pipe attatch a funnel and put that into your dish. since amm onia is so readily absorbed in water other liquids
a vu cum e is often produced, but now when it does, it will TRY suck up your liquid, get so far up the funnel and drain yor dish
untill air com es in and releases it :)
it also has the advantage of giving your am monia gas a greater surface area in which to react with your liquid :)
all the best :)
frogfot July 6th, 200 3, 07:36 AM

yt20 95, you're genious! This is a great idea, thanx :D
Now, wonder how one could maintain steady gas production.. i'll test this again with m ore finely devided particles, m aby water
produced in reaction will keep reaction going all the way.
FragmentedSanity July 7th, 200 3, 04:22 AM

Lo a ll :)
check the hive - or rhoidium s s i t e m i g h t b e q u i c k e r . I v e s e e n a c o u p l e o f a m m o n i a g a s g e n e r a t o r s . T h e o n e s i r e m e m ber
s e e i n g a r e f o r m aking anhydrous NH3 gas - to be condensed into liquid NH3 for use in birch style reductions. Seeing as this
process requires LOTS of gas (fairly constantly) the generators described m ay be quite useful.
FS
John A shcroft July 19th, 20 03, 07:4 1 PM

W hat reaction are you using to prepare acetam i d e ? A r e y o u g o i n g t o b e b u b b l i n g a m m onia into ethyl aceta te (nail polish
remover)? Acetam i d e * c a n * b e m ore easily prepared by simply heating am monium acetate, distilling off H2O , a n d t h e n
acetam ide (separating fractions, of course).
frogfot July 19th, 20 03, 11:1 8 PM

John, yes, preparation method requires bubbling of amm onia gas (through a mixture of 20 g ethyl acetate and 30 g 25%
a m monia)
I'm really grateful for suggestion, i'll try both m ethods. It's not the final product thats m y goal (though it is also..) :)
Searching for rhodium site i found this:

www.rhodium.ws/chem istry/birch.m rclean.htm l
NH3 is prepared by m ixing powders of NaOH and am m o nia salt. Testing this i found that one have to sit by apparatus and
s h a k e t h e v e s s e l e v e r y 2 m inutes.. too much work.. the n I ran out of NH4Cl had only ~20g no won der it wasnt enou g h ( g o n n a
m ake half kg today)
T h e n a g a i n s o m e w i s d o m cam e from old books, they drop conc. KOH solution onto solid NH4Cl and dry gas with KOH (not
nescessary in my case), now this seem s to be comfortable m eth od. It would be quite logical to think that solubility of NH3 in
conc. basic solutions falls drastically, therefore, m aby NaOH will do just as fine.
IPN August 10th, 2003, 12:33 PM

I f y o u d o n ' t h a v e m u c h a m m onium chloride you could use urea instead, I think it would be cheaper than am m o n i u m c h l o r i d e
a s u rea is easily acquired as a fertilizer.:)
The reaction is as follows:
2 NaOH + C O(NH2)2 --> Na2C O3 + 2 NH2
Y o u m a y n e e d t o h e a t t h e m ixture a little to get things going.
Mumble August 10th, 2003, 04:59 PM

I f y o u h a d t h e n e c c e s a r y h e a t i n g a p p a ratus around, you could just heat the urea to decm pose it into Amm onia and cyanic acid.
Even though you don't need it to be, it is dry. The only water present would be that which is in the air. If this is possible for
you, I don't really see why not use it. Urea is m o r e e c o n o m i c a l t o u s e t h a n a n a m m o n i u m salt and NaO H, for me at least.
mongo blongo August 10th, 2003, 08:36 PM

IIR C you can prepare dry NH3 from Am m onium Sulphate (from a garden centre) by heating.

True, and the NH4HSO4 left behind can be used, after converting it to the sodium or potassium salt, to make SO3. Search a n d
ye shall find...
A l t h o u g h h e a t i n g a m m onium s u l p h a t e d o e s p r o d u c e d r y a m m onia, which is nice, I've always preferred using NH4X + NaOH. I
don't like having to heat my glassware up that much, because I always e nd up breaking it with therm al sho ck :(.

W ait, wouldn't am m o n i u m s u l f a t e g i v e o f f b o t h N H 3 a n d S O x? If not, this would b e a g o o d m a s s p r o d u c t i o n p r o c e s s f o r s o m e
p e o p l e . I t h a v e d e c o m p. tem p. at 280*C , so thats ok for an am ateur experim e n t e r . N o c o m p l i c a t e d e q u i p e m e n t i s n e e d e d ,
just a big iron good sealed jar on a fire place :)
Btw, gardening stores here sell for the most only m ixed fertilisers/other chems.
Mumble August 13th, 2003, 06:06 PM

The way people were talking, It appeared that the Am m onium Sulfate just gives off one m olecule of Am m o n i a g a s , l e a v i n g
Am m o n i u m B i s u l f a t e . I b e l i e v e t h e d e c o m p o s i t i o n o f A m m onium bisulfate will give off the SOx. I'd imagine the decom position
t e m p e r a t u r e o f A m m onium bisulfate is higher than that of Am monium Sulfate. If it wasn't, the Amm onium bisulfate would be
d e c o m p o s e d a s s o o n a s f o r m e d . T h u s p r o d u c i n g a c o n t a m inated product.
Just bubble some of the gas into water. Then evaporate the water. If the res any SOx there will be crystaline solid at the
bottom . You could also bubble it throught a saturated solution o f CaCl2, any SO x will be rem o v e d b y t h e
form ation of Calcium Sulfate. Don't use the gas you bubble through. It will be contam inated by HC l.
frogfot D e c e m ber 12th, 2003, 04:07 PM

Found a pic in nonorganic boo k o f a n a p p a r a t u s t h a t s u p p o s e t o produce c o n t i n i o u s l y g a s e o u s a m m onia, h eres a it:
http://www.geocities.com/frogfot/stuff/am m o n i a a p p 2 . g i f ( C o p y & P a s t e )
This vessel is welded from a peace of iron pipe (11 cm heigh and 9 cm in diam eter). Vessel is filled to half with water and
h e a t e d t o 9 8 * C , a f t e r , a q u e o u s a m m onia is added with required speed to m aintain wanted NH3 flow. Liquid is drained from
vessel through pipe 1 (on pic). Evolved NH3 is dryed by KOH.
If properly regulated, author claim s, this apparatus m a y o p e r a t e i n s e v e r a l h o u r s l e a v i n g b e h i n d < 2 % a q u e o u s a m m o n i a .
C o u p l e m inutes of thinking gave m e this sim ple to m a k e a p p a r a t u s t h a t o p e r a t e s s i m ilarly:

http://www.geocities.com/frogfot/stuff/am m o n i a a p p . p n g ( C o p y & P a s t e )
Here, it is simpler to m onitor liquid level inside flask.
O f c a u r s e , o n e c a n u s e p l a i n f l a s k w i t h o n e o u t p u t i f o n e n e e d s o n l y s m a l l a m m ounts of NH3.
I havn't tryed this yet, any suggestions?
Btw, 24,5% amm onia is very comm on in this country, lucky me :rolleyes:

a n d I m provised C hemistry > Ice Baths
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disarmme July 7th, 200 3, 01:57 PM

i'm new to pyrotechnics (and also to chemistry in general) and i'm the kind of person who wants to do things EXACTLY right.
i've noticed alot of projects require a "salt-ice b ath". i know basically what that is, but i was wondering if there was any precise
m e t h o d a n d m e a s u r e m e n t s t h a t m ust be used. i'd liked to hear everyone's personal method as well. sorry it's a dum b
question, but that what the water cooler is for i guess. n ewbies. thanks.
rooster July 7th, 200 3, 01:58 PM

W hat is the best form of ice bath you guys have m ade with OTC chemica ls?
By "the best" I mean for nitrations (or other ex othermic reaction s).
I a m not looking for what you norm ally use, bu t what you have had the best effect with.
Is the one with NH4NO3, NH4Cl and wa ter stronger than the one with just NH4NO3 and water?
Also I read that CaC l2 x XH2O is endohtermic in reaction with water. Maybe this could be used?
The regualr one with NaCl, ice and water seem s uneffective.
I know of the one with acetone and dry ice that is fucking cold. The reactions will likely stop or be slowed too m uch down if not
the reaction is VERY exotherm ic. Anyways, dry ice is not too easy to com e by is it?
W hat are your best ice baths?
yt2095 July 7th, 200 3, 02:10 PM

disarm m e ,
the fact is, that for PYRO ice baths are rarely to never needed, in fcat a ball m ill will be your m ost used peice of kit along with
seives of various m esh widths.
ice + salt (NaCl) and bit of water m a k e s a f r e e z i n g m i x f r o m r e g ualr ice, takes the tem p down to a bout -7(ish).
that`s usualy used fo r HI-EX or crystalisation of a difficult solution or wea k solutio n to cyrystalise in PYRO .
reducing the water content by evaporation is usualy sufficient for crystalisation in pyro.
the odd exception is for deliquescent or efflorescent (sp?) chems that m ake require active drying, they are rarely used in PYR O
anyway :)
a s e arch here will tell you ALOT m ore than i`m likely to in a sing le post :)
All the best :)
knowledgehungry July 7th, 200 3, 02:27 PM

Dry ice is very easy to com e by, look for it in th e p h o n e b o o k . I c e c r e a m places sell it.
kingspaz July 7th, 200 3, 02:55 PM

i f i n d a m m onium nitrate and ice works quite well. gets a nice chill going. also to im prove perfromace of an ice bath rest it on a
polystyrene sheet (insulator) of about 2cm thick to reduce heat flow into the ice b ath from the work bench. also wrap it in foil to
reflect the infra red radiation coming from other objects in the room. that should increase the lifespan of th e icebath. i find it
annoying when it begins to run out halfway through a re action.
ALENGOSVIG1 July 7th, 200 3, 03:38 PM

I v e r e a d t h a t C a C l2 ice baths can reach -20 to -30, and that NaCl ice baths can reach -10.
R e m ember, its im portant that the ice is well crushed.
W hat are you preparing that needs this kind of an ice bath?
disarmme July 7th, 200 3, 05:38 PM

thanks for th e correction yt2095. now that i think about it you're very right. i've been interested in pyro and HE's, an d it's true
that they don't use it much in pyro. i wasn't thinking. is there a real term for working with HE's? the y have "pyrotechnics" of
course (i know it's alot different from HE's), i was just wondering if there was an official term for working with HE's. i have alot to
learn. i hope i can learn alot from you guys at The Forum . thanks for the info (an d honesty).
grendel23 July 7th, 200 3, 06:06 PM

A cooling bath can range from a half liter of water with a few ice cubes flo ating in it, to a container of crushed ice with rock sa lt
or NH4NO 3 added to lower the temperature, to a jacketed reaction vessel with dry ice cooled acetone in the jacket.
I think what is m ore im portant is to un derstand the "why" things are done the way they are. If a re action is exotherm ic and
m ust be kept at a certain tem perature, you can try with a very sm all am ount of reactants and see for yourself how robust your
cooling m ust be. W hen you have a handle on the small reaction, scale up slowly, larger am ounts are much more difficult to
cool.
T h i s i s a g o o d idea for all unfam iliar reactions, start small because unexpected events will be less dangerous.

disarm m e , i r e c o m e n d y o u l e a r n a s m u c h c h e m istry as you can whilst reading your way through the threads of the forum and
its a rchives. try and find som e beginner chemistry sites to get you into the basics. the basics are what you m ust not forget a s
chemistry will always come back to them .
blindreeper July 7th, 200 3, 08:06 PM
- 2 0 t o - 3 0 s e e m s off because when ever I have m a d e a s o l u t i o n o f C a C l2 it gets hot, I think thats one of the reasons it's
used as ice melter. O r maybe once it cools down it can go to tho se temperatures :rolleyes:
knowledgehungry July 7th, 200 3, 08:39 PM

C a C l 2 m ay indeed be exothermic when dissolved in H2O, but it cools it d own when added to ice. I dont feel like explaining BP
changes and the effect of that on a solution bu t suffice it to say that whe n ice me lts it cools the surrounding area.
0EZ0 July 8th, 200 3, 02:58 AM

W hen I wish to keep m y beverages nice and cold, I use a pre chilled CaCl2 ice bath. Works wonders, and stays nice and icy
cold:). NH4NO3 cooling baths have the advantage that you can prepare a bath on-site (va cation;)) without prior chilling of th e
cooling m ix. Even when this m ix is spe nt and starts to warm to room tem p, the m ix can be placed into a freezer and re-cooled.
Since dissolving NH4NO3 in water also lowers th e freezing point, it can be re-used like this as a salt/ice bath mix. There are
m any alternatives to using salt/ice as a cooling m ix. Think of glycols, volitile solvents, dry ice mixes, etc.
Most salt/ice baths work on the principle that with the salt disolved in the water, the freezing point of the mixture becom e s
lowe r. W ith a lower freezing point, the m ix can be very cold while still retaining m ost of it's liquid properties. Liquids conduct
temperature better than granulated ice, giving better co oling.
So obviously if you want the m ost efficient cooling, you would wa nt a cooling mix that stays liquid even at relatively low
temperatures(-25 to -50). If that can be achieved, then you can seal the liquid in a plastic satchel and m old it around the item
you wish to have chilled (just like an oversized ice-pack). W hen doing this you can avoid the m e s s / c o m p l i c a t i o n s a s s o c i a t e d
with direct application of your cooling m ix to your container (with item to be chilled inside). This m ethod is a good way to avoid
contam inatio n of your sam ple/drink/etc. with the ice bath liquid and to help stabilise the container that you are chilling. No
m ess, no fuss:). People with vacuum sealing equipment may wish to try this.
W hat is everyone's favourite cooling bath?
nbk2000 July 8th, 200 3, 04:21 AM

There was no need for two different threads about ice baths, so they've been joined. :)
rooster July 8th, 200 3, 02:32 PM

ALENGOSVIG: I thoug ht that m ore effe ctive ice baths will allow you to make m ulti-step nitrations in fewer steps, for exam ple
TNT or TeNN. It can also serve other non-explosive purposes (in m y case, for example neutralizing HNO3 with NaOH to m a k e
NaNO3. This gives off a lot of heat.
C a C l 2 c a n b e f o u n d i n m a n y d i f f e r e n t f o r m s: the anhydrous form, the dihydrate, and the hexahydrate. I believe it is the
hexahydrate that reacts endotherm ically with water, and the anhydrous that reacts exothermically.
Does anyone know how to make the two useful form s(anhydrous and hexahydrate)? Heating will be good, but how m uch heat
and for how long will it be required to fully dehydrate it?
As for the he xahydrate, I guess it will just be to dissolve CaCl2 in boiling water, and collect the crystals when it chills?

both m ethod s s o u n d g o o d t o m e. i would heat it at about 120*C and m e a s u r e t h e m ass of it every 15 m inutes until there was
no mass change. then you would know it had lost all the water it could at that tem perature.

a n d I m provised C hemistry > Extraction of Nitroglycerin from DBSP
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Cricket July 16th, 20 03, 05:4 4 AM

I a m very interested in extracting NG from DBSP. I have been looking for a suitable solvent that will dissolve NG, bu t leave the
NC be. I found this webpage (http://www.wolff-cellulosics.de/index.cfm?PAGE_ID=1076) that deals with the solvents of NC. I
haven't found much of anything on NG solvents. Does a nyone know of such a solvent or m ethod of seperation? Any help is
m uch apperciated.
DBSP July 16th, 20 03, 06:1 6 AM

Even if you would find a sutible solvent the % of nitro in the DBSP would probably be very low. I belive to low to actu ally be
worth the trouble, mu ch easier to make it then. It wouldn't be very cheap nitro either, unless you stole a truckload of it.
H a s a n y o n e g o t a n y i d e a o f t h e % o f n i t r o i n c o m m on DBSP.

I just found this page that said "Double-base powders differ in the use of a non-volatile organic nitrated com pound, in this
case a liquid gelatiniser that rem a i n s a m a l g a m ated with gun cotton. The solvent-free powders contain between 20 and 50 per
cent nitroglycerin. The action of the gelatiniser is highly dependent on the presence of nitrogen in gun cotton; in som e c a s e s ,
an auxiliary solvent such as acetone m ust be u sed.The oldest variations or brand s of double-base powders were called
Ballistite and Cordite.". Here is the URL (http://www.nob elsport.fr/gb/PAGES/29_32.htm ) if anyone is interested. 20 to 50%
s o u n d s g o o d to m e! And I would use the NG to detonate the NC (or binary explosive I would make with it) anyway, so I would
have to buy the DBSP in either case. Thanks.

S o m e com mon NG so lvents are: ethan ole, m ethanole, ether, be nzene, nitrotoluene, conc. acetic acid and chloroform.. the first
two don't dissolve NC for sure, id try m ethanole cause it's always sold as 100% (will dissolve more NG).
Cricket July 16th, 20 03, 08:0 9 PM

W onderful! I will try this with, if not pure m ethanol, then denatured alcohol. I will post the results this week most likely. Thanks
everyone!
Frog fot, I know you are in Sweden, but what can you buy pure m ethanol as? Maybe de-icer in a can?
Shit. I just read m eth anol is a solvent for NC. I will try a nyway, m aybe with diminished purity.
frogfot July 17th, 20 03, 04:2 4 AM

It cannot be possible that methanole dissolves NC.. i tryed this som e s e c o n d s a g o a n d N C c o t t o n r e m a i n e d a s c o t t o n . . e v e n
s m a llest fibe rs rem ained intact.
M e O H com es from a reliable source (lab).. :rolleyes: However, i think i saw it som ewhere as cleaner (gonna hunt for this). I
think it's legal when some stinky crap is added so that people can destin guish it from ethanole.. this crap should be below 1 0-
20%

I h a v e r e s e a r c h e d f o r h o u r s a n d h o u r s a n d c a m e to the conclusion that maybe methanol will dissolve the less nitrated form s o f
NC, but propellant grade shou ld be fine. So you are correct (I hope). It m ay be a while before I fin d out though. I found out
that my local store doesn't even carry denature d alcohol any mo re :( . They still have acetone though :D. Oh yea, a little sliver
of info, I read that Alliant Bullseye contains 40% NG (by weight I am guessing). So it will be m y powder of choice for this
e x p e r i m ent, and all in the future :D. Thanks fo r all the help everyone.

a n d I m provised C hemistry > how to guess the reaction will be cool or hot?
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aster July 17th, 20 03, 10:5 6 AM

since we m ay m ix m any things together, i am sometim es wonder, when i am reacting m ercury with nitric acid it is cool, but
when i am re acting m ethylam ine with nitric acid there are a lot of heat released, how to predict a reaction will be coo l or hot, in
the another word will be exoth erm ic or endotherm ic, right? sorry because i am not chem ist, so i think there must be a guidance
to determ ine whether a reaction will be , or we just know this by trial and learn from previous try? th a n k s a l o t :D
knowledgehungry July 17th, 20 03, 11:0 1 AM

Y o u c a n l o o k at the Delta H of the reaction if it is negative energy is released, if positive than energy iss re quired for the
reaction.
aster July 17th, 20 03, 11:2 9 AM

where i can get learn about "d elta H" in sim ple word how to calculate them ?:confu s e d :
knowledgehungry July 17th, 20 03, 11:5 8 AM

W ell you can look at the heat of form ation of a chemical, look for it online m a y b e c h e m f i n d e r . c o m h a s ? a n d a d d t h e h e a t o f
form ation of the reactents and then subtract the sum of the hea ts of form ation of the products from it and that lets you kno w
the free energy, if positive than requires enrgy/heat, if negative than gives off.
E x a m ple:
H2SO 4@-450kj mole+2KNO3@-215kj mole-->2 HNO3@-200kj m ole+ K2SO 4 @ - 1 5 0 k j m o l e
-450+2(-215 )=-880Kj
2(-2 00)+-150=-550KJ
-880Kj-(-550 KJ)=-330kj so you have e n e r g y b e i n g r e l e a s e d
*heat of formation num bers pulled out of my ass for demonstrtion purposes.
aster July 17th, 20 03, 01:0 5 PM

thanks, it's helpfull
Arthis July 17th, 20 03, 01:3 9 PM

The merck index will give you the "delta H", which is btw called e nthalpy of form ation of th e c o m p o und.
T h e n y o u s u m the different enthalpies, pondered by the coeff. before them in the reaction. Note that a product will be counted
a s n egative.
A + p*B --> m * C
p, m a r e n u m b e r s , A , B , C c o m p o u n d s .
Enth alpy of reaction : DeltaH(A) + p*DeltaH(B) - m * D e l t a H ( C )
inFinie July 18th, 20 03, 06:3 6 AM

There is a search form on NIST
http://webbo ok.nist.gov/chem istry/form -ser.htm l
R e s u l t s s e e m s com plicated, m a y b e i t ' l l h e l p t o s o m e o n e
Tuatara July 18th, 20 03, 07:1 1 PM

Or if you can't find exactly what you are looking for, go back to first principles and add up the bond energies of the reactants,
t h e n a d d u p t h e b o n d e n e r g i e s of the products. If you have m ore energy on the reactant side then your reaction will be
e x o t h e r m ic. Simple.
TheMaddHatter A ugus t 7t h, 2003, 09: 02 PM

It m ay also be worth your tim e to look up Gibb's Free Energy Equation....it can be use to predict whether a reaction will take
p l a c e b a s e d o n e n t r o p y a n d e n t h a l p y a n d t e m pature. Though it has m any form s the basic is G = H- TS or Free Energy
Constant = enthalpy - tem pature(entropy). Where if G is negative than the reaction will likely take place. It can be interesting
as it can really bring a lot together. Anyway just a further applica tion for delta H.
The/\/\addhatter
P.S. i think i got the uses and spelling of enthalpy and entropy right but they could be switched....m ain thing to rem e m b e r i s
that H is (in a nutshell) exothermic or endothermic and S is the "m essiness" of the reaction and T is of coa rse tem pature.

M e s s i n e s s o r c h a o s a r e b a d e x a m p l e s t o e x p l a in entropy.
A better explanation would be that if the entropy of a compound increased, it has lost som e of it's ability to perform work.
F o r e x a m ple, you have 2l of water in a n therm ically isolated vessel, separated by a wall. 1l is at 300C, the other at 350C . If
you pull the wall away the water will m ix, forming 2l at 3 2 5 C . W h ile there has not been any energy exchange with th e
environm ent, the entropy did increase.
You can easily see, that if you want to reverse the process, you'll need to invest energy, e ven if yo ur not changing the total
internal energy of the water. That's the energy that got "lost" with the entropy increase.
zeocrash August 8th, 2003, 05:58 AM

y o u a l s o h a v e t o r e m e m ber that just b ecause a reaction doesn't feel hot doesn't m ean it's not exotherm ic. m ixing sodium
bicarbonate with vinegar doesn't feel like it's givving off any hea t, but it's very slightly exothermic.

True zeocrash and ve ry im portant to consider when you are thinking about upscaling.
Slight exotherm ic reactions will be slow in sm all quantities becau se they produce just enough heat to activate the reaction.
In larger batches (+1kg) you can easily get a chain reaction and your slo w and easy reaction will derail into vigorous boiling
and splattering.
metafractal August 8th, 2003, 09:13 AM

Knowledgehungry, those calculations are correct for the am ount of engergy released in a reaction. The energy given off by a
reaction can be expressed in a number of ways, another being light, for exam ple. W hile e n e r g y i s o f t e n e x p r e s s e d a s h e a t ,
this is not a reliable way of calculating the precise enthalpy of a reaction.
...or is knowledehung ry no longer with us?
knowledgehungry August 8th, 2003, 09:33 AM

I'm still here, I was m erely giving him a g e n e r a l i d e a o f a s i m ple way to tell whether the reaction will m ost likely be hot or cold,
I know energy is not only heat, but in m ost cases the m ajority of energy is given off as heat. I'm just takin g a break from
m aking anything, im into theory only for a while at least.

a n d I m provised C hemistry > Another m e t h o d o f K C l O 3 p r e p a r a t i o n
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M a d e p o t a s s i u m c h l o r a t e b y p assing chlorine through boiling potassium cabronate solution. This m et ho d i s m ainly for fun.
In original description (old chem book) they didn't mention how one should pass chlorine into solution, so I passed it through
5 m m glass tube which was tapped in short while.. cork in chlorine washer flyed out (luckily i did this outside). I lost some
chlorine.. then I replaced glass pipe with an up-side-down turned funnel, this gave nice results, no tapping :D
The theoretical yield is slightly less than 15 g, i got 10 g. This is quite good since I lost some chlorine and som e of chlorate
was lost while recrystollising (2 tim e s ) . T o m y surprise there was no chlorine escaping solution! ..well, smell appeare d in the
end of reaction.
This was m y first tim e m a k i n g so much chlorine, was literally shaking in the beginning for som e r e a s o n : r o l l e y e s : I u s e d
rubber gasoline pipes which showed to be good , no deterioration was noticed on walls :) (apparatus was left standing filled with
chlorine for about 3 h )
Described the method here:

www.geocities.com /frogfot/synthesis.htm l#chloratedisprop
Also, sam e p a g e g o t a p i c o f m y improvised pressure equalising funnel (under "chlorine").

frogfot, thats a really good m ethod by the sounds of it. a chem ical process to pre pare it is good because it can be done in b ulk
quantities.

Mass production would be possible, but chlorine is expencive to produce (at least for m e . . K M n O 4 ) . 5 0 g K 2 C O 3 t o 1 5 g K C l O 3
m ay not be profiteable but it's sure faster than electrolysis and one get lots of KCl (45g). One goo d thing is high purity of the
product (no Na or other things like in electrolysis)
Arthis July 18th, 20 03, 06:3 2 AM

W ouldn't it be possible to produce chlorine from table salt (NaCl) ? I think electrolysis could do tha t. As chlorine is a gas, there
wouldn't be purity pro blem s, and that would be extrem ly cheap.
HCl too, m aybe ? I need to search a little.
Maybe chlorine for po o l s c o u l d b e u s e d t o o .
a_bab July 18th, 20 03, 09:2 3 AM

Frog fot, in order to get chlorine cheaper, try alternative m ethods for oxydising HC l, like MgO2 (from batteries, use it as it is
without purification). Another m ethod which worked grea t for m e (by accident of couse) is to m i x 5 0 : 5 0 i n v o l u m e s H C l a n d
H 2 O 2 ( 3 0 % ) a n d a d d Al foil. It rocks, you'll see ! You dont need to heat the mix, it'll reacting as soon as you'll add the foil.
Experim ent first in sm all batches of course.
O h , t h e s e o l d c h e m s books are really fun to read...
Arthis, producing Cl2 out of NaCL by th e m eans of electrolysis is possible of course. The problem is that the amout of chlorine
obtained in a given tim e i s t o o s m a l l u n l e s s u s i n g h u g e vessels/industrial quantities of electricity.

Duh!! I didn't even th oat about electrolysis, haha. a_bab, youre right that it will be slow, but assem bling one on 15A will give
a b o u t 2 0 g / h t h a t s n e a r l y s a m e s p e e d I a d d e d C l 2 i n m y e x p e r i m ent. Another problem i s e q u a l i s i n g t h e p r e s s u r e ( i n a n o d e
a n d c a t h o d e c h a m bers)
Am I thinking right about following?

Both electrolytical and abovenam ed method of chlorate preparation requires 3Cl2 to produce 1KClO3, however, first method
gives 60-70% efficiency while second gives 100 %. So, is second way m ore effective, or is there some catch?
a_bab July 19th, 20 03, 07:5 7 AM

I would stick to the first method as is cleaner. The second method requires lots of heat, chlorine production on site (a tank
would m ake wonders, m ore setup).
The first one is slow. The second is faster and the product is pure.
W ell, if you have the resources, both methods are good. I'd choose the second one if I would be able to get a tank of chlorine.
jeffchem2000 July 24th, 20 03, 05:2 8 PM

if yo u add an acid to bleach chlorine gas is gen erated. I did this by m istake but luckily for m e it was extra thick bleach so the
chlorine took a long time to reach the surface. (enough time to get it outside) also if you add am m o n i u m h y d r o x i d e t o b l e a c h
chlorine is given off. but with different am o u n t s o f a m m onia can lead to NCl3 being produced and in differe nt conditions
hydrazine. so this way isn't ad visable.
Skean Dhu August 18th, 2003, 10:14 PM

why go through all of that trouble when you could make it mcuh simpler via the m ethod found in NBK2000's PDF? (which i ho p e
he dosen't m ind me posting)
1200g HTH(Calcium hypochlorite 65% sold as a pool chlorinator) + 220gKCL mix with boiling water and let the Calcium chloride
precip. out then filter while boiling hot and let the KCLO3 precip. out.?
0EZ0 August 18th, 2003, 11:25 PM

I think you will find it rather difficult to crystallise CaCl2 out of solution as it is very soluble in water (75gm per 100m l W ater).
Destruction of hypoch lorite to yield chlorate is tedious and usually gives a very po or yield. I'd prefer a chem ical m e t h o d m y s e l f
to electrolysis, but I would not choose the hypo chlorite m e t h o d d u e t o t h e a m o u n t of work n e e d e d a n d s m all yield.
The idea frogfot put forward was to show another way of producing chlorate relatively quickly with good results. In the coming
weeks I may try this m yself out of curiosity. Sounds like a good way to use that e xcess chlorine that escapes from a chlorate
cell.
Nice work frogfot :coo l:

W ouldn't there be too sm all am m ount of chlorine from chlorate cell? My cell (68W /2,6l) gave off <7g chlorine per 24 h
(calculated from added HCl). So alot tim e w o u l d b e n e e d e d . T h o u g h o n e g o o d t h i n g i s t h a t K 2 C O 3 solution probably wouldn't
have to be heated since such low conc of chlorine would react at room tem p, or?
W ould be nice to carry out the reaction till the end, it's interestin g how much chlorine will e scape at the end. (don't wanna up set
neig hbours, and this would be too m u ch e q u i pe m e n t to t a ke t o t he f o res t ..)
0EZ0 August 19th, 2003, 07:02 AM

Yes thats quite true frogfot. The amou nt of chlorine liberated from a chlorate cell would be rather small and probably not worth
it sm all scale. It may well be a nice way to prepare a side sam ple with high purity and no need for laborious task of rem oving
graphite/carbon impu rities though.
A n o t h e r i d e a t o e x p l o r e m a y b e t o u s e N a 2 C O 3 i n s t e a d o f K 2 C O 3. Although I have seen no reference to using Na carbonate

instead. Solubility between Na and K chlorates is supposed to be considerable, which m a y n e g a t e t h e u s e f o r a f u n n el to feed
the chlorine into the scrubbing solution. Once the reaction is com plete, convert to KClO 3.
There are a few chem ical methods of producing chlorine , some more attractive than others. The main issue is the rate at which
the reactions liberate Cl2 and in what quantity. Too m uch at the wrong tim e m ay lead to g assing the surroundings with noxious
chlorine. An alternative to producing chlorine ch emically would be to use a chlorine/hydrogen cell with a m e m b r a n e s e p a r a t i n g
the anode and cathode. This solves the flow rate, and maintaining the cell to produce C l2 would be a whole lot easier.
A few chemical reactions to produce chlorine below:
2 HCl(aq) + NaO Cl(aq) ----> Cl2(g) + NaC l(aq) + H2O(l)
M n O 2(s) + 4 HCl(aq) ----> C l2(g) + MnCl2(aq) + 2 H2O (l)
2 KMnO4(s) + 16 HCl(aq) ----> 2 MnCl2(aq) + 2 KCl(aq ) + 8 H2O (l) + 5 Cl2(g)

W ith Na2CO 3, form ed NaC l would still tap the tube. Rea ction also have to be driven to the very end, since it would be
im possible to rem ove Na2CO 3 by recrystallisation.
I was thinking about m aking a chlorine cell, but corrosion of graphite electrode annoys m e.. Hopefully electrodes will last lon g
with efficient cooling. I also found som e i n f o i n a b o o k o n a s b e s t o e s m e m branes, hopefully, usual glass-wool will do as
m embrane.
Mendeleev Novem ber 16th, 2003, 12:44 PM

C a n p o t a s s i u m c h l o r a t e b e s u b s i t u t e d f o r p o t a s s i u m nitrate in black powder, I don't want to waste and potassium nitrate which
I u s e t o m ake nitric acid. W ill potassium chlorate affect the power of m y black powder?
Bert Novem ber 16th, 2003, 01:37 PM

If you directly substitute chlorate for nitrate in a black powder mix, it will be considerably more powerful and have a much
greater pressure exponent. The net result, it will be dangerous to use in black powder arm s . R o c k e t s m a d e with it will blow up
unle ss you greatly en large the nozzle or add phlegmatizers such as oil or excess charcoal to the m i x . S u c h m i x e s f i n d u s e i n
salutes and for bursting small fireworks star shells. They are dangerously friction and shock sensitive, and m a y b e c a p
sensitive high explosives depending on the ratios. The French government tried to substitute chlorate in military gunpowder
very briefly a t the end of the 18th century- in 1788, the pilot powder plant blew up, killing several people and the attem pt was
a b a n d o n e d . T h e m ix involved was 6 parts chlorate, 1 part Sulfur and 1 part charcoal.
metafractal Novem ber 17th, 2003, 01:04 AM

Substituting chlorate for nitrate in black powder is silly. Even if you do the stichom etry and change the ratios, suphur and
c h l o r a t e s d o n o t g e t a l o n g . T h e m ix will be shock sensitive and prone to spontaneous ignition.
There is no real substitute for black powder using chlorates. H3, however, can be m ade with charcoal and chlorate. It behave s
differently to blackpowder- m arkedly, its m ore energetic, but it is still insensitive and nice to work with. It can still be used in
rockets like BP with som e m odifications. Som e popular ratios are 10:3, 7 5/25, an d 77/23 with about 2% binder. Many sources
suggest hem p coal should be used.

This H3 is intriguiging... I will have to try it very soon. As far as the chlorate sulfur m ix, I think I will try that anyway ;), in very
s m a ll quantities, no more than a gram . It is useful in blasting caps I hear, perhaps mixed with som e t h i n g e l s e s u c h a s M F .
Thanks for the info, twas' indeed helpful.
0EZ0 Novem ber 18th, 2003, 01:32 AM

I would be careful with any com position involving chlorates. They tend to be rathe r sensitive to mechanical provocation. I'm
sure one of our m embers (Arkangel wasn't it?) had an accident while pressing a chlorate com position sim ilar to H3 into a
rocket tube.
Chlorate & Sulfur is one of the prim ing compositions of old. To my knowledge it was NEVER used in comm ercial blasting caps.
The mix is so sensitive that it can ignite if you try to m i x t h e c o m p o n e n t s i n a m ortar and pestle (even gently). If that
sensitivity is not scary enough , s p o n t a n e o u s c o mbustion can ensue with contaminated sulfur (with H2SO4) thanks to formed
HClO3 which is dange rously re active and explosive. W hat you were referring to wa s probably it's use in im pact ignition primers
used in old firearms. Since then there have been MUCH better, safer alternative priming com positions.
Bert Novem ber 18th, 2003, 03:05 AM

C h l o r a t e a n d antim ony sulphide, with various other goodies added were the basis of the o ld corrosive prim ers. Corrosive
b e c a u s e o f t h e K C l p r o d u c e d . C h l o r a t e a n d s u g ar was what got Arkangel, as I recall. According to Shim izu, m ore friction/im pact
sensitive than chlorate/charcoal. H3 isn't very im pact sensitive by itself, I've hit it on a clean anvil with a steel hamm e r a n d
b e e n u n a b l e t o m ake it go off. When in contact with sta rs primed with Su lfur containing BP, it's another story! I've used H3
burst, but no w I tend to use perchlorate based whistle m ix with BP coated hulls for sm all b all shells (less than 6"). Just slightly
s a f e r in my estimation.
Unburied Novem ber 21st, 2003 , 08:40 PM

Chlorine gas was once produced industrially by treating table salt with strong sulphric acid. Dont do it in the kitchen.
Draw the chlorine gas through a 20% NaOH solution to produce Chlorine bleach (NaOCl). You m ay need to provide cooling;
when the NaOH saturates, oxygen will flash out of solution and foam it over.
S o d i u m C h l o r a t e c a n b e s y n t h esised by carefully adding HC l to Chlorine bleach (try for a pH of 7) and gently heating (60 deg.
C). The reaction is rather slow but its cheaper than electrolysis. The colour of the solution should go from that sick-piss yello w
to clear.
blindreeper Novem ber 21st, 2003 , 11:50 PM

Sorry to bust the bubble but you can't m a k e C l 2 f r o m NaCl and sulfuric acid. The reaction goes like this:
2 NaCl + H2SO4 -> 2 HCl (g) + Na2SO4
I have tried this myself so you can't say I am wrong :PI don't suggest you try it b ecause hydrogen chloride screws o ver most
m etals in the vacinity. Most of the m etal stuff in a 2 M radius of my lab is corroded :D
Yay 250 posts

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Purification of OTC
Paraformaldehyde
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View Full Version : Purification of OTC Paraformaldehyde
nbk2000 July 23rd, 2003, 01:19 AM

I finally broke down and bought myself a box of Campa-Chem dry chemical toilet deodorizer, which is paraformaldehyde.
And, as I expected but hoped not, it is blue dyed. :(
I'm not sure if the dye would have any effect on making hexamine, or whether it'd carry through the nitration process to result in smurf colered RDX :D, but I'm willing to give
it a go.
But, it'd also be nice to be able to be rid of the blue shit in my shit, nigga. ;)
I'm thinking sublimination, but I'm not sure if it subliminates, or simply decomposes.
I've attached a picture showing what the para looks like.
Any suggestions, or has anyone else tried using this material in a process?
BTW, it might make a good area denial material. I spread about a tablespoons worth out in the yard, and hours later it still is unpleasant to stand downwind from the spot. I
could envision sprinkling a bit of it about in areas where you don't want little pikers to hang out at.
I've got just the spot in mind for testing. It's a pedestrian train overpass that the local teenies hang out at and posture for each other at. It's annoying to have to walk through
the crowd of lil' shits.
blazter July 30th, 2003, 12:17 AM

I have taken a few stabs at washing off the blue dyes on campa chem. Methanol seemed to do the job well, and cold water seemed to do just as good as job much cheaper.
As for attempting to produce hexamine from the washed solids...well thats where the trouble comes in. Adding the white cleaned solids to clear household ammonia solution
and boiling does seem to dissolve the paraformaldehyde with difficulty. HOWEVER, as the solution becomes more concentrated, a scum of sorts seems to appear, and on the
sides of my glassware a rather tenacious soap scum deposited :mad: This scum that precipitated did not appear to be crystaline at all, in fact it appeared to be some sort of
detergent. Evidence that this white scum is detergent is observed by the white film that was left on the glassware. Even scrubbing with abrasive sponges hardly touched it, I
finally had to soak it in full strength muriatic acid. I am quite sure that the ammonia is not to blame since I used it a while ago to prepare some NH4Cl by neutralizing it with
HCl.
As for subliming it, that was the only method that seemed to show promise. The thing to really watch out for is suckback which is what killed my heating "flask". I used an old
bottle and stuffed a bit of tubing in the end of it and led the vapors to a bit of water. White fumes were produced which appeared to condense as a solid in the water IIRC. I
never continued with the sublimation route because of a lack of suitable glassware to use.
nbk2000 July 30th, 2003, 03:28 AM

Sounds more like you were doing a vacuum distillation, rather than a sublimination.
I'm going to try it using a jar and a metal pan full of iced water. The heated vapors should condense on the bottom of the pan as crystals (hopefully), unless it decomposes on
heating into gaseous formaldehyde.
I figured there was some sort of "added" crap in my crystals. My hexamine came out blue and crunchy, looking like instant coffee crystals...only bluer. :p
Unfortunately, the manufacturer of the chemical doesn't have a website, nor a phone number that I've been able to find. :( So no MSDS yet to tell me how much para there
actually is in the shit.
vulture July 30th, 2003, 08:23 AM

Adding the white cleaned solids to clear household ammonia solution and boiling does seem to dissolve the paraformaldehyde with difficulty
You first have to break down the polymeric paraformaldehyde into formaldehyde, because paraformaldehyde is nowhere as reactive as the very reactive formaldehyde.
Heating does decompose paraformaldehyde into formaldehyde, which has a very low boiling point. You'll need to dissolve it in water.
inFinie July 31st, 2003, 02:45 PM

Paraformaldehyde (trioxan, 1,3,5-trioxacyclohexane) is stable in acidic condition (no more details like btw. which pH's). So maybe adding some base like NaOH will decompose
it to HCHO, NH3 is a base indeed. But i'm not sure NaOH will work. This was from a school book.
To prepare HCHO trioxan is heated.
In some resources paraformaldehyde is stated as a polymer, and in some it is stated as a trimer. I am not sure which one is true.
mongo blongo August 1st, 2003, 08:37 AM

If your goal is to make Hexamine then maybe it would be a good idea to decompose your OTC paraformaldehyde by heat and bubble the resulting formaldehyde into
ammonium hydroxide.
nbk2000 August 1st, 2003, 06:59 PM

That's what I'm going to do. :)
Though it'd have been nice if it was pure enough to use in the Para/AcO/NO3 reaction for RDX production. :(
vulture August 2nd, 2003, 08:31 AM

Purification isn't that hard, considering that your product will probably contain dyes and other crap with a rather high boiling point. Simple destillation or absorbing in water could
easily reach 98% purity, even more if it doesn't contain any other very volatile substances.
BTW, you got AcO? :eek:
EDIT: Just got an email from a certain Tri-x who can't post because he reregistered himself.
Anyways, he sent me the link for the MSDS:
http://www.thetford.com/msdsforms.cfm
nbk2000 August 2nd, 2003, 03:26 PM

I wish I had AcO, but that's in the future, once I build a ketene generator. :)
You have no idea how hard it is finding someplace local that sells black rubber stoppers. :( It's easier to score drugs than find a rubber stopper in this town! :o How fucked up is
that?
Tuatara August 3rd, 2003, 06:15 AM

Got a brewers supply shop there, NBK? They'd have rubber stoppers, both plain and single hole. Not a great size selection usually, but 'beggars can't be choosers' as the saying
goes.
bombtech September 17th, 2003, 09:35 PM

Well, I've been browsing the forums for some time now and finally have worked up the nerve to post a reply (and hopefully not getting banned or fragged to hard!).
NBK,
have you been able to successfully purify your campa-chem? I also bought some of this for the synth of hexamine and was pretty ticked off to see it was not pure.
Also, I recently purchased some trioxane. can this be used in the same manner as the para to evolve formaldehyde? Would the para/trioxane be disolved in water before
heating or is this done dry? When this is heated and the resultant formaldehyde gas is fed into some water, how can I measure the resulting concentration, i.e. density(specific
gravity), weight? or does this even matter for the hex synth?
please be gentle!!!
bobo September 18th, 2003, 07:04 AM

I did hexamine and it seems not to matter what stoichiometry you use. I used too much ammonia and a very good yield was obtained after boiling off water and ammonia.
The ammonia was rather pure though (25% or something). If you want to try leading formaldehyde gas through water why not lead it to ammonia immediately?
bombtech September 18th, 2003, 11:48 AM

if the stoichiometry is not so important, then thats what I would do. I just want to make sure I'm not wasting to much of either.
bobo September 18th, 2003, 02:23 PM

The losses of home scrubbing are probably considerable depending on your setup. Bubble size affects diffusion of course but also retention time so the thing to do is disperse.
With a funnel on a tube I got the ammonia smell through the house very strongly when concentrating from 5%:(
The free ammonia and formaldehyde worry me more than the inefficiency.
Zio Matrix January 10th, 2005, 09:07 PM

This is a pretty old thread, I dunno if anyone's still trying to clean OTC paraformaldehyde, but:
I have a box of Coleman's dry holding tank cleaner, and it seems to be somewhat less contaminated than the Campa-Chem stuff, as it only took about 5 rinses to get out
most of the blue dye as opposed to 10 for the Campa chem, and the "perfume" seems to wash out as well. Sadly, the only place I've been able to find the Coleman's stuff is
at K-Mart a while back, and they don't seem to stock it anymore, but I just thought I'd let you all know to snap it up if you find any, because it's certainly easier to purify than
that CC shit.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Medical Treatment
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View Full Version : Medical Treatment

As we deal with many, many poisons and such i think it would be good to compile a first aid style guide. From things as simple and minor as treating NG headaches to things as
serious as treating 3rd degree burns and HCN poisoning. I may w ork on it but im not sure whether i would do it as a website PDF or what. Any comments/help is appreciated.
GibboNet July 27th, 2003, 02:04 AM

I'm sure people here would be help, and I know there are a few people that will be able to give details of accidents they have had, and what injuries they have recieved, big or
small.
I have basic military training in burns (chemical, heat, liquid, radiation, friction) haemmoraging (bleeding) Fractures (compound, simple and complicated) Snake bites, Spider
bites, and a bunch of other stuff I can't remember now. I can find more information if you like. I also have the lab safety guides and emergency procedures from UNI. (Chem
classes)
yt2095 July 27th, 2003, 06:47 AM

I have several surgery manuals, pharmacy handbooks, poisons/antidote guides if you have anything specific in mind, I`de be pleased to help you out :)
blindreeper July 27th, 2003, 07:47 AM

I (from experience) can tell you w hat to do in case of chlorine gas poisoning. Your chest will feel tight and your breathing restricted, as you beathe in at a certain ammount of
air you will feel extreme pain. So you have to pant. But after a while you will find you can take deaper breaths and you will feel better. Also Ventalin puffers w ill help if you can
get it down to the bottom of your lungs (if you do it will cause excrusiating pain)
I felt really hot and sweaty and felt like I was going to throw up (never did).
My mum rang the poisons hotline and they reccomended Ventalin.
I ended up in hospital (20 minutes later) and was feeling much better. I got on the oxygen tank for about an hour and by the end of it w as feeling quite happy (didn't know O2
made you feel happy)
My contribution :p
Imperial July 27th, 2003, 10:33 AM

I have a basic first aid certificate w hich I completed recently, which means I w ill be able to cover burn first aid and cut first aid.
As for poisons, I can give many accounts of accidents I have had with them (not not on other people :P). I know their effects, and how to treat some of them.
I will be more than willing to help in this, for I feel that it is important that if w e are dealing with explosives, weapons, and poisons, that we can at least do it with some degree
of safety. Email me if you would like more information on any aspect of the above.
knowledgehungry July 27th, 2003, 03:22 PM

Alright i have decided that i w ill undertake this task. I plan on having a couple of main topics. General first aid(cuts, burns, bruises), treatment of specific chemicals ie chlorine, a
list of the hazardous chemicals(and w hat they do, and how much is lethal), and a prevention section. I am going to first start w ith the list of chemicals, not all chemicals just
those that we use. The task of listing them all is bound to be hard im going to start w ith megas precursors section, but more will be needed to be added im sure. Fortuantely my
father is a doctor so he w ill most likely have some information of value, or at least be able to translate some of the medical mumbo jumbo that you get on some sites. Well i
wont be bored now. If anyone has any ideas/comments you can email me or write them here. I will post my tenative list of chemicals as soon as it is done, just the list not the
effects or details as i wont begin that untill i have all the chemicals listed that i should cover.

Here is a very tenative list, mainly taken from megas precursors. These are only the chemicals, i will also list explosives but not now. Please feel free to comment on additional
chemicals to be included, and maybe some that we could do without.
[list removed]
EDIT: edited list added some, removed others, will most likely do again, let me know of any doubles i.e both hexamine and methenamine. Feel free to mention any chems that
should be added. Most likely i will delet a good deal of chemicals as i do research on them, if i find they are harmless.
irish July 27th, 2003, 09:41 PM

This is a very good idea but you have a few non-toxic chemicals in that list, ie calcium carbonate,
water etc.
It may be best (and take less of your time) to just list the more toxic chemicals.
If I can help in any way send me an email,
Good luck with it .

I'd cut it down to the ones that people here are actually likely to be using. I mean, how likely is it that someone here w ill be poisoned by allyl methanesulphonate or nitrosyl
tetrafluoroborate?

You are correct Mr. Cool, how ever i got those from Mega's precursors section. As I have said that is only a tentative list, and I appreciate comments such as yours(makes my
job easier). Well I'll edit the list once again to get rid of the less than useful ones. I am also going to make a list of all the explosives used because i also w ant to deal with their
toxicity such as PA.

If no one has any additions/subtractions to this list i will start work on the toxicity and how the chemicals affect you. I'll w ait until tomorrow until i start w orking on it to give any
people a chance to comment if they need to. I w ill let you know w hen that part is done.
yt2095 July 30th, 2003, 10:39 AM

just an idea, but if you do a search on here for each of the chems you`ve listed, Keep the ones that show a result.
It`s a massive list and at face value IMO it`s very daunting/off putting. esp when some like Tannic acid (edible) don`t even realy belong on there :)
not in the capacity of Toxicology anyw ay.
refine the list a little so it`s at least in workable chunks and rellevent, then maybe some way of distributing it in these chunks so that we`re not all working on "Acetaldehyde"
etc... at the same time :)
feel free to pass on the things to me that no one can get any real info about, I`ll use the old fashioned Book method :)
`t aint like I`ve got anything else better to do atm :)
All the best :)

Ok I did as you suggested and searched for all the chemicals in posts here, I got rid of 16 of them(havent removed them yet as i can't edit the list) and found 7 to add. So that
makes me have 9 less to research. I am waiting to see if the webmaster will give me permission to edit my list, if not i w ill just have to repost my list.
yt2095 July 30th, 2003, 01:24 PM

oh dear :(
seems like that`s quite a chunk to work through!
look, if you have any difficulties w ith some of the more "abstract" chems on or not on your list as yet, mail me, NO promises, but I WILL do my best to get you answers :)
I can`t say fairer than that :) as for the bulk of your list Id`e hazzard to say that 99.999% of it will be freely available on the net anyway. the other 0.0001% let me know :)
knowledgehungry July 31st, 2003, 04:12 PM

Here is the list that i will start working on: Mods please remove list from first post(i cant edit it anymore) thank you.
Acetaldehyde
acetamide
Acetylsalisylic Acid
acetic acid
acetic anhydride
acetone
acetyl chloride
aluminum(fine powder)
aluminum chloride
ammonia
ammonium carbonate
ammonium chloride
ammonium hydroxide
ammonium nitrate
ammonium perchlorate
aniline
aniline acetate
barium chloride
barium carbonate
barium chlorate
benzal chloride
benzaldehyde
benzene
bromine
bromobenzene
boric acid
calcium hydroxide
calcium sulfate
carbon disulfide
carbon tetrachloride
chlorine
chloroacetic acid
chlorobenzene
chloroform
citric acid
copper
copper oxide
cyanuric acid
cyclohexanone
cyclohexanol
m-cresol
cupric sulfate
dextrin
dicyanodiamide
diethanol amine
dihydrogen sulfide
m-dinitrobenzene
ethyl acetate
ethyl alcohol
ethyl chloride
ethylene dichloride
ethylene glycol
ethyl ether
formaldehyde
formamide
formic acid
gasoline
glycerol
HBIW
n-hexane
hexachloroethane
hydrazine
hydrochloric acid
hydroflouric acid
Hydrogen cyanide
hydrogen iodide
hydrogen peroxide
iron oxide(red and black)

iodine
isoamyl alcohol
isocyanic acid
isopropyl alcohol
isopropylamine
lead acetate
lead monoxide
lead nitrate
magnesium oxide
magnesium styphnate
maltose
manganese
mannitol
mercuric nitrate
mercuric oxide
mercury
mesityl oxide
methenamine
methyl alcohol
Methyl ethyl ketone
methylamine
methylene chloride
naphthalene
nitric acid
nitric oxide
nitrobenzene
nitrogen
nitrogen dioxide
nitromethane
nitrous oxide
oxalic acid
oxygen
paraffin
paraformaldehyde
paraldehyde
parlon
Pearlman's catalyst
pentaerythritol
perchloric acid
petroleum ether
phenol
phosphorus
phosphorous pentoxide
phosphorus oxychloride
phosphorus trichloride
picramic acid
picryl chloride
polystyrene
polyvinal alcohol
potassium chlorate
ptassium dichromate
potassium hydroxide
potassium iodide
potassium nitrate
potassium perchlorate
potassium permanganate
n-propyl alcohol
propylene glycol
pyridine
PVC
silver iodide
silver nitrate
sodium
sodium acetate
sodium azide
sodium benzoate
sodium bisulfate
sodium bisulfite
sodium chlorate
sodium dichromate
sodium hydroxide
sodium hypochlorite
sodium nitrate
sodium nitrite
sodium salicylate
sodium silicate
sodium sulfate
sodium sulfite
stearic acid
strontium carbonate
strontium nitrate
strontium sulfate
sulfur
sulfur chloride
sulfur dichloride
sulfuric acid
tetrahydrofuran
tin chloride
tin tetrachloride
toluene
trifluoroacetic anhydride
urea
urea nitrate
xylene
zinc
knowledgehungry August 5th, 2003, 10:21 AM

I am going to try to finish this depite w hat happened. http://www .roguesci.org/theforum/showthread.php?s= &threadid=2931
However im not sure w hen i w ill really start w orking on it again, hopefully soon so it can help prevent more accidents.
Arthis August 5th, 2003, 12:43 PM

After w hat happened, I understand that it may be difficult to work on a project, but this one may help staying off pyro activities, purely medical treatments... there is no direct
connection, apart from the choice of compound you made ;).
If I can help, tell me. What type of information do you w ant to give ? A first choice source would be the MSDS, but w hat do you want to add more than that ? A complete
description of what occurs when contamined (chemical processes and their consequences... ?).
scooter12589 September 16th, 2003, 11:00 PM

Hi, I am new to the forum.
For help with treatment for exposure to chemicals you can use MSDS sheets.you can do a search for them at http://www .msdssearch.net/. I hope this helps and I really like the
idea.
knowledgehungry September 17th, 2003, 08:48 AM

The person above you mentioned MSDS sheets, and yes that was where I was going to start:rolleyes: . However I do appreciate you bringing this back to my attention as I had
nearly forgot about it, I will try to work on it some more, but I have been busy as hell lately what w ith school starting, nice weather, girlfriend etc. I have done a little bit more
work on it, but no where near done. If someone wanted to do a section on first aid for cuts, burns, shrapnel wounds and chemical burns that w oud decrease the time needed
before it is done, e-mail me if you are interested [email protected].
knowledgehungry January 8th, 2005, 11:44 AM

Well I am working on this project again. I'm only doing a PDF on the toxicity and carcinogenity of these chemicals at the moment. And I am only doing those involved in
explosive synthesis right now.
Pb1 January 13th, 2005, 11:11 PM

Im surprised that this has not been m entioned yet, J TBaker (http://www .jtbaker.com/asp/Catalog.asp) has a lot of good MSDS sheets.
Chris The Great January 14th, 2005, 04:21 AM

Since it was mentioned that it shouldn't cover uncommon chemicals, that would be a horrible thing! Chances are, if it's uncommon you're not going to have much info on it, and
so it w ould be necessary to include it in the guide if it was to be a good safety guide.
This seems like a great idea. Perhaps grouping some chemicals together (ie acids) w ould save time. For example, have an acid section, list all the dangers of conc. acids, and
then some little blurbs about any special features some acid might have (for example HF's ability to attack bones, H2SO4's dehydrating properties etc.)
This would be something I wouldn't mind helping out with, I have alot of experience with 'safety' (or lack of). I have a fair amount of time on my hands, so it's easy for me to
search for an hour or two a day, if you're having trouble researching such a huge list of chemicals. That's average of course, right now my time is limited due to finals coming up
etc.
Gedi January 15th, 2005, 06:25 PM
If you go to www .skyscape.com you can dow nload a free palm file called 911. It is a first aid reference and has information about bioterroism. Not sure, but you might be able
to convert it to a w eb document.
I also have the skyscape crack for the other files on their site as well as several medical texts in Palm format if anyone is interested, i can upload them to the ftp.
croc January 23rd, 2005, 11:56 PM

I have found a good w ebsite w ith something on it. http://ww w.drugnet.com.hk/tox/tox_antd.htm
Also on homedistiler.org it has something about the cure for methanol is ethanol but it has to be taken in a specific w ay over a period of time
MazdaBoi June 16th, 2008, 12:41 PM

I know this is a really old thread, but I wanted to post info about one of the chemicals... Maybe it will save someone's life someday...
Ethylene glycol... It's used in anti-freeze mainly, but can be found in the coolant used in water cooled computers, capacitors, and various other places...
The best way to treat ethylene glycol poisoning is to use ethanol. Get the person drunk. Ethanol binds to the same enzymes as ethylene glycol, thus competitively forces the
ethylene glycol out of the system.
CALL 911 too... Hospital treatments consist of an IV of ethanol, and a gastric lavage to remove any unabsorbed ethylene glycol... Another drug called Fomepizole is available to
hospitals that blocks the formation of the toxic metabolites. It is used in conjunction w ith ethanol.
If the metabolites have already began to form, dialysis is also used to support kidney function and help remove the toxin.
Time is of the utmost importance... Once the ethylene glycol binds to the enzymes, the damage is already in progress and cannot be ceased. The sooner you can get ethanol
into the system and get the person to a hospital, the more of a chance the person's life can be saved.
To reiterate:
1) IMMEDIATELY CALL 911 AND GET AN AMBULANCE EN ROUTE. TELL THEM ETHYLENE GLYCOL IS INVOLVED SO THEY WILL HAVE IV ETHANOL AVAILABLE.
2) Get the person drunk... Don't overdo it, (ie, don't give them alcohol poisoning in addition to ethylene glycol poisoning), but give them enough to get pretty intoxicated. Do
this ASAP after it is realized that ethylene glycol was ingested. Time is of the essence.

a n d I m provised C hemistry > C hemistry Referen ce?
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Bo bo August 1st, 2003, 07:15 PM

I have spent an age looking through the www b ut i cann ot for the life of m e f i n d a n y g o o d s i t e s f o r C h e m istry reference. I was
look ing for the solubillity curve of sodium chlorate but i couldn't find it any where! Could anyone be so kind as to to me the
address of a site which has the solubillity curves of most of the comm on salts? or any other useful sites regarding chem ical
data?
Marvin August 2nd, 2003, 04:04 AM

Should this be in links and lit?
http://www.ucdsb.on.ca/tiss/stretton/chem2/compound_solub2.htm l
4 tem peratures, easily enough to draw a curve yourself.
www.kerr-mcgee.com /techdatasheets/English/1181.pdf
Has a curve, but beware the units are different, as are the units in the table next to it.
Both in the first 4 pages of go ogle '"sodium chlorate" solubility'
The internet is always disspointing for this sort of thing, get a 'CR C h a n d b o o k o f c h e m istry and physics' stu dent edition. Not
m uch specific about most salts except 2 tempe rature solublityies, but about 2500 pages of data I think and rather taking th e
term 'handbook' to new extrem es, but a very u seful reference.
Bo bo August 3rd, 2003, 05:56 PM

C h e e r s c h a p , m o s t h e l p f u l l ! Y o u m u s t h a v e b e t t e r e y e s t h a n m e because i couldnt find an y t h i n g o f m u c h u s e o n G o o g l e .

a n d I m provised C hemistry > sillicon tetrachloride
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zeocrash August 7th, 2003, 08:37 AM

ok i was browsing through my big book of chem icals the other day when i cam e accross sillicon tetrachloride. among it's uses
was millitary sm o k e s c r e e n .
i was wondering if anyone kne w how this worked, i was thinking that maybe the sillicon tetrachloride decom p o s e d t o e i t h e r
sillica, sillicon or sillicon oxychloride (not sure if this exists). under heat. but i'm not sure.
any ideas
yt2095 August 7th, 2003, 09:05 AM

The only reaction I re meber with SiC l4 was to do with bonding traits, we also com pared it agains Carbon Tetrachloride.
the O ne test was reaction with water, SiCl4 + H2O left SiO2 + HC l
p e r h a p s ( a n d I ` m guessing) that the SiO 2 could be used if fine enough to create a white "smoke" effect in the air?
s o m e type off reaction that emits wate r vapour as a combustion product while mixing with the SiCl4?
that`s the only Smoke like effect I`ve seen from SiO4, my logic is that the Silicon is critical, because if it wasn`t, then Carbo n
Tetrachloride would be used instead as it`s MUCH cheaper to produce and friendlier to handle (think Dry Cleaning fluid)
all the best anyway :)
nbk2000 A ugus t 7t h, 2003, 03: 27 PM

Military sm o k e s y s t e m s u s e d a m monia gas in conjunction with the SiCl4 to produce the sm oke screen. It would form particles
o f a m m o n i u m chloride and silicon hydrate that would form t h e o b s c u r i n g s m o k e .
SiC l4, by itself in air, would form HCl by hydrolysis with am bient hum idity, so it only works if there's m oisture in the air. Dry air,
like in deserts, greatly decreases such hydrolysis, m aking it ineffective.
Titanium Tetrachloride is much more e ffective as a chemical sm o k e a g e n t .

Sadly carbon tet can't be used, the poor little carbon has no d orbitals to accept e lectrons and form the interm ediate in the
reaction. I th ink it's to do with the d orbitals, anyway...
Plus CCl4 has a tiny little carbon atom surrounded by four huge chlorine atom s, so there's little room for attacking species to
get to the carbon.
Pitty, isn't it? CCl4/NH3 sm o k e w o u l d b e c h e a p .

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > HCl + nitrate
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metal dragon September 6th, 2003, 08:26 PM

Hello all,
Concentrated HCl has a p. H of 1 meaning it is extremely strong acid. When could HCl acid and a nitrate be used as nitrating mix? Say for nitrocellulose or mono-nitro-
naphthalene? HCl I will be using is 30% but in quantity is not a problem. HCl should be the origin of H+ ions. In Alen, Mega and Mr cool all have a synthesis in which HCl is
used with a nitrate (of memory I think it is hexamine-di-nitrate) Any comments are all welcome.
Thanks all!
knowledgehungry September 6th, 2003, 11:46 PM

IIRC the reaction HCl+nitrate <=> HNO3+chloride favors the left side so most nitrations arent succesful.

Formation of nitro esters (for example NC) also needs this to happen:
HNO3 + H+ ==> NO2+ + H2O
HCl is probably too weak for this. I once tested to make NC by HCl/KNO3 without any success, however maby this method can be improved somehow??
Oh, and hexamine dinitrate is a nitrate salt, so thats another thing.

metal dragon, you will not recieve instant banning for the crime of posting a new topic with a low number of posts as i feel this topic is worth discussing and i have things to
add :)
just be aware of the rules of the forum and the unofficial rules found in the water cooler as a sticky thread.
i don't believe this method will be of any use for any real nitrations. only for formation of nitrate salts. as other have stated.
the way i thought it worked is that HCl (being quite a strong acid) would donate H+ to any NO3- ions in the solution since NO3- is a stronger base than Cl- (well, thats what i
remember). Thus you get a solution of HNO3 when you react a nitrate salt with a solution of HCl.
to form nitrate salts you just need a base. so if you throw hexamine into the now HNO3 solution you get HDN.

I thought Cl was stronger(not right word) than NO3. I thought the H+ were drawn to the Cl- cuz its more electronegative, but im not sure.

No, Cl will draw electrons to itself, making the formation and dissociation of H+ favourable.
Al Koholic September 7th, 2003, 07:05 PM

Think of it in terms of affinity. Cl- has a higher affinity (this can be determined by the acids dissociation constant) for H+ than does NO3- hence the lack of formation of HNO3.
Sulfuric acid on the other hand has a much lower affinity for H+ than even NO3- and hence vacuum distillation of weaker HNO3 is possible from H2SO4 and XNO3.
The differences in affinity are caused by differing stability of the anions in question. Cl- happens to have a noble electron configuration, happens to be fairly electronegative,
and happens to have a fairly large atomic radius leading to a good amount of stability in its charged form. Nitrate and sulfate are heteroatomic, double bond containing anions
and hence can form resonance structures leading to a higher stability in a charged state and therefore less need for a proton to increase stability.
metal dragon September 8th, 2003, 04:43 AM

Thanks everybody, SWIM is going to test NC via HCl + KNO3. SWIM will be using 30% HCl, pure KNO3 and pure cotton. Does anybody know the correct formula and ratios for
these chemicals? As soon as that is figured out I should be ready to begin. Maybe the reaction should be heated in order for the H+ ions to react. Any help would be
appreciated? Thanks
IPN September 8th, 2003, 05:16 AM

I would use 3mols HNO3 to one mol of cellulose, although there is nothing to remove the water formed...
But anyways I would use the following amounts of chemicals:
109,374 ml HCL (100%, you will have to calculate the correct amount for 30%)
303,33 g KNO3
~10 g Cellulose (It's a small amount but considering the concentration of the HNO3 in the nitrating mix...)

IPN, exactly. esterification reactions are equilbirium reactions. thus if you can't remove the water you aren't going to form and ester (NC).
so in short metal dragon, its not going to work period.
knowledgehungry September 8th, 2003, 08:19 AM

Maybe if you bubbled 100% HCl through the reaction as it was occurring that might help in some way, it would shift the equilibrium.
Al Koholic September 8th, 2003, 01:16 PM

I still don't think you are even going to have a high enough concentration of HNO3...
You really need an acid with a larger Ka than HNO3 has in order to make a favourable equillibrium and HCl just won't cut it.
Think about it, the dissociated acid leads to an H+ and a conjugate base. When mixing KNO3 and HCl you are going to be left with an equilibrium that departs little from the
initial conditions, IE: HCl, and KNO3.
Not to mention that there will be excess water all over the place. If you are going to attempt this I would agree with the above post in that you need dry HCl gas.

knowledgehungry,
cellulose + HNO3 <=> H2O + NC
equilibrium shift to counteract the change you put on them. thus, if you remove all the cellulose then any NC will turn back into HNO3 and cellulose to try and replace the
ceullulose taken away.
so, to shift it the way we want (to make lots of NC) we must remove either the NC or the water. the NC is impossible to remove as it will be infinately mixed with ordinary
cellulose fibres and in most cases attached to un nitrated fibres. thus, for a complete nitration all the water must be removed to convert ALL cellulose into nitro cellulose.
this is true of most exterification reaction, such as those of NG and MHN....
Arthis September 8th, 2003, 04:58 PM

Kingspaz you're right about the equilibrium phenomenom, but as cellulose is in a solid phase, its quantity in the mix will not affect the equilibrium point as long as there's at
least a single cristal (fiber in this case :)).
Here, as water cannot be removed either due to the azeotrope formed with the remaining water, an excess of HNO3 is required to complete the reaction.

Adding more HCl would affect the equilibrium, but you would have to add more KNO3 also to make it shift to more NC, i forgot about that, but I meant that if you had excess
HNO3 it would push the reaction right, very inefficient however.

Arthis, you're dam right. i forgot about that! :cool:
Milamber September 9th, 2003, 12:18 AM

Three suggestions... What if you make the nitric acid in some solvent that KNO3 is soluble in but KCl is not? The KCl would then precipitate and push the equilibrium to the
nitric acid side. Only problem is finding a solvent - glycerol came to mind, but it might be nitrated in the reaction, which would probably not be a desired outcome under most
circumstances...
Second, if I remember, isn't the pKa of HCl about -7, that of H2SO4 about -3 and HNO3 -1-ish? If this is right, HCl should be excellent for producing nitric acid... besides, even
if the equilibrium made it inefficient, you could always just add extra nitrate to make it more favourable and then recover it later - a little more tedious, but might be useful for
someone who has trouble getting sulfuric acid.
Finally, if you wanted to remove the water from a nirtation of cellulose, couldn't you use a dehydrating agent in the mix? The most obvious choice would be MgSO4, since not
only is it common, but the worst thing that could happen if it reacted would be that you get H2SO4 and MgCl2 produced and that makes more nitric acid (by both moving the
HCl equilibrium to the right and also due to the action of the sulfuric).

Is it -7 in concentrated liquid form, or diluted?
Btw, there are another crap, the chloride would be oxidised by nitric acid producing free chlorine and NOx. This reaction is seen with diluted HCl/nitrate salt, and it will be faster
with more concentrated HCl. So we loose lots of produced nitric acid.
(Oh, forgot to mention that CaCl2 as dehydrating agent doesnt seem to work here..)

anhydrous calcium nitrate can be used to dehydrate a mixture of HNO3 and glycerine to form NG.
Arthis September 9th, 2003, 10:03 AM

Making the reaction in a solvent where KCl is non soluble is a way to over-complicate things. Anyway, you need dry HCl gas, or your solvent needs to be non miscible with
water.
Correct me if I'm wrong or if I missed something, but wouldn't this just be a complication and a all-in-one process for the good NA from DCM extractions process ?
John Ashcroft September 10th, 2003, 04:55 PM

In order for nitration to occur, the HNO3 must be protonated to yield a significant concentration of nitronium ions [NO2+]. They are the attacking species in a nitration. Aqueous
HCl will not protonate HNO3 to a significant enough degree. In fact, you'll get more oxidation of HCl than nitronium ions (say hello to aqua regia whether you're mixing ionic
nitrate with excess of HCl or nitric acid with excess of HCl).

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Mercury
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Nehebkhau September 28th, 2003, 04:28 PM

i had a mercury thermometer and it broke inside one of my beakers, a white crystal-like substance came out along with the mercury. What is the white stuff? Also, why do
they still sell mercury thermometers? are they better than others?
DBSP September 28th, 2003, 04:38 PM

Was there anything inside the beaker when it broke?
danmcl2002 September 28th, 2003, 04:53 PM

as far as your question regarding why they still sell mercury thermometers, it depends on your application.
1. mercury thermometers arent very useful for colder temperatures as the mercury can become a solid at temperatures below -38.9C whereas as an ethyl alcohol
thermometer is still useable at
-114C
2. they are much more useful at temperatures over 100C as alcohol boils at 78.4C and a gas is no use in measuring temperature (in a thermometer anyway)
anything above 356.7C and you will need to use a scope of some sort to get your temperature as mercury boils at this point.
i think that the white powder may be a dehydrating agent, so that if the thermometer goes above 100C there is no steam produced which may rupture your thermometer
releasing mercury, which would be bad.
hope this answers your question, im not sure about the white powder but that would be my best guess.

the thermometer broke in a beaker containing sulfuric acid, during the purifying process. thx for the info

Why would there be a dehydrating agent in it? It's filled with mercury, which isn't affected by water in anyway and the thermometer is vacuum sealed anyway!
Sarevok September 28th, 2003, 05:04 PM

Originally posted by Nehebkhau
the thermometer broke in a beaker containing sulfuric acid, during the purifying process.
Your white stuff is mercuric sulfate. Concentrated sulfuric acid reacts with mercury to form mercuric sulfate, which is a white salt.
PS: I think mercuric sulfate is toxic.

I've seen alcohol (red liquid) thermometer that goes above 200*C.. well, had to share this with someone :rolleyes:

Originally posted by Sarevok
Your white stuff is mercuric sulphate.
what exactly is mercuric sulphate used for if anything....and why didn't all of the mercury combine with the sulfuric acid
Sarevok September 28th, 2003, 05:20 PM

Originally posted by Nehebkhau
what exactly is mercuric sulphate used for if anything....and why didn't all of the mercury combine with the sulfuric acid
Its used to manufacture mercuric chloride, which is used to amalgamate aluminum, which is used to make methamphetamines.
For all the mercury to react, you need to do a decent procedure (like the one in the end of this post), not just throw the mercury on the acid...
--
Measure 20g Hg and place in a 100mL conical flask. Do not use a round bottom flask, as all the mercury will not react. Add 60 ml concentrated H2SO4 (should be at least 94%)
to the flask and fit a single hole stopper with a tube leading outside. This reaction produces lots of SO2 that will give you chemically induced asthma if breathed. Now slowly
heat the flask. Bubbles of SO2 will rise from the acid/mercury interface. Maintain a vigorous bubbling of SO2 by adjusting the heat. A white crystalline deposit of HgSO4 will
appear. The mercury should be completely reacted after about 30 minutes. Allow the reaction mixture to cool and pour off the acid. Pour the crystals/acid into 750 mL hot
water and filter. Source (http://www.rhodium.ws/chemistry/mercurychloride.html)

Mercury is a noble metal, therefore it will only react slowly with acids.
Sarevok, subscript is instead of [sub].
T_Pyro September 29th, 2003, 07:48 PM

Originally posted by danmcl2002
a gas is no use in measuring temperature (in a thermometer anyway)
Not heard of a gas thermometer? They're undoubtedly the most accurate thermometers around, as far as reproducibility and resolution go. Click here (http://
www.unidata.ucar.edu/staff/blynds/tmp.html) for more info.
Originally posted by frogfot

I've seen alcohol (red liquid) thermometer that goes above 200*C.. well, had to share this with someone
Now I haven't heard of that before! Is the alcohol under high pressure in the thermometer? If that's the case, then there'll be loss in accuracy at higher temperatures to to the
alcohol vapours...
Anthony October 3rd, 2003, 03:54 PM

Just because somebody made the scale go up to 200*C doesn't mean it necessarily works at it ;)
frogfot October 3rd, 2003, 04:14 PM

But why can't alcohol be used?? It's still liquid under confinement.
T_Pyro October 3rd, 2003, 06:10 PM

Ah yes! Forgive me, for I looked, but did not see! A thermometer beyond 200*C need not be a working thermometer!
Theoretically, an alcohol thermometer CAN be used beyond 200*C, provided you can fulfil the following prerequisites:
1. The glass wall of the thermometer should be strong enough to firstly withstand the temperature, and secondly, high pressures.
2. A sensitive microscope would have to be kept ready to take the readings. As the temperature reaches (and crosses) the boiling point of alcohol, alcohol vapour starts forming
in the free space above the liquid, and exerts vapour pressure on the alcohol column. Due to this, the sensitivity of the thermometer would start decreasing exponentially with
the rise in temperature. Hence, for example, at 200*C, there might be a 1mm rise for 1 *C, but at 400*C, there would be something like a 0.01mm rise for 1*C !
3. You should have a good scientific calculator (and a hell lot of patience!!) at hand to calculate the temperature, by applying gas laws, then the ideal gas correction...
frogfot October 4th, 2003, 04:58 AM

Accuracy may be not that bad..
From http://www.stao.org/safeart2.htm
...alcohol thermometers "have a lower usable range than do mercury thermometers, typically being accurate only below 300C"...
There doesn't have to be a big rise in pressure to elevate boiling point with 100-200* and bring vapor pressure to normal. And since capillary is very thin, walls can be made
thick and compact enough to hold this pressure.
Though there are other liquids that can be used for this purpose, dunno how one can assume "red liquid" to be alcohol, lol.
T_Pyro October 4th, 2003, 08:38 AM

At the end of the day, the question that must be asked is: "Why use alcohol at all for high temperatures?"
Mercury thermometers are perfect for high temperatures, and if you want more accuracy, you could always go for electronic thermometers, so why bother using alcohol at all?
Trinitrotoluene October 10th, 2003, 10:38 PM

If your trying to measure the temperature that's above the boiling point of mercury, then mercury thermometer is consitured useless. I perfer mercury thermometer over an
alcohol filled sprint thermometer, one reason mercury is more accerate, as mercury does not cling to the walls of the thermometer and alcohol does, making acceracy slightly
off.
senjoronie January 27th, 2004, 02:53 AM

Just found this thread and thought I would comment. I don't think the alcohol in an 'alcohol' thermometer is really ethanol. I broke one once by accident, and the liquid seemed
oily, more like a heavier alcohol or perhaps kerosene. That's what I thought they were filled with, kerosene or something like it.
Mumble January 28th, 2004, 12:53 AM

The liquid is some usually sort of glycol. Propylene Glycol is is probably the one in mine(-20 to 150). I'm sure there are other sorts of compounds that can be used, but glycols
are cheap and fit the purpose.

a n d I m provised C hemistry > C hlorinated aspirin
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Hystrix S e p t e m b e r 2 9th, 2003, 12:48 PM

Hi all. Yesterday I was trying to chlorinate the aspirin. Aspirin (3 tablets, cca 1.5 g ) was ground with the pestle and the mortar
and then it was added to approx. 30-3 5 m l of chlorine-containing bleach (I think this bleach contains at least 1 m ol/l of
hypochlorite). Alm ost im mediately this m ixture had darkened and started the gassing (it had resulted in covering the solution
with thick layer of foam ) . T h i s g a s h a d n o s m ell, I think it was CO 2. IMO this process follo ws this schem e:
1. Hydrolysis of aspirin to CH3COOH and salicylic acid ('cause bleach is strong alk aline);
2. Chlorination of salicylic acid ;
3. Elim i n a t i o n o f C O 2 .
T h e r e f o r e , I s u p p o s e m y p r o d uct contains a m ixture of chlorophenols and probab ly chloroquinones. What do you think abou t
this stuff?
zeocrash S e p t e m b e r 2 9th, 2003, 01:37 PM

h m m, bleach, is certainly a strong alkaline, but that is caused m y the NaO H in there to stabilise the NaClO
I M H O this would cause the asprin to hydrolise, but inste ad of forming salicylic acid, the Na+ ions would react with the salicylic
acid to form t h e s o d i u m salt of salisylic acid, sodium salicylate the metyl group would then hydrolise to form methane IIRC,
which would probably be that colourless odourless gas that is produced.
if sa licylic acid had been produced, it would have caused the hyp ochlorite to break down in to chlorine gas, but since the gas
p r o d u c e d h a d n o s m ell i'd say it wasn't chlorine
hypochlorite + acid ==> chlorine + salt + water

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > solubility of potassium
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dmitri October 12th, 2003, 08:27 AM

This thread was originally divided into three single ones. Merging them might have affected their order somewhat, so take that into account when reading.
Rhadon
++ ++++ +++ ++++ +++
Can somebody help me with advise?
I am going to use potassium perchlorate as an oxidizer which has to be introduced

in nanopores (typical size is 100-200 A) of porous silicon (fuel).
Since its surface is organofillic it assures complete filling of the pores by organic liquid.
The problem is that solubility of KClO4 in ordinary liquids like methanol or ethanol is extremely low,
while pore filling factor is crucial for explosive interaction. This binary system can be used as an efficient microexplosive. We have realized combination of porous silicon with
other solid oxidizers, it works very well
but all of them are hydrofillic.
Do you have any ideas about solubility of KClO4 in other organic liquids?
Or probably one can suggest another procedure (chemical, electrochemical)to fill the pores by KClO4?
Dmitri

I think this thread would be more suited to the Chemistry Related forum.
You have broken one of our golden rules by creating a new topic on your first post, however it is an interesting question and your application is unique.
Care to give us some background information on the application?
vulture October 12th, 2003, 11:51 AM

This seems to be quite interesting. Silicon has a very high burnenthalpy, in combination with KClO4 it should form an insanely hot pyrotechnic mixture.
How about solvents like DMSO or DMF? Acetic acid? Trifluoroacetic acid/anhydride? Trichloroacetic acid/anhydride? Or will the last 2 attack silicon?

A few comments concerning this system:
Porous silicon can be produced by electrochemical etching from ordinary bulk
silicon wafers. It consists from nanometer-sized silicon nanocrystals w hose surface is terminated by one monolayer of hydrogen or oxygen.
Total internal surface is 100-1000 m^2 per 1 cm^3 and almost each 4th Si atom lies on the surface.
Porosity is easily tuned from 10 to 90% and stoichiometric mixture w ith oxidizer can be achieved.
Another crucial difference w ith gun powder is that system is selfconfined: nanocrystals are mechanically interconnected and porous silicon (fuel) matrix is solid and stable. In
some sence system is similar to high chemical explosive: fuel atoms (silicon) and oxidizer molecules are in atomic contact along huge internal surface.
Therefore a chemical reaction (oxidation) proceeds in time scale of 100s of nanoseconds (measured).
System is highly explosive, energy gain we achieved so far (measured) is ~ 8 kJ/g and for optimized system can be as high as 10 kJ/g.
The interesting point that it can be exploded very efficiently in negligible amounts, say in micro- milligramm range. Therefore on one bulk Si wafer a big amount of single
explosive elements can be produced which can replace ordinary pyrotechnical elements used in industry, say airbag igniters.
According to my experience it works very efficiently already w ith few oxidizers but all of them are hydrophilic.
KClO4 probably can be the best one but its solubility in ordinary liquids is low .
Thank you for advise concerning solvents, I w ill try them.
Dmitri
vulture October 13th, 2003, 04:14 PM

Those energy outputs are normal for pyrotechnic mixtures, but for a HE it is indeed very high! :eek:
BTW, w ould you be on the same research group that had this "accident" w ith porous silicon, the very cold silicon that exploded w hen the protecting hydrogen layer was
disrupted by oxygen?
dmitri October 13th, 2003, 05:29 PM

Indeed I am leader of this group.
Energy yield is similar to ordinary pyrotechnics but this number is not crucial for explosive interaction.
Burning fuel gives more. As I mentioned above this system is mechanically self-confined in nanometer size range and no additional geometrical confinement like for gun powder
or other pyrotechnic mixtures is required.
Therefore pressure and temperature rise (and rate of further oxidation) is very fast.
Having some experience w ith this system I w ould not classify it as an ordinary pirotechnics. It is rather high microexplosive. You can look on our institute webpage: http://
w w w.e16.physik.tu-muenchen.de/. Look on NEW, there you can see explosion of only 6 milligramm of porous silicon. You can compare this explosion with ordinary
pyrotechnics.
Dmitri
rikkitikkitavi October 14th, 2003, 03:16 PM

A solvent for KClO4 w ith fairly high solubility I can not think of. Since the pores are extremely small it is impossible to create a suspension of fine (nm sized) KClO4 crystals and
let these attach themselfes. The crystals probably also need to grow on the Si-surface for adherence?
However , have you considered NaClO4 or NH4ClO4?
/rickard
zeocrash October 14th, 2003, 04:17 PM

would an alcohol solution w ork. the chlorate w ould disolve in the water, that would mix w ith the alcohol, then the alcohol would be absorbed into the silicon.
i'm probably talking out of my ass but it's worth a shot
also how about using an oil, water detergent mix as a solvent same principle again, the silicon attracts the organic molecule, that in turn attracts the detergent molecule that in
tern attracts the chlorate solution
Crazy Swede October 17th, 2003, 02:27 PM

I'm quite convinced that ethanol will not work! It might be so that the solubility is higher in methanol, especially if heated. But, I guess you will never reach an efficient
concentration of the oxidizer.
My advice is to check out supercritical fluids since they are known to have great solving powers. Maybe supercritical carbon dioxide w ould work?
Good luck, and please inform us of any success! :)
Snipie October 18th, 2003, 05:01 AM

Maybe you can form the KClO4 inside the porous silicon, by fractional crystallisation.
NaClO4 + KNO3 are both very soluble.
First you add the (hot) NaClO4 solution to the porous silicon, and after that you add the (hot) KNO3 solution, and then you cool it.

Thanks a lot for advises. I am almost sure that ordinary solvents will not work, solubility of KClO4 is too low. Fractional crystallization and supercritical fluids, especially
supercritical carbon dioxide sound very promising. Within one month w e are going to try supercritical drying procedure with CO2, this idea also came to our mind. Unfortunately
the price of the supercritical drying machine is quite high (40K) but probably this is only the way. Do you know any data on solubility of salts, especially KClO4 in liquid CO2? I
can not find references. Another problem is that it is not clear whether KClO4 will stay in the pores. According to our experience only a few salts can be fixed in the pores, most
of them slowly migrate to the surface of porous silicon layer.
Dmitri
Haggis October 19th, 2003, 03:10 PM

This did not require a new topic. You should have just made a reply to your existing topic on this subject. Do this in the future.
DBSP October 19th, 2003, 05:11 PM

Locking this thread, dmitri this could have been posted in the already existing topic...
If any senior mod could merge this thread with the existing one on the subject it would be good.
Or should it simply be deleted?? up to you to decide.

Anhydrous lithium perchlorate is very soluable in Acetone, slightly less in Ether and slightly less in Ethyl Acetate. Roughly of the order 1 part salt by mass dissolves in 1 part
solvent.
You could either try these solvents, or lithium perchlorate itself, which would probably perform very well as an oxidiser.
I'm interested in nanosilicon, what are the conditions to electrolytically etch the wafers?
Current density, makeup of the eletrolyte?
Have you thought about using a convection type crystal growing method to grow a single crystal of oxidising salt around and through the nanosilicon wafer? It w ould be
interesting to see the results. How are you applying the salts currently, are there voids in the material?
If the reaction takes place within 100ns, does that mean the material is supporting a detonation w ave?
Crazy Swede October 20th, 2003, 08:47 AM

Dmitri wrote:
-------------------------------------------
Thanks a lot for advises. I am almost sure that ordinary solvents will not work, solubility of KClO4 is too low. Fractional crystallization and supercritical fluids, especially
supercritical carbon dioxide sound very promising. Within one month w e are going to try supercritical drying procedure with CO2, this idea also came to our mind. Unfortunately
the price of the supercritical drying machine is quite high (40K) but probably this is only the way. Do you know any data on solubility of salts, especially KClO4 in liquid CO2? I
can not find references. Another problem is that it is not clear whether KClO4 will stay in the pores. According to our experience only a few salts can be fixed in the pores, most
of them slowly migrate to the surface of porous silicon layer.
Dmitri
-------------------------------------------
I'm sorry, I have no data for the solubillity of potassium perchlorate in supercritical carbon dioxide. But, there must be sources at any modern university or technical library!
dmitri October 20th, 2003, 01:11 PM

Unfortunately lithium perchlorate according to our experience does not stay in the pores for a long time and
is hydroscopic.
Micro-(2-5 nm size of silicon nanocrystals) or meso-PS layers (10-20 nm) can be prepared from boron doped Si substrates, with a typical resistivity of 1-10 Ohm cm and 1-10
mOhm cm respectivily. The electrochemical etching is done in a Teflon cell containing ethanoic hydrofluoric solution, with a Pt wire as a cathode. The etching solution is a 1:1 by
volume mixture of hydrofluoric acid (49 wt.% in w ater) and ethanol. The etch current density is 30-100 mA/cm^2. The anodization time can be tuned from a few tens of
seconds up to a few hours in order to obtain different layer thicknesses ranging from 1~micrometer to 500 micrometer.
Concerning supporting a detonation wave: geometrical configuration of this explosive is rather unusual.
It can be considered as two-dimensional system: thickness of the layer (say 100 micrometers) is much smaller than lateral sizes (centimeters).
Therefore ordinary detonation wave propagation concept should be reconsidered. Under local ignition of stripe (say by laser pulse) the lateral velocity of reaction propagation is
at least 2 km/s. What it will be in ordinary bulk conditions(say cube or sphere configuration)I can not say, to my opinion it should be much faster.

dude, you should use the new reply button, not the new thread button to post your replies. it angers the mods when you keep creating new topics. anyway, i took the liberty of
pasiting what you had to say into the current thread

since he seems to keep posting his replies as seperate topics, :S i thought i'd relay his w ords to you all in the main thread
Originally posted by dmitri
Unfortunately lithium perchlorate according to our experience does not stay in the pores for a long time and
is hydroscopic.
Micro-(2-5 nm size of silicon nanocrystals) or meso-PS layers (10-20 nm) can be prepared from boron doped Si substrates, with a typical resistivity of 1-10 Ohm cm and 1-10
mOhm cm respectivily. The electrochemical etching is done in a Teflon cell containing ethanoic hydrofluoric solution, with a Pt wire as a cathode. The etching solution is a 1:1 by
volume mixture of hydrofluoric acid (49 wt.% in w ater) and ethanol. The etch current density is 30-100 mA/cm^2. The anodization time can be tuned from a few tens of
seconds up to a few hours in order to obtain different layer thicknesses ranging from 1~micrometer to 500 micrometer.
Concerning supporting a detonation wave: geometrical configuration of this explosive is rather unusual.
It can be considered as two-dimensional system: thickness of the layer (say 100 micrometers) is much smaller than lateral sizes (centimeters).
Therefore ordinary detonation wave propagation concept should be reconsidered. Under local ignition of stripe (say by laser pulse) the lateral velocity of reaction propagation is
at least 2 km/s. What it will be in ordinary bulk conditions(say cube or sphere configuration)I can not say, to my opinion it should be much faster.
Rhadon October 20th, 2003, 02:38 PM

Dmitri, please be so kind and put your replies into existing topics using the New Reply button (not New Thread!). This saves us a lot of w ork and confusion.
dmitri October 21st, 2003, 05:05 AM

Sorry,
it was my mistake, in future I will use NEW REPLY option.
Dmitri:(
Chade October 21st, 2003, 06:06 PM

And here I thought solid state physics would never yield anything fun. I w as just reading the 'sister' thread 'superpow erful explosive' and from w hat Dmiti is saying, I really have
to start to wonder. Megalomanias big list of explosives and weapons patents includes a patent relating directly to this that has a very interesting idea. US 2003148569 A1, and
I'm guessing Dmitri knows about that, as I strongly suspect it's his patent. (does that mean we have to bung him a few quid if w e w ant to try it?)
The porous silicon mixed w ith oxidiser is used as a primary explosive, but can still be integrated on a regular semiconductor chip. Any chip w hich needs extreme protection
against copying can include the ultimate self destruct mechanism.
What I started to wonder about is, how far along could a dedicated home experimenter get with the manufacture of this stuff? I think it'd be fascinating if you could create your
ow n sample, how ever poor, of such a new explosive. Cutting edge technology. (I might not be saving up for one of those 40K supercritical fluid machines though.)
I know you can make polysilicon* at home from glass if you can get hydroflouric acid, and I think you could simply etch that to form the porous silicon, rather than worry about
the extremely difficult step of forming a silicon crystal. I don't imagine proper researchers would use polysilicon, as the crystalline defects would just make the results less
predictable, as far as investigating this new explosive goes, especially if silicon crystals could be bought from industry. The HF could then also be used for the etching, as
described.
Then it's a matter of applying the oxidiser as described in both this thread and the patent. The more I think about it, the more possible it seems to be. The alternate method in
the patent of starting from colloidal silicon also seems possible in a home lab.
* polysilicon: lump of silicon with no regular structure over any significant distance. Polycrystalline silicon.
vulture October 22nd, 2003, 01:46 PM
I know you can make polysilicon* at home from glass if you can get hydroflouric acid, and I think you could simply etch that to form the porous silicon,
You're not going to get silicon when etching glass with HF:
SiO2 + 4HF ----> SiF4 + 2H2O
You w ould then have to reduce the SiF4 with a reactive metal like magnesium. However, this requires severe heating under inert atmosphere and SiF4 is a toxic gas, so you'll
get serious problems from pressure buildup.
Chade October 22nd, 2003, 06:26 PM

I'm sorry, that was my fault for being vague. I should have phrased it as follows: I know a method for getting elemental silicon in a home lab, and the most difficult aspect to
this method is acquiring hydroflouric acid. That's why I said you could do it if you could get hydroflouric acid, but looking at it, my method also requires elemental sodium, w hich
is also hard to get.
Actually, I'm not sure if it's ever been discussed here before, despite the fact that elemental silicon does burn fairly w ell as a pow der.
OK, I'll give the full method I have here.
Hydroflouric acid, to start w ith, can be made from flourspar (a common mineral, and I've mentioned it in another thread) mixed with sulphuric acid and heated using appropriate
containers. HF gas is then passed into water to make a saturated solution.
HF can then, as described by vulture, make SiF4. In a resistant container (described in the hydroflouric acid synthesis thread) of the same type as used to make the HF solution,
you add the acid and a ground silicate powder. Sand is ideal, but any silicate works. You can grind down glass, or even quartz or flint. To grind dow n something like flint, heat it
to a white heat in a furnace, then throw it in a bucket of w ater to shatter it. Then use an iron mortar & pestle to pow der it.
The HF/SiO2 mix forms SiF4 as vulture says in a gaseous form. This is in the body of the still used earlier for HF formation. It is placed w here the H2SO4/flourspar mix was, and
the SiF4 fumes bubble through the water. This gives:
3(SiF4) + 2(H2O) -> SiO2 + 2(H2SiF6)
Ideally, you should bubble it through a thin layer of mercury into the water to stop the tube being clogged with forming silica, but it's not vital.
A white precipitate forms, which can then be heated to form pure silica. This is the SiO2 bonding to water. Not sure of the exact details of this, but the w ater is driven off by
heating.
Anyway, we're not interested in the pure silica, although you could use it and start the process again to ensure a very pure sample of silicon. What w e're interested in is the
H2SiF6 solution, which we seperate from the precipitate. Then add Potassium Nitrate (Hmmm, where could I get that I w onder...) and observe the solution very closely. After a
time, a near transparent precipitate is formed. It is this that we filter off, and now appears as a very white powder. My reference* doesn't give a formula for this compound, but
I think it should be K2SiF6, with the potassium directly substituting the Hydrogen.
Then this white powder is mixed w ith the sodium, cut into small pieces, and heated in a covered crucible at high tempreature for around an hour**. You will end up with a
brown powder, insoluble in water. This is Silicon. You can burn it already in air, and even better in pure oxygen, to again form pure silica as a w hite powder.
To make polysilicon, heat the silicon in a covered crucible with Zinc at a high enough temperature to melt the zinc but not boil it for, again, an hour. This is then covered with
Hydrochloric acid w hich removes the zinc, but leaves the iron grey silicon crystals behind.
Like I said, not the easiest method for the amateur.

I think it should be possible to use any salt of a substance with a higher reactivity than hydrogen to precipitate the H2SiF6. I'm also keeping my fingers crossed that Magnesium
powder might work instead of sodium to produce the elemental Si. I can get magnesium from firelighters. At an extortionate price, mind you, but if I can produce my own
silicon, it'd be worth it for that alone. Lithium would be more likely to work, but is even pricier.
Once you have your own silicon crystals, you can try Dmitri's amazing exploding silicon. Or perhaps you could take the Si powder and try to make it as small as possible and
approach it that w ay? It may even be easier. Can ball milling get pow ders down to colloidal (nanoscale) sizes?
Also, no-one thinks of explosives w hen they think of silicon, so if you say you're approaching it to study the electronic properties of Silicon, you will find it much easier to get
hold of the neccesary chemicals.
* As I said in the other thread, my reference here is a turn of the century (C19) book called 'Science for all'. I'm working on scanning the useful articles, but I've got a lot on at
the moment. When they're done, I'll host them on some free website for y'all.
** Unfortunately, no detail is given for the temperature required for this step. I'm guessing it would suffice to leave it above a bunsen burner or camping gas stove on full for an
hour.
Crazy Swede October 23rd, 2003, 10:51 AM

Chade, wouldn't the use of magnesium metal, instead of metallic sodium, produce magnesium silicide?
Chade October 23rd, 2003, 02:54 PM

Crazy Swede: Quite possibly. My chemistry knowledge isn't that great. I suppose I should try to predict w hether it would work before just trying it, and wasting a lot of time,
effort and materials.
Bit of a shame if group II metals don't work, as I've got some Calcium as well.
[Edit: Did some research and added follow ing]
It seems Mg2Si can form. As can Na4Si, but that doesn't happen w hen sodium is used, I presume as they use approximately stochiometric amounts. I think this is one of those
cases where the reduction of the compound occurs first, then, if there's any excess reactive metal, it will form a silicide. So I think magnesium should w ork. (You can't see, but
I'm crossing my fingers here)

Si pow der in combination w ith oxidizer will work like ordinary gun powder. I do not think that
ball milling would allow to get sizes significantly smaller that 1 micrometer. For this size internal area is about 1m^2/cm^3 while for porous silicon it is in the range of 100-1000
m^2/cm^3. Therefore for Si powder
burning rate w ill be very small, like for ordinary pyrotechnical powders.
Second important point is that as I wrote porous silicon is selfconfined sponge-like structure.
For powders additional geometrical confinement to increase burning rate due to rising pressure is required.

and Improvised Chemistry > alternatives to chloroform
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seth October 17th, 2003, 08:18 AM

hi all,
i spent a couple of hours browsing through various forums now, searching for info on sleeping gasses, and all i came up with
was clorophorm related stuff.
now when i was taking chemistry lessons i can remember i digged it up, and what i came up with was that it must be
administerd in extremley controlled amounts to avoid death, and also it takes at least a minute to be effective, plus having
an extremley detectable smell.
So i was wondeing if there is a more stealthy alternative, witch also acts faster.
I am not asking for ways of producing the alternative chemical, just names and opinions about it.
greets
Seth
grendel23 October 17th, 2003, 09:02 AM

Anything that is fast is also frequently fatal, read about the Russian's attempt to use a soporific gas last year, 129 dead.
Chade October 17th, 2003, 09:05 AM

My god, there's a fetish for everything. I searched Chloroform on the net, and came back with porn sites of women getting
chloroformed. Anyway, it does work, but isn't instant. It's very handy as it's so easy to make. Even if you don't plan to use
that, there's little reason no to have a go at making it anyway, just to give you an idea of working with a soporific substance
like that.
True, if you fall unconcious in a room with the gas, then carry on breathing it in, you'll die, but a napkin full of it over the
mouth and nose for about a minute will put someone out, according to descriptions on this forum. The film Suicide Kings has a
classic scence where they attempt to chloroform someone in a car, in a fairly realistic scenario. The guy shakes free, grabs the
wheel, and the jolt makes the guy drop the bottle of chloroform in the car. Not the easiest thing to use, but the easiest thing
to make.
Look here: http://en2.wikipedia.org/wiki/Chloroform
and then decide for sure that you really want to try making something else. After all, it was used as an anesthetic for years.
I notice you got the wrong spelling, which may be why your searching of the forum (which I'm sure you did) didn't get any hits.
Not that I'm criticising, I always want to spell it cloroform for some odd reason. Anyway, this'll give you 54 threads, and info on
other sleep agents. I'll be amazed if there's not loads on how to use them as well.
I always think the idea of chloroform in a bottle is a little clunky. Try to use it in a fight, and you look like Kryten from red
dwarf. 'I'm coming round behind you to take you by suprise now sir. You may experience a slight smell of chloroform.'
[edit: rather than type a new post]
Hell, I'm in no position to complain. I make five good mistakes before breakfast. Yes I get what you mean there. I found the
thread I was thinking of
http://www.roguesci.org/theforum/showthread.php?s=&threadid=1540&highlight=chloroform
I've not been able to find any threads discussing different types of knockout gases, or their effectiveness, besides that one,
which pointed out that holding someones face to a napkin of Chloroform is a world apart from throwing a gas canister into a
room they can run out of. Exposure times need to be VASTLY increased, and by difficult to predict amounts. So likely, that
would increase the difference required in lethal dose and effective dose to be much higher.
http://www.osha.gov/dts/osta/anestheticgases/anesthetic_gases.html
This page lists the medical anesthetics over the years, and looking for the effective doses and the lethal and toxic doses
should give a kicking off point. The synthesis of these is gonna be harder, and if there was a really effective knockout gas, I
think it'd be used more often.

hey ched, was a typo. i was just eating breakfast while writing, so forgive me :)
anyhow, i do remember the russian issue, and my rough guess is that they so totally got the wrong dose... but that of course
is just my opinion.
anyhow.. ok that whatever is breathed for longer time is lethal, but considering a relativley spacy environment, witch is
potentially ventilated, this risk should not be existing. Or?
well coming back to the main issue, the point is that i need something effective in less than 30 seconds, and with
chlorophorm.. wel.. that just is not realisic.
Consider that maximum exposure time will be approx. 1 minute after dozing off, and that oxygen may also be supplied to
victims immediatly in a 2 minute time range.
do you get what i mean?

i believe the problem with the russian situation arrised from the fact that they were using a medical anesthetic to gas a
building. and medical anesthetics are usually used with strict control on the supply, depending on the state of the patient,
rather than just turning the gas up to full and hoping for the best. i'm curious to know where they got such a large supply of
medical anesthetic at such short notice, but i guess they're the government, they can do anything.
i heard that a blast of ether in the face will knockyou out, or at least pacify you. but i dont know much about it
Anthony October 17th, 2003, 02:51 PM

As grendel pointed out, things that drop people very quickly also tends to kill them. There isn't really an effective, non-
dangerous "knock out" gas like you see in films.
What are you trying to do anyway?
Chade October 18th, 2003, 12:57 AM

Also, ether is still used as a recreational drug by certain people. (common term refers to diethyl ether) Try to knock out a
druggy, and there's always a chance he'll just start laughing in your face. There's been at least one case of someone who's
drunk a full pint of ether daily. If you're trrying to incapacitate a drug user (not that unlikely a scenario) You'll haveto account
for their increased tolerances to certain substances.
By way of analogy, imagine trying to put a drug in a pot of food to intoxicate (but not kill) a dinner party. You don't know the
toleranes of anyone there, how much they'll eat, or if they'll have an adverse reaction. Just 'cause you're putting the drug in
the air, doesn't make dosege any simpler (in some ways it's more complicated.)
Remember, even in hospitals, sometimes people just die going into surgery, before the doctor even lifts a scalpel, as they
have a bad reaction to the anesthetic. Not too common, but not that rare either. And that's with them varying the doses
according to age, desired effect, weight, and other narcotics the person has taken. You'd have to go around the room doing a
survey to find out this stuff about your target group, and god forbid there be a baby or a child in there.
I've heard the Russian theatre attack used Fentanyl, a medical anesthetic, but obviously the government won't admit or deny
this. They got the dose wrong, but my question would be, is it actually possible to get the dose right? I'd imagine even an
anesthetist trying to knock out twenty people at once would have a hell of a job on.
The russian siege had a fatality rate of over a huindred out of over 700 people. that's a 1 in 7 fatality rate. Maybe you could
get a better figure than that with more controlled circumstances, but you're still talking about losing a few people.
Do you actually need to knock them out? Perhaps some drug that has them rolling around on the floor, or just very stoned
and giggly would work?

wel.
thaks for the massive interest :)
well the idea is to take out a party of no more than 3, no children, and possibly drug use in the targets.
For anyone wondering what i wanted to do.... its very simple: my softair team is bored of using flashbangs to temporarley
(how do you spell that) take out enemies, and we wanted to take a different approach to stelthy penetration of the objective
structures.
Also, its not an absolute requirement that the targets lie in a comatose state on the ground, its just necessary that they are
unable to react (that can involve lying on the ground rolling for laugh gas or something that heavily stones them).
I hope you understand why i want to avoid anything fatal... such as overdose...
well...
what could an effective solution be?

You want to risk peoples' lives for the sake of a airsoft game?!
When we're talking about "knock-out" anything, we're imagining scenarios such as kidnappings, where death is a major
concern despite the fact that a serious prison stretch for kidnapping is already a cert if caught.
General anesthetics (particularly powerful ones like you're requesting) are not trivial toys, you will be putting the lives of others
at risk and you're own personal freedom, for the sake of something so stupid.
As has been said, even professional anesthetists sometimes stuff up, and for that reason general anesthetic is avoided
unless necessary. These people know what they are doing and have experience and they won't do it uncessarily, so why do
you think it's safe for you to do it for shits and giggles?
Seriously, your attitude towards this serious subject matter puts your maturity and trustworthyness with potentially lethal
materials into serious question.
Hang-Man October 18th, 2003, 10:13 AM

my softair team is bored of using flashbangs
on that topic- your using flashbangs in airsoft games? you must be damn good at making them if you feel you can thow them
into a room of people and not find them with blood running out their ears when you come in.
seth October 18th, 2003, 06:24 PM

erm...
ok..
just to clear things up..
1) flashbangs == magnesium powder fired up by the explosion of a small firecracker. pretty harmless, if not used in a too
stupid way.
2) real scenario is of course not wargaming, but my teammates were interested in this idea, so if something useful comes out
of it, it'll be used if possible.
Chade October 18th, 2003, 11:35 PM

I've never used drugs myself, but how about a handful of shredded marajuana leaves on a flashbang? There's something with
no recorded fatalities that could, to some degree, sedate them, but it might not make them all that inclined to get out of their
bunker. I leave it to someone who has more dope experience than me to comment.
It'd certainly make the games more fun though...
[edit: Oh well, nice try. Thanks ALENGOSVIG1.]
ALENGOSVIG1 October 19th, 2003, 12:00 AM

Haha theres no way thats going to work. First of all, you don't even smoke the leaves, but rather the flowers or buds of the
plant.
All it's going to do is spread particles of pot everywhere, or burn it; in which case the smoke would be contaminated with
smoke from the FB. It'd be so harsh i doubt they could inhale it if they wanted to.
Also the cloud of smoke wouldnt be around long enough for them to inhale enough THC for any effects to take place.
Oh yeah, and high temperatures (like that from exploding flash powder) destroy THC. And even if it did work, You would have
to wait a few minutes for the effects of the drug to be felt and theres no way that they're going to be so impared that they are
unable to play.
Unless there a serous lightweights anyhow. :D
zeocrash October 19th, 2003, 07:36 AM

yeah weed isn't powerful enough to be incapacitaiong in the way you mentioned. LSD on the other hand would fuck them. but
do you really want to risk permenant damage, a to their minds and b to you if they have a bad trip believe they really are in
battle and decide to murder you or something.
the flash bang and weed idea would probably work better when used with a large sack of snack food, as a munchies bomb.
seriously i wouldn't use real anesthetics in airsoft, why not just agree some rules with the other team for mock ansethetics.
they dont really need to be incapacitated.
edit: does anyone know about heroin fumes, they would probably be more effective in a grenade, i know my mate once had to
share a bus shelter with 2 guys who were chasing the dragon, the fumes wafted over him and he came into college totally
mashed.
Anath October 19th, 2003, 09:03 AM

Well, this thread is really silly, but.. Here's some ideas for non-lethal, not likely to get you put in jail or hospital, airsoft /
paintball "B0mbz".
Try getting one of those compressed-air "honkers" they sell at the footy, or sports shops. cut a bicycle tube into 1" wide
'ranger strips' or fat rubber bands, put the rubber band lengthwise on the can (over the horn). When you come up the
structure full of opponents, slide the rubber band over the Honkers push button to hold it on, and toss it into the structure, the
LOUD noise will distract and disorient them.
Black Cat fireworks sell cheap 'flashers' (magnesium strobe fireworks) that may blind someone with sensitive eyes on a dark
night. They would perhaps serve to distract your opponents while you take them out, or you could mould a few together for
more effect.
fill a plastic bag up with 'baby powder' or similar, maybe some pepper too. put in a large maroon. ignite fuse and toss into the
'fort'.
These should servge your purpose without any risks. leave the serious chemicals until you -really- need them. I guarantee if
you start throwing incapacitants like Chloroform, LSD, Heroin fumes or more serious things like Chloropicrin or Acrolein around,
you'll be getting shot at with something a little more dangerous than airsoft guns!
FragmentedSanity October 19th, 2003, 09:50 PM

Lo all :)
I find this an interesting idea, provided everyone in the game is aware of the dangers and obvious precautions are taken. I
could be wrong, because im an Australian and Airsoft is just too dangerous for us to own :mad: but isnt the idea something
like a training simulation. **rehashing something NBK said in an old thread somewhere** to really know how to go about
knocking someone out with chloroform you need to know how it feels - on both sides of the equation, ie how it feels when you
get anethestised and how much someone can struggle before they go under. The important part is knowing how much is too
much and stopping before you reach that point. But this isnt just something you can read on a website - I mean research is
vital - but its the hands on that really lodges the knowledge away in the brain for later use.
Still - chlorofor wouldnt be my choice for a simulation, as Im almost certain (never tried it on myself) that it results in a nasty
"hangover". But if the intent really is a training sim or such then thats the price you pay to learn I guess.
Seeing as Seth said that total incapacitation wasnt necessary you could only make them breath enough to go a little fuzzy -
then the player would become "unconcious" therefore out of the game / unable to shoot or move or whatever.
One substance that comes to mind in this vein is Amyl Nitrate - used as a heart medication, I remember it being big in some
gay/club circles - called names like stud - or rush, as it supposedly intensified orgasm if you inhaled at the right time
:rolleyes: Anyway - the one time SWIM experienced it - hold little bottle of solvent to nostril, inhale deeply - SWIM found it to
be fairly disorienting - SWIMS head felt too big and kind of floaty...Southpark fans just think of the drugs are bad episode with
the counciller tripping. The plus side was that it peaked at about 15 to 20 seconds and after 1 minute all was normal.
Of course this carries the similar risks to other solvents - I remember reports of youg people on Amyl having heart attacks.
But if your generally healthy - no heart conditions - blood pressure and such it should be relativly harmless - I know people
who could breath this stuff like air.
You could try nitrous oxide - it would have to be administeresd through some kind of mask - like a nebuliser. Is also very fast
acting and fairly safe - mix in like 1 quater oxygen and you can stay on it as long as you want .
As for the russian hostage gassing - the results were still less than if the bomb went off - and the majorityof people who died
were elderly or just unwell to begin with. Opiates effect everybody slightly differrently - maybe some of the deceased ate a
grapefruit for breakfast or some prescription medicin that potentiates the opiate gas.
Now to the suggestion of using weed - it would probably work, the only problem is you could probably retire on he net worth.
You CAN smooke the leaves just the same as Buds, but the desired product is strictly the little crysals that stick to the outside
of the plant.
So for incapacitation - you'd need to find the heavies couch lock indica you vsn lsy your houde on - extract it to oil then
vaporise that - in a cinfined sapce theoretically the target should be rushing bigtime.
not - ive been awake for more than 60 hours - sorry for any typo's
ALENGOSVIG1 October 19th, 2003, 09:59 PM

Smoking pot leaves? Eeeeew!

my primary concern is to get a group of peolpe impossible to react to a threat situation, and for those who still havent
understood it its not an airsoft scenario.
A "weed bomb" is simply unefficient both for the reasons explained by someone else (cant remember the name right now)
and both because the effect (it it WOULD work) is not sufficiently powerful.
Consider the scenario as a situatiion of real threat to your personal security, witch involves being stopped by the opponent to a
situation whitch can lead to serious personal injury, so a knock-out similar situation is required.
I assume that a substance that produces an orgasm similar experiance will possibly create high blood pressure, having more
celebral/fisical activity potential as a consequence, so not defeating the target in a semi-permanent way.
VX October 20th, 2003, 11:12 AM

GHB, the date rape drug, could be very useful. Lets face it, this is what it is used for! Although it isn't that fast working, the
advantage is that you can give it to someone, and they wont know that they have had it and so won't have any reason to be
alarmed, untill at some point, for no apparent reason they don't have a clue who they are :D

yeah i heard about that drug, and actually was interested in it when i was in london this new years for .. well.. you figure out
what. too bad i didnt find any in the stables market area.
anyhow my idea was more in the form of the "chloroform bomb" in some other section of this forum, so some volatile
chemical is more the case against this, witch has to be ingested.

i believe amyl nitrates, or poppers as they are known over here are prefered in gay clubs because they relax your sphincter
muscles (asshole).
infact one of the side effects of giving up my poppers habit was terrible constipation :( eew
still poppers have some nasty side effects and can kill anemics. also they sometimes give the user a splitting headache, wich i
dont imagine they would be too pleased about after the game
edit: just to clarify, i did not use poppers for the purpose of widening my asshole, that was an unwanted side effect
FragmentedSanity October 21st, 2003, 03:23 AM

Lo again - I just woke up and looked at the last bit of that post - eeek, anyway it wont let me edit it anymore so ill give you all
the jist of what my sleep deprived brain was tring to type.
A weed bomb IMO would be possible - and effective, but if you sold the weed you used to make it instead you could prolly buy
a small island or such - but if you were a Government that wouldnt be a problem and the results would be better than killing 1
in 7 people. So for the purely theoretical here is the idea. Now we know that the plant matter in the weed to fairly worthless -
its the crystals that stick to the outside of the plant that gets you high. These crystals can be extracted fiarly easily into a
super potent oil. Now if a quantity of this was instantly vaporised within a confined space everyone in that space is going to be
jello for the a while.
There is a bunch of different strains of MJ that all act slightly differently - for incapacitation cannibus indica, well matured,
would be preferable - as its more prone to giving the user "couch lock" as opposed to an immature stavia variety, which has
more "trippy" cerebral effects.
For those that still doubt the ability to incapacitate heres a lesser known fact about weed - its not actually a depressant - but is
rather a hallucinagen, which is why some forms of injestion seem to work differently for the same amount of material - its the
speed/quantity that you absorb it that determins effects. So if the room is full of super potent oil vapours then anyone in the
room will be looking for the handlebars on the floor so they dont fall off. Sort of like the ultimate compression session :p
Oh - About the amyl-asshole effects thats new to me - but I only tried it once, I used to know a few people who could have
told me more im sure :rolleyes: - lets just say this, gay guys are fun to party with - hardly ever any violence, lots of dancing
and music, but the best part is that strait girls are drawn to them like flies and feel totally safe - so they get blitzed, then by
the end of the night when the guys start leaving together, the girls get depressed... and can be very accomadating to any guy
that happens to take an interest in them :D
Anyway to go back on topic - if this is a threat to your person - whats wrong with a lump of pipe to the head? its probably got
about the same chance of you stuffing up and killing them as an anasthetic and is onlys slighty more prehistoric than
chloroform / chlorobutanol and the like. Unless of course your some kind of chemist and can whip up synthetic opiates at will -
and have the knowledge required to use them without killing the recipient. But if it is really a threat situation, and your not just
throwing out hypotheticals to justify your asking, Id say go for a rapid addition of lead to the cranium.
nbk2000 October 27th, 2003, 05:09 PM

A dilute solution of hydrazoic acid, explosively dispersed, would cause their blood pressure to drop so low that they'd pass out.
'Course, nasty side effects like death could occur, so it's not for silly games, but for serious matters.
Remember that anything capable fo causing unconciousness can also result in death, so the term "non-lethal" is inaccurate,
while "less-lethal" (than bullets and frags) is more appropriate.
Knocking someone upside the noggin with a pipe means skull fractures, brain swelling, and death. Not a less-lethal approach
at all.
FragmentedSanity October 28th, 2003, 08:18 AM

hehe - I know a pipe to the head is hardly LTL, my piont was that its roughly compareable to an inexperienced person trying
to make and then administer archaic anesthetics.
I may have been a little blunt about it, but i was a tad annoyed by the scenario change - going from a game with friends to a
direct threat totally changed the situation. Im of the opinion that a "... real threat to your personal security...(that) can lead to
serious personal injury..." deserves a direct response, like a shot in the head, bullet or pipe or whatever you fancy. I see very
little point using an anesethetic to knock them out, unless you plan on "playing" with the victim while they are out.
Consider for a moment getting caught - if you made and used some "knockout drops" on someone you would end up with a
huge list of charges against you - assult, endangering life, - anything they can think of + drug charges. Being post 9/11 you
might even end up with manufacturing / using chemical weapons or some such rubbish.
Or you bang someone on the head because they threatened you - you still get charged but it wouldnt be as serious, most
likley only a single charge - Assult with a deadly weapon - or casuing GBH or similar - without the drug charges.
LTL combat options make an interesting topic, as would the airsoft scenario - but IMO asking for one when you want the other
just results in the thread being filled with responses that arent applicable and wastes peoples time.
seth October 28th, 2003, 02:41 PM

Hi all, sorry for the late replys but i had no net access for some time.
Thanks to NBK2000 and fragmentedsanity for the comments....
Now i found out that NaN(3) is very interesting.. this is what i found:
"
Acute inhalation by humans of hydrazoic acid vapor (which forms when sodium azide contacts water) results in lowered blood
pressure, eye irritation, bronchitis, headache, weakness, and collapse (Fairhall et al. 1943/Ex. 1-130; Graham 1949/Ex. 1-
109). The exposure levels that produce these effects were not reported by these authors.
"
Also:
"
Haas and Marsh (1970/Ex. 1-121) reported that exposure to concentrations of hydrazoic acid vapor as low as 0.5 ppm
"cause[d] some discomfort to laboratory personnel."
"
now i would define "discomfort" as the early symptoms of the basic intoxication, and probably it is nothing more than
breathing problems and eye irritation. Headaches should not be present because the dose is not high enough to lower the
blood pressure. Of course this is just my opinion.
So the question is: what is an effective dose?
Consider this:
"An intravenous dose of 1 mg/kg was reported to lower blood pressure in cats (Graham 1949/Ex. 1-109). "
now a cat is average 4 kg, and an average human is 70.

70/4=~20 , so we have that a 20mg dose (intravenous) is more than enough for humans.
Now there must be a ratio or similar to convert that amount into a vaporous ppm amount, so if you have clues about it, drop a
note.
rancid_matt February 7th, 2004, 07:53 AM

If you want to know something about sleeping inducers (shit like barbiturates), just have a look at rhodium's page.
www.rhodium.ws there's even a section about synthesising chloroform.
zeocrash February 10th, 2004, 01:19 PM

yeah we know about rhodium's page and we know about chloroform synthesis. this thread is more to do with the aplication of
these substances rather than the production though
streety February 10th, 2004, 04:11 PM

I don't think you can easily convert an intravenous dose into a ppm dose. Your drug would need to cross membranes where it
could be metabolised out f existance. There is also the problem of it taking more time to be effective if inhlaed as opposed to
injected.
I read a while ago that a large dose of DMSO applied to the skin will cause unconsciousness with a very wide margin for error
in terms of causing death. The source I read this in is not very reliable and I have been unable to find any other references to
this use so it is probably incorrect. However DMSO does excellerate the movement of drugs across the skin so it may be a
faster, more effective way of causing unconsciousness than vaporising your drug in the air. The risk of contaminating yourself
whould also be reduced.
NightStalker February 11th, 2004, 04:43 AM

For a chemical with a molecular weight of 43, 1 ppm = .0018 mg/Liter OR 1mg/Liter = 556 ppm
mg/L = gm/Cubic Meter = ounce/1000 CFT
If we assume a lethal dose equal to HCN (very probable) of <20mg (absorbed), and a breathing rate of 8 liters of air per
minute (resting, likely much higher), and a concentration of 1 oz/1,000 CFT, then that'd put a lethal dose in the target in less
than 3 minutes, which would scale well with HCN toxicity of .3 oz/1,000 CFT/10 minutes (Prentiss).
Though, because of the rapid loss of conciousness and subsequent inability to flee the toxic atmosphere, you can assume it
to be one-breath lethal at that concentration, as they'd take a breath, immediately start hyperventilating as they become
disoriented and fall to the ground, there to die as they continue to breath in the poison, unable to escape it.
NIOSH exposure limit for an HN3 contaminated atmosphere is .11 ppm, for any length of time. Oh, and it's absorbed through
intact skin too, so you'd need a suit for working in toxic enviroments, otherwise you'll get zapped that way. :(
If .5ppm is "irritating", than 5ppm should be positively toxic, eh? That's about .02 oz/1,000 CFT.
If you had control of the enviromental controls for the target, you might be able to inject the HN3 in a massive doseage, then
immediately purge the atmosphere with fresh air. The intense initial concentration puts them out in a breath or two, with the
fresh air purging possibly preventing lethal intoxication.
However, regardless of the purging, you're still very likely to have some fatalities. This is unavoidable. Especially if there's any
old/sick/young people present.
The fentanyl series have been well studied and tested by a former superpower (russia) and when they used it in the
checkneyan (SP?) theater rescue, they still killed about 15% of the people present.
And some of them have lethal doses less than that of VX, for gods sake!
What hope does some schmuck cooking up toxic shit in his kitchen have of not stuffing it up BIG TIME and killing every
mutha-fucka' up in there? Not a whole hell of a lot, I think, whether it's chloroform, hydrogen azide, or fentanyl. :D
You'd be much better served to use an extremely debilitating arsenical chemical agents like adamsite or blue cross to reduce
them to puking and twitching, and with dosages far below what you'd need with chloroform or such, as well as having lethal
dosages far above (10,000+) that needed to have dramatic effects.
I recently found a US site that's selling 1oz bottles of arsenic pentoxide for $5, not including shipping, of course. There's less
than a dozen left. Any staffers interested in this, ask NBK for the source, as I've already e-mailed it to him and my e-mail isn't
working at the moment. Everybody else, don't even bother asking, as I am NOT sharing this source, Hive rules.
Silentnite February 4th, 2005, 03:10 AM

Hate to bring up an old thread but after some searching I still haven't found my answer and I don't want to start a new thread.
That being said:
I accidently/on purpose made a batch of Chlorform. Unfortunately I made ALOT of it. By using NBK's 2nd method, I came up
with about 50mL's the first time but most of it evaporated and I ended up almost passing out. Fun times. So I tried again.
The second time I filled 2/3 of a 2L bottle with Bleach, and then the rest with Acetone, put the cap on and threw it in the snow.
Damn near the entire bottle was full.
After experiencing its effects, I am still left with quite a bit and I was wondering if anyone knew of a safe way of disposing of it.
From what I understand it should evaporate quite readily if I pour it out. I just would like to make sure.
It's in a 2L pop bottle, and the weather is snowy.
Jacks Complete February 4th, 2005, 01:08 PM

The biggest problem with Chloroform is the vapour pressure! The stuff boils at a low temp, and so evaporates really, really
quickly.
I knocked myself out with it one time, you get the same awful headache that has been mentioned before - it is worse than
Nitro (same sort of duration of hangover), or poppers (far shorter hangover), but not as bad as zinc (I doubt anything is as
bad as Zinc! It lasted for 3 days) I took a good deep breath, another, then I screwed the top back on tight, and headed for
bed. I think it affects the memory a little, as I don't recall getting into bed, but I woke up in bed some four hours later, head
pounding. Total time, about 30-45 seconds, I reckon, from first breath in to reaching bed. This was 100% pure, chemical
supplier bought stuff. Note that this was at gone 4 in the morning, exhausted but not able to sleep. Woken by alarm at 8. How
long it would have kept me out for without being very tired, and actually sleeping, I canot tell.
Unless you could overpower your enemy/target completely for a full minute, I would suggest this would be a bad way to go.
Someone with a bit of training will throw you off in seconds, to the extent of not holding the rag properly. The other way to go
might be to throw a cup full over the target, as they could run, but would still fall down quite rapidly. A guy would be unlikely to
scream, and you have to take a deep breath first!
Might be better using the "ziplock garrotte" and then cutting it away with specially made pliers, carefully using the chloroform
to keep them out.
As for disposal, just pour it down the path, walking upwind. It will just disipate. The bleach will kill the grass, though!

a n d I m provised C hemistry > DNA chem istry
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View Full Version : DNA chemistry
brannon October 20th , 2003, 12:43 AM

Hello Everyone. Fascinating place you have here. I've been lurking but here is m y first post.
I f o u n d s o m e interesting subjective threads on DNA in earlier m essages but rather than continue those threads I'd like to
initiate a new one in this forum which may be a m ore appropriate forum than the others. Not sure.
How much DNA does a person leave in/on the clothing and boots they we ar? What m ay be the useful analytical life of such DNA
if sa id articles were buried in a sem i-arid location?
Thanks,
brannon
DBSP October 20th , 2 0 0 3 , 0 6 : 2 3 P M

Newbies are adviced not to post questions on their first posts, allthough not forbidden the post mu s t h a v e s o m ething a bit
m ore substantial than this lou sy question:rolleyes:
At that newbies are encouraged to post replies to existing topucs a while before p osting a new thre a d . Y o u d i d t h e e x a c t t h i n g
but backwards...since thats "good" but backwards theres yet another resason to get rid of you....it's no fun to ban p eople but if
we are to keep the good standard we have on the forum things like this m u s t b e d i s c o u r a g e d , e v e n t h o u g h s o m e g o o d p e o p l e
will be sacrificed along with the bad ones becau se of the crim e s t h e b a d o n e s c o m it.
If you have been lurking here since oct 1 then you should have been able to read the rules during that time, now you
obviously haven't, and you will therefore not be around much longer.
Gettin fucking tired of all these newbies, am a z e d h o w t h e y a l l s e e m t o m iss the rules, it's not that hard to read them a n d
u n d e r s t a n d t h e m . I can understand the difficulties english can cause when it's not once native language bu t if they can't
understand the rules then they can't understand whats dicussed inside the forum so I just don't get it...

and Improvised Chemistry > The theory of OTC tetrahydrofuran (THF) synthesis
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View Full Version : The theory of OTC tetrahydrofuran (THF) synthesis
megalomania October 22nd, 2003, 09:27 PM

Some months ago I desired to use THF as a solvent for a Grignard reaction in the preparation of benzene from para-
dichlorobenzene. Since then I have learned THF is not necessary, but I did begin a side journey in learning how this solvent
could be made from all OTC materials. THF is still a very valuable solvent useful in numerous chemical reactions of interest
to the improvisation al chemist. T his usefulness has also earned THF a spot on the DEA s list of watched chemicals, s o som e
may be wary of purchasing this chemical from reputable vendors.
THF is of interest to those who synthesize the drug GHB as its direct precursor 1,4-butanediol can be used to make
butyrolactone, the precursor for GHB. There is an excellent article on the Hive describing how THF can be distilled from OTC
pipe cement (for plastic PVC tubing). Some question as to the purity of this form of THF is still being debated, but for most
having an easy OTC source is nice. Unfortunately, this particular source is quite expensive for obtaining THF in any but small
q u a n tities. I think it average s out to som ething like $100 a liter wh en procure d in th is m anner. That s way to expensive for
the likes of me.
Making THF is easy enough once you have 1,4-butanediol, but getting that precursor is the tough part. I think they regulate
that as well since it is considered a GHB precursor. My first instinct was to try some sort of chain extending reaction to create a
butanol molecule. The tricky part is having the hydroxyl on either end of the butane chain. One method of extending a chain
is through the Grignard reaction of an epoxide. This epoxide, for example ethylene oxide, can be added to a halogen
containing molecule. The good part about this reaction is it turns the oxygen of the epoxide into an alcohol, and that is half
the work. Now all we have to do is make sure the halogen containing molecule is an alcohol itself. That molecule being
ethylene chlorohydrin. The ethylene chlorohydrin has an alcohol at one end and the ethylene oxide adds an alcohol to the
other.
The good news here is that one can make ethylene oxide from ethylene chlorohydrin, and one can make ethylene
chlorohydrin by electrolyzing a solution of ethyl alcohol and salt. The jury is still out on how much ethylene chlorohydrin can
feasibly be made via electrolysis as they usually require lengthy periods of time to return any useful yields. The bad news is
the hydroxyl hydrogen of ethylene chlorohydrin will interfere with a Grignard reaction. That means we need to append a
protecting group, and protecting groups tend to be a bit on the sophisticated side. One might as well just buy THF if you have
to resort to buying a protecting group for the reaction. I even researched how to make chlorotrimethylsilane, a protecting
group for hydroxyls, but that turned out to be a rather complex reaction, although doable.
Subsequently I have found a possible alternative method that closely resembles one of the earlier industrial methods of THF
preparation. This process satisfies the requirements of all OTC reagents and can potentially prepare large quantities of THF
rather cheaply. The process begins by reacting acetylene gas with a 50% solution of formaldehyde to make 2-butyne-1,4-diol.
This is a rather straightforward reaction that combines these two chemicals. Both are available OTC and do not require any
special equipment. Then comes the hard part. The second step is to hydrogenate the 2-butyne-1,4-diol to 1,4-butanediol.
Catalytic hydrogenation is a quite useful tool in chemistry, but is it as useful on an improvisational scale? I have been
studying quite a bit about catalytic hydrogenations lately and I believe it can be done.
The problem with a catalytic hydrogenation lies in our choice of catalyst and our ability to sustain tremendous pressured.
Industrially, or in a professional laboratory, they would use a special hydrogenation tank pressurized to 100-300 atmospheres
and use expensive platinum oxide catalysts. These would be the optimal choices for the complete hydrogenation of an
acetylene bond without hydrogenolysis (clevage) of the alcohols. On an improvised scale we lack the ability to pressurize a
container any more than a few atmospheres, and platinum is just to damn expensive.
There are ways around these problems as I shall discuss. First of all we don t have to use platinum. One excellent catalys t is
something called Raney nickel (W-6). Raney nickel has about a tenth of the reactivity of platinum, but it is about a
thousandth of the price. The trouble with Raney nickel is you have to make it by reacting a 1:1 alloy of nickel and aluminum
metal with sodium hydroxide. The prospect of making such an alloy seems a bit daunting to me. There is an alternative;
something called Urushibara nickel, which has a reactivity right on par with Raney nickel. This stuff is made by adding zinc or
aluminum metal to a solution of nickel chloride and digesting with acid or base. Acid digestion makes a version called U-Ni-A,
which is what we want because the hydrogenation of acetylinic bonds is promoted by the acid. With base you make U-Ni-B,
which has an inhibiting effect on our type of hydrogenation. The acid used is 18% acetic acid (you cannot substitute any other
acid like HCl or H2SO4, they have a poisoning effect on the catalyst).
I remember inquiring some months ago about the feasibility of acquiring nickel metal from nickels (US 5 cent coins). I think
you can react the nickels in HCl to make nickel chloride. If anyone has any information on this I would like to hear about it. I
have not looked into this lately. I am sure the Hive must have something because I remember reading about Urushibara
catalysts there. I am sure there are ways to e asily acquire nick el metal without the hassle of being put on The List. It s a
catalyst anyway, so you can recycle the stuff almost indefinitely once you have it.
Our biggest problem is the lack of our ability to produce high pressures in catalytic hydrogenation. The reason they use such
high pressures is to increase the rate of reaction. A reaction that takes 24 hours at 1-3 atm can take 5 minutes at 300 atm!
There are a few ways we can compensate for a lack of pressure. The first is time. Industrial people are always in a hurry
because time is money. They want to produce product as quick as they can, and if that means a little pressure, so be it. We
on the other hand have the luxury of time. Nobody likes the prospect of waiting around hours and hours for a reaction to go to
completion, but that is the price of improvisation. The second thing we can do is use more catalyst. Catalysts use is not linear;
double the amount of catalyst in a reaction and you can increase the rate by 4-5 times. Since we will be using cheap nickel
catalyst we can pile it on. It is recommended one use from 10-20% by mass the weight of catalyst vs. the weight of reactant
when using nickel catalysts. That means we need to use 200 g of nickel per 1 Kg of 2-butyne-1,4-diol. Using 400-600 g would
greatly increase the rate of reaction. A third thing we can do to increase the rate of hydrogenation is to scale up the reaction.
Maintaining the same ratio of catalyst to reactant, 1 Kg of reactant will hydrogenate faster than will 100 g. Scaling up the
reaction has a similar effect to increasing the ratio of catalyst. Many people may not want to run this reaction on a multi liter
scale, but it will give better results.
What about o ur choice o f hydrogenation container? I have h eard at the Hive such a thing as a win e bottle hydrogenato r
which is exactly what it sounds like, a wine bottle. Wine bottles offer large capacity, often 750-mL or more, and have a heavy
wall construction capable of withstanding several atmospheres of pressure. The downside of course is glass+pressure= trouble.
I would not want such a container exploding on me. These containers may be safer at lower temperatures, but we will have to
heat our reaction to increase the reaction rate, and that can weaken the glass. If I had to choose the best container I would
use a 20-L propane tank. These tanks offer many advantages including stainless steel construction designed for pressure
allowing safe operation up to a few dozen atm, large capacity allowing for a scaled up reaction, and ubiquity since the things
are everywhere.
I was resea rching Urushibara catalysts today in th e lib rary, and while rea ding Feiser s R e a g e n t s for Organic Synthe sis I just
happened to notice the next page was about hydroxyl protecting groups. Specifically it was about how one can use boric acid to
make a boron ester that is easily removed under mild acidic conditions. Imagine my happiness since boric acid is sold in just
about every drug store for some purpose that escapes me. I have a ton of the stuff. This puts the Grignard epoxidation route
back in business. I know the complexity of a Grignard reaction vs. a hydrogenation reaction is probably 6 of one and half a
dozen of the other for improvisational chemists.
All of this may be daunting to some and seem laughable to others, but bear with me I am just theorizing. My theory is backed
by hard fact though, and I believe this can be done. There are other issues to cover, like generating hydrogen and
pressurizing it for the hydrogenation rxn, producing magnesium metal for a Grignard reaction, getting nickel from OTC
sources, the exact conditions of the formaldehyde-acetylene rxn, practical and safe hydrogenator construction, and probably
many more issues that escape me at the moment.
I hope my introduction to OTC THF production may serve as a springboard for others to start their own investigations. I know
I will be con ducting further re search into this goal. I certainly don t like the fact the go vernm ent has closed the ta p on this
most useful of solvents and anything I can do to make impotent their misguided Gestapo tactics would be a great service to
our community.
John Ashcroft October 23rd, 2003, 11:07 AM

The synthesis involving acetylene seems promising, but the one involving Grignards seems too challenging for something so
simple as THF.
As for nickel from coins: http://www.sciencemadness.org/talk/viewthread.php?tid=534
Keep in mind that nickel oxide and nickel carbonate are sold by pottery suppliers: www.clayartcenter.com
frogfot October 23rd, 2003, 12:17 PM

IMO, protecting group on hydroxyl in ethylene chlorohydrin isn't neccessary, because Grignard part is more reactive than an
alcohol group. However, the addition of alcohol to epoxide would be probably catalysed by present water, which leads to a
problem.. how can an amateur experimenter find absolutely dry solvents?
Dunno about 300 atm, and such complex hyrdogenation, but I would first experiment with simpler things like formaldehyde
production since it seems to appear as precursor for many things.
Tuatara October 23rd, 2003, 05:42 PM

Nickel also is to be had from NiCd or NiMH batteries. Can't get better OTC than that!
FYI if pressurising a wine bottle, use a champagne bottle and check very carefully for chips and scratches. The normal
champagne process usually results in a pressure of around 4 atm inside the bottle - so I think this pressure could be safely
used for the hydrogenation, given the bottle should have been designed with a considerable saftey margin.
Milamber October 23rd, 2003, 06:48 PM

frogfot, the problem isn't that the alcohol would react with the epoxide, the problem is that the alcohol will readily react with
the grignard - an R-OH group reacts basically the same as H-OH, and we all know water stuffs things up (this is because
grignard's are very strong bases - they react with anything that can be acidic, like water or alcohols, quite readily. This is
because a grignard is a much stronger base than either of these types of compounds, easily taking the acidic hydrogen).
These bases can act as nucleophiles, and happily react with the grignard reagent, in this case to give ethanol... we dont need
that!
As fara as a wine bottle, perhaps you could wrap it with electrical tape to try and prevent flying glass in case of explosion -
might not be totally effective, but it should help. But I was thinking, what about using a pressure cooker as a reaction vessel?
You could sit a big beaker with your stuff in it in there, pressure it up... I'm just not sure what sort of pressures can they hold?
Certainly better than the bottle, and safer, too!!
frogfot October 24th, 2003, 10:02 AM

Forgot about that one.. This will be too much work then. How do one protecs -OH when there are reactive -CH2-Cl present. For
example, the cheapest protective group for an -OH I could find in Vogel is a ketone. But ketone will most likely react with -
CH2-Cl. :(
Also, is it possible that HO-CH2-CH2-Cl will polymerise in conditions used to place protective group?..
How is bottle catalyst used, shouldn't this be a continious process?

megalomania, I dont understand why you think the reduction would be anything other than first order with respect to catalyst.
Particually in the case of a hydrogenation I would expect reaction rate to be directly proportional to the surface area of the
nickel exposed.
On the subject of THF, a few thoughts occur. Furfural is reported to be prepaired by the dry distillation of sugar. Though if
sucrose will do isnt specifically said. It can also be prepaired by acid dehydration? of pentoses, which is what makes me wonder
about the exact meaning of the word 'sugar' in the older reference and by treating material with pentoses in with dilute acid
and distilling, somewhere I have a method for making it from bran. Removing the CHO aldehyde group in 1 or 2 steps gets
you furan, and reducing say with a dissolving metal gets you THF. I dont know the yield from bran but I suspect you'd need
sizable quantities, maybe even semiindustrial for a litre of THF at the end.
1 part bran is mixed with 1 part sulphuric acid in 3 parts water.

Mixture is distilled and the distillate saturated with sodium carbonate, then mixed with salt, and redistilled. On adding salt to
this distillate furfural seperates.
Suggested oxidising agent here is silver oxide, but I'm sure we can find something cheeper.
Orgsyn has a method for converting the acid into furan though its method for converting furan into THF is hardly applicable. It
does suggest that its been done with raney nickel at 50C in butyl alcohol.
On another tack, we know we can make it by dehydration of 1,4-butylene glycol which we cant make easily, but we can make
1,3-butylene glycol easily from acetaldehyde, so this makes me wonder if it could be persuaded to rearange in the vapour
phase dehydration to produce THF.
Ethylene chlorohydrin can be made easier than electrolysis by reacting ethene with hypochlorite though I dont have a specific
synthesis handy.
Tell us more about the borate ester protecting groups please, they sound useful.
Edit, ethylene chlorohydrin can also be made from ethylene glycol and hydrochloric acid.
Al Koholic October 25th, 2003, 04:58 AM

Chlorohydrin Synth from lets seeeee....Journal of American Chemical Society....
I have here a paper detailing the results of a bunch of experiments on diols...
Without further ado,
- A mixture of 20.3g of the glycol and 271cc of conc. hydrochloric acid (one molecule of the glycol to 9 of the acid) was heated
at its boiling point for 4.5 hours. The product was then fractionated with a Le Bel-Henninger tube. The fractions containing the
chlorohydrin and the glycol were neutralized and extracted with ether. The ethereal solutions were dried over anhydrous K2CO3
and distilled. Yield of chlorohydrin was 12%; bp 127.6-128.6; d=1.194. The glycol recovered weighed 10.5g. -
Bad yield, and to get ethylene glycol you will -most- likely have to distil from antifreeze. This sounds trivial but really isn't as it
boils at 760mm at 197 degrees and I believe forms an azeotrope with water (not totally sure about this). Either way, one can
definetly obtain the pure glycol but using water diluted stuff will lower yield of chlorohydrin even further. The glycol is also
verrrrrrrrrry hydroscopic. However, all my bitching aside....this is a cheeeeeeap source and worth the distiling.
Yes, furfural can be obtained by boiling cellulose in hydrochloric acid....orgsyn detailed a synth with corn husks or something...

I too would expect hydrogenation to proceed in a linear fashion with increasing amounts of catalyst, but I have half a dozen
books on hydrogenation sitting right next to me and they all mention the rate of reaction increases non-linearly with increasing
catalyst. None of these books give any explanation as to why this is, only that it is an experimentally determined fact of
hydrogenations.
I checked up on the procedure in Organic Synthesis for the production of furfural, and it is quite interesting. The starting
material is ground corn cobs. I cannot imagine something easier to get. The only other ingredients are sulfuric acid, sodium
hydroxide, and salt (this has the makings of a tasty dish). I am sure furfural could be hydrogenated easily, but how to remove
the aldehyde? As luck would have it I am planting corn next year.
Ahh there is an orgsyn procedure for preparing fura n that uses furfural as a starting mate rial, althou gh technically the
detailed procedure uses furancarboxylic acid. There is another orgsyn procedure that converts furfural into furancarboxylic acid
although half is also converted to furfuryl alcohol. Again this procedure requires only sulfuric acid and sodium hydroxide.
There are also several references to using oats as a starting material for all this furfuryl/furan stuff (with patents). I wonder
which material would be cheaper? One could go about collecting corn cobs from friends and family, although they would
probably think you were a bit off your nut. Corn on the cob is also somewhat of a season thing. A big tub of Quaker oats
could be purcha sed anytime of the year, and oats have the a dded be nefit o f alrea dy being gro und up to bits. I don t care to
imagine how one would go about grinding down a bunch of corn cobs. For those of us in the country there are farms aplenty
with corn just waiting to be taken. Actually some farmer may be nice enough to part with their corn cobs, I think the only
commercial value they have nowadays is as a fuel or compost.
I found the bit about using boric acid on page 29 of volume 3 of Fieser and Fieser Reagents for Organic Synthesis. The
information in the article is tantalizing thin on details, but promising all the same. And I quote:
Protection of hydroxyl groups. Although boric acid esters have been known for some time, these have not been used to any
extent for protection of hydroxyl groups. Fanta and Erman1 have found this means of protection useful, especially in a
synthesis of dihydro-b-santalol. The esters are prepared in quantitative yield by refluxing the alcohol with one third molar
equivalent of boric acid in benzene with constant removal of the water formed. They are readily hydrolyzed in an aqueous
medium, neutral, acidic, or basic, during workup.
1W.I. Fanta and W.F. Erman, Tetrahedron Letters, 4155 (1969)
It looks like the downside here is the ester is so unstable to water, which is produced in the formation of the ester, that not
much can be made unless you remove the water. I am not sure how this could be done since ethylene chlorohydrin is miscible
with water; how would you separate it? Maybe calcium oxide or anhydrous magnesium sulfate could be added to the mixture to
absorb the water? I suppose the presence of benzene (although I think toluene would work just as well) may be able to
separate the water. Then all one needs is an improvised Dean Stark trap.
There is a graphic that goes along with the boric acid ester; to sum up 1 molecule of boric acid can esterify 3 molecules of
alcohol, so 3ROH + H3BO3 = (RO)3B + 3H2O.
I have read about the glycol methods of making ethylene chlorohydrin, but the reason I suggest the electrochemical method
is becaus e I believe it to be the most economical. T he sta rting materia l is only ethanol and salt, and you don t get much
simpler than that. Of course in my experience electrochemical reactions give a rather small yield despite considerable lengths
of time. A reasonably high current source would be needed to drive this reaction to give good yields in a short amount of
time. I wonder if the improvised electric furnace setup with its salt water rectifier could do the trick? There is a document that
was on the FTP, and it s somewhere on the net a s well that is th e scan o f an old science book that describes making an
electric furnace from line current (sounds dangerous I know). You just yank a plug from an extension cord or something and
drop the two ends in salt water connected to lead anchors to regulate the current (by moving them closer or farther apart). I
know this sounds excee dingly dan gerous, but this bo ok was geared to school children (oh the good old days of 1950 s
science books).
Anyway, this is just one example of how an electrolysis of alcohol could be conducted to give large yields in a minimum
amount of time. I am sure the situation is far more complex than this. Such a large current load through water would cause it
to he at up real quick, extern al cooling may be needed, or one cou ld start with ice water. I don t kno w how safe it would be to
run this thing continuously because I would imagine it would still require quite a few hours of running the electrolysis to
produce sufficient quantities of product.
Al Koholic October 25th, 2003, 07:21 PM

If you are really looking for the cheapest substitutes for corn cobs, I believe you could probably get away with using any kind
of plant matter at all. Leaves, sticks, grass, etc, etc. If I'm not mistaken, the point of the corn cobs is the high lignin content
which provides the 5 membered ring. Any cellulose based matter should be able to be treated similarly.
Milamber October 25th, 2003, 09:38 PM

Mega, as far as having to remove water for formation of the ester, you're gonna have to do it sooner or later anyway if you
want to do a grignard... what about distilling the chlorohydrin/water azeotrope through a drying tube with a good dessicant, and
having dessicant in the receiving flask. The success of this would probably depend on the composition of the azeotrope, of
course - too much water and the tube would need to be too long and losses would be huge. I think the BP of the azeotrope is
around 96oC, but I cant find the composition. Anyway, assuming it worked, you could then form the ester in the presence of
dessicant, which should soak up the water that forms.
Hey Al, I think that you've just come up with the perfect incentive for mowing the lawn - I knew there had to be a reason to do
it!! ;)

Lignin is a sort of gum based on aromatic rings but lignin and cellulose generally occur together with sizable amounts of
hemicellulose which is composed mostly of pentose monomers.
I think the corn cob method on orgsyn is very important becuase it gives a yeild, and its a damn good yeild. Are corn cobbs
sold as animal feed at all?
I understand nbk has a synthesis somewhere of ethylene chlorohydrin by bubbling HCl gas into ethylene glycol, I would think
this gets better yeilds, but I dont seem to be able to actually find the method in either the forum or his pdf. He has also listed
a brand of antifreeze that is a mixture of only methanol and ethylene glycol, this should be fairly easy to seperate.
The borate ester method looks interesting, but not being acid or base stable is a problem, being water sensitive is also a
problem and in this instance Id be worried the boric acid would attempt to esterify both OH and Cl.
On the speed of hydrogenation, this is very strange, but I'll defer to the people with the books.
On electrolysis, this seems like a bad method. The ethanol salt mixture probably does not conduct electricity very well, and as
for using rectified line current, this is wasted energy, the high voltage is only overcoming the high resistance of the cell, over
95% of the power used is wasted.
Cannizzaro is certainly one way to go for producing the carboxylic acid from the aldehyde, but as you said this puts half of the
furfural into a useless state. Much better would be to find a cheep, mild oxidising agent that will oxidise the aldehyde but not
the double bonds. Silver oxide will do this and with recycling this would end up dilute nitric acid which is good or bad depending
on your point of view.
markgollum October 29th, 2003, 08:51 PM

About synthesizing nickel chloride:
NiCl2 can be made by reacting HCl with nickel according to the following equation. Ni(s) + 2HCl(aq) > NiCl2(aq) + H2(g)
I think that this reaction occurs quite slowly, so if you wish to accelerate it, you could probably electrolyse HCl with a nickel
anode.
The nickel chloride produced via this equation is green,
because of the hydrated nickel(2) cation Ni(H2O)6 2+.
Anhydrous NiCl2 is yellow.

I received a large load of books from the library yesterday and as luck would have it I found a synthesis for ethylene glycol
that is the best I have seen yet. I rather liked the electrolysis method because up until that point the only method I had
uncovered was a mid 19th century process that forced hypochlorous acid into pressurized containers of alcohol that required
some weeks. Compared to electrolysis they both seem exceedingly slow, except for the fact improvised chemists are
probably far less likely to be able to conduct the pressurized reaction, nor are they likely to be able to make more than
s m all a mounts of hypochlorous acid. Electrolysis wins by d efault. Hmm, tha ts n ot just a 19th century me thod, that s the
method they used until the mid 20th century when the catalytic oxidation of ethylene came into vogue.
Now of course I have found a chemical method to prepare ethylene glycol from (hopefully) all OTC materials. The problem with
distilling ethylene glycol from antifreeze is the stuff is rather expensive. I have a slow leak in my radiator, believe me I hate
buying antifreeze because it costs too damn much. I think the scheme I have here is doable and more importantly is quite
economical. The process involves producing ethylene gas that is immediately bubbled into bromine and converted into
dibromoethane. The dibromoethane is then reacted with a strong base to make ethylene glycol. The glycol is converted into
ethylene chlorohydrin merely by adding conc HCl (for some reason only 1 of the hydroxyls is replaced by chlorine).
Ethylene can be generated by heating ethyl alcohol with sulfuric acid, or it can be made by passing heated ethyl alcohol vapors
through a heated tube of aluminum sulfate. The ethylene gas immediately reacts with bromine by bubbling the gas into it. I
have to check, but I believe bromine can be made from OTC bromide salts quite readily. Of course the bromine can be
recycled in this process since upon reaction with sodium or potassium hydroxide the dibromoethane is rendered into a sodium
or potassium bromide salt (and ethylene glycol of course).
Nbk2000 does have a method of converting ethylene glycol to ethylene chlorohydrin in his mustard gas document, but I
d o n t think that is in general circulation (n or does he want it released, so I won t pass it around ). His method involves heatin g
ethylene glycol to 148 degrees C while passing in a continual stream of hydrogen chloride gas. The ethylene chlorohydrin and
water are distilled off as they are formed. At the end of the operation the temperature is raised to 160 degrees C to distill off
the last traces of chlorohydrin. According to his notes the processing of 100 g of glycol takes 16 hours. The distilled ethylene
chlorohydrin is washed to sodium carbonate solution to neutralize and hydrochloric acid, and later washed with 2-3 times its
volume of ethyl ether. The ether solution is removed and completely dried over freshly melted sodium carbonate. Yield is
about 60%.
I have a note here in a book that says ethylene chlorohydrin can be made from ethylene glycol by heating with concentrated
hydrochloric acid. Although that is the extent of it this sounds somewhat easier than passing hydrogen chloride gas into
glycol. In fact one could probably just add a gallon of antifreeze directly to a jug of muriatic acid without bothering to distill the
former first. The acid will eventually be neutralized as it forms chlorohydrin and water. Some antifreezes come watered, so
maybe that isn t such a good idea all th e time .
The same book says ethylene oxide is made from the chlorohydrin by adding concentrated potassium hydroxide. I assume
sodium hydroxide would work just as well. Ethylene oxide is soluble in water, but it is a gas at room temp (bp 10.7 degrees C).
Since the ethylene oxide must be free of water for a Grignard reaction, the post reacted chlorohydrin and base could be boiled
to liberate that gas, the vapors passed through a drying tube to remove moisture. It could also be extracted with ether by
shaking it with the (salted out) aqueous solution.
The preparation of ethylene glycol proceeds from 1,2-dibromoethane through the intermediate glycoldiacetate.
Glycoldiacetate: A mixture of 63 g (0.33 mol) of ethylene dibromide, 20 g of glacial acetic acid, and 60 g of freshly fused and
finely powdered potassium acetate is placed in a short necked, round-bottomed flask (500-mL) provided with a reflux
condenser and is vigorously boiled for 2 hours on a sand bath or on wire gauze over a large flame. The flask is then
connected by means of a bent tube with a downward condenser and the reaction product is distilled over by means of a large
luminous flame, which is kept in constant motion and is made progressively less luminous towards the end of the distillation.
The distillate is then mixed with a further 60 g of ethylene dibromide and 80 g of potassium acetate; the mixture is vigorously
boiled for 2 to 3 hours on a sand bath as described above and is again distilled. By means of a Hempel column of about 10
cm length the distillate is fractionated and the following fractions are collected separately: 1. up to 140 C, 2. 140-175 C, 3.
175 C to completion. Fractions 2 and 3 are then redistilled separately, when pure glycoldiacetate passes over between 180 and
190 degrees C (the bulk at 186 C). Yield is about 70 g.
Eth ylen e glycol: In order to obtain free glycol from the acetate ester, the la tter is transeste rified by boiling with a solution of
hydrogen chloride in absolute methyl alcohol. This solution is prepared by passing hydrogen chloride gas into cooled absolute
methyl alcohol, while excluding moisture, until the concentration is about 3%, as indicated by the increase in weight on a
balance sensitive to 0.1 g. If too much hydrogen chloride is passed in more alcohol is added.
Glycoldiacetate (49 g, 0.33 mol) is boiled under reflux in a 200-mL round-bottomed flask with 60 mL of the hydrogen chloride/
methyl alcohol solution for 30 minutesand then methyl acetate and part of the methyl alcohol are removed by distillation
(slowly at first) through a downward condenser, and the rest under vacuum at about 50 degrees C. In order to separate small
quantities of unchanged ester from the glycol remaining in the flask, the latter is closed by a rubber stopper, and the contents
are shaken with 50 mL of absolute ether, in which ethylene glycol is insoluble. Adherent ether is then removed on a boiling
water bath and the hot glycol is poured into a small distilling flask, fitted with an air condenser, and distilled. The main portion
passes over at 195 degrees C. Yield is 17-18 g (80-90%).
The potassium acetate used above is prepared by heating the hydrated salt (made by neutralizing vinegar with potassium
hydroxide or carbonate and boiling off the water) over a naked flame in a shallow iron or nickel dish. After the water of
crystallization has evaporated the material solidifies. By careful heating the anhydrous salt is now also fused. After
resolidification the still warm substance is powdered and immediately transferred to an air-tight container. Commercial
anhydrous potassium acetate should also be fused before use.
The preparation of 1,2-dibromoethane (ethylene dibromide) proceeds directly from the synthesis of ethylene gas. A freshly
prepared and preferably still warm mixture of 30 mL of ethyl alcohol and 90 mL of concentrated sulfuric acid is heated not too
strongly to 160 degrees C with 60 g of fine sea sand (helps remove water) or an equal weight of anhydrous aluminum sulfate
in a large round-bottomed flask (about 3-L) over a flame or sand bath. The flask is stoppered with a very tightly fitting 2-
holed cork (or rubber). Through one hole is pushed a thermometer which dips into the liquid and through the other a T-tube. A
dropping funnel with a long stem is inserted through the upper constricted opening of this tube and fixed with a small piece of
rubber tubing, while the end of the side tube is also constricted, and is connected with some receiver bottles (see illistration,
#49). Before the cork is pushed in, the stem of the funnel, which is constricted at the end by drawing out, is filled by suction
from a mixture of 190 mL of ethyl alcohol and 170 mL of concentrated sulfuric acid.
As soon as the vigerous evolution of ethylene has set in, the alcohol/sulfuric acid mixture is dropped in at such a rate that no
copious frothing occurs and a regular current of ethylene is evolved. The temperature is kept continually under control (small
flame!).
In order to remove alcohol and ether the gas is passed through a wash-bottle containing concentrated sulfuric acid, and
sulfurous acid is removed in a three-necked wash-bottle containing 4N sodium hydroxide and provided with a safety tube. The
gas then passes into two moderately wide wash-bottles each containing 25 mL of bromine. In order to reduce loss by
evaporation the bromine is covered in a layer of water 1 cm deep and the two bottles are kept cool in a vessel of cold water. If
the pressure permits, the last receiver in the train is a Peligot tube containing 2N sodium hydroxide solution; if not, the
bromine vapor which escapes is absorbed in sodium hydroxide solution in a corked Erlenmeyer flask (notch the side of the
cork!) in which the delivery tube is above the surface of the liquid (shake from time to time). The first two wash-bottles are
conveniently closed with rubber stoppers. See illustration #50 for an example of the glassware setup. As soon as the bromine
has been decolorized or, at least, as soon as bromine vapor is no longer visible over the brownish-red reaction product
(usually after 2-3 hours) the flask is disconnected from the receivers. Then the crude ethylene dibromide is shaken in a
separating funnel with water and sodium hydroxide solution until decolorized and washed repeatedly with water. After drying
with calcium chloride it is completely purified by distillation. BP 130 degrees C, yield 125-150 g.
Even if one does not appreciate the route to THF that uses ethylene glycol, it is still nice to have this information handy for
mustard gas preperation.
Milamber October 31st, 2003, 10:00 PM

Hey Mega,
Just thinking... if you're going to make ethylene and convert it into the dibromide, then to the glycol then to the chlorohyrdin...
sounds long and tedious and, since working with gases at at least some point, potentially very easy for losses to occur. I have
two suggestions that may work - at least worth considering.
First, what about, instead of bubbling the ethylene in bromine, we instead bubble it into aqueous sodium hypochlorite - if
memory serves, this should add OH and Cl across the double bond and thus give the chlorohydrin directly. Other advantage
here is not having to deal with bromine... Disadvantage is the fact that you're doing it in water, of course, perhaps leading to
purification problems.
Second, if this doesn't work, what about using only 1 equivalent of NaOH and, instead of converting the 1,2-dibromide into the
glycol, we replace just one of the bromines and get the bromohydrin (which would be a better choice than the chlorohydrin
anyways, as it would be more reactive, and higher boiling as well for easier handling). Of course this way you'd have to purify
carefully, as you'd have a mix of unreacted dibromide, bromohydrin and glycol, but the bromohydrin should be the major
product.
Worth thinking about, anyway!
Marvin November 1st, 2003, 12:58 AM

I do bilieve Ive accidentally stepped into the twilight zone.
Probably the fault of the last person to give me directions.
If we want a diol from an ene we only need oxidise. Only problem normally is stopping the reaction going furthur, ultimatly to
cleaved acids. If memory serves cold dilute and neutral permanganate will do this.
If we are going the ethene route to chlorohydrin though, why are we not using the hypochlorite method?
Bubble the ethene into hyperchlorite/acid (free from chloride!) or chlorine in water (aparently this works too) for hypochlorous
acid in situ and get ethylene chlorohydrin directly.
If you do try electrolysis for chlorohydrin, Id be very interested in details, such as electrode dimentions, cell resistance etc. I
still think it will be more trouble than its worth, but the method might be useful for other things.
I think the chlorohydrin method of making mustard gas is suitably convoluted and best kept that way.
Edit,
Milamber has basically beaten me to the punch while trying to check a few things, but I'm not sure if alkaline hyochlorite will
work or not. I am still clearly in the twilight zone however.
snuk5 January 25th, 2004, 11:45 AM

Re:
__________________________________________________ ______________________________
ethylene ch lorohydrin by electrolyzing a solution of ethyl alcohol and salt
try electrolysis for ch lorohydrin & such as electrode dimensions, cell resistance etc
__________________________________________________ ______________________________
I have no experience with this particular electrolytic synthesis, but I had to device a method to make dimethoxyfuran from
furan and methanol in an electrolytical cell.
The fact that dimethoxyfuran is not too stable and the whole thing had to be done in my refrigirator s freezing compartment
did not help the conductivity a lot either!
Because that is the whole rate-determining factor in syntheses like these,
I ll give some recomme ndatio ns to the problems at hand :
1) Consider some other electrolyte than salt. It will be very insoluble in EtOH. (Unless you feel that you can have quite some
water prese nt but I do nt think yo u want that ) Perha ps am moniu m chloride could do the job. I used ammonium brom ide at
the time, but I could do so as the halogen derivative of my compound was only an intermediate, not a product that has to be
isolated.
2) The cell resistance is inversely proportional to both the surface area of the smallest electrode and the distance between
them.
Use a graphite rod for your anode; they stand up very well in non-aqueous electrolyses. (Get it from the people who make
up carb on brushes and electrodes for EDM engineering.) If you can t get this, break u p som e batteries a nd put the anodes in
parallel.
3) For the cathod e use stainless ste el mesh; roll it into a cylinder around the anode. Sew this up with s trands of the mesh
and keep the distance small -use spacers at the bottom and the top. (Preventing shorting and allowing for adequate flow).
4) Provide some means of agitation, (magnetic stirrer) as local depletion of the electrolyte slows down things.
5) Depending on the current and surface area, nature of the reaction cell, cooling might be required. (We are pumping
ele ctrical curre nt here) But if things don t decompose, the higher the temp, the lower the resis tance and thus the lower the
voltage we can employ.
6) Electrolytic synths take time, but they proceed smoothly and just about quantitatively -the driving force is a current that we
can modulate by fiddling with the voltage. (Start with higher V than for aqueous electrolyses.)
7) Use an ammeter, as well as a thermometer.
8) If you keep a log of the time and the current, you can take your pocket calculator and get a nice idea of how many
Coulombs have gone down and thus how many moles of product you have made already!
If I were to do this thing and I meant b usin e s s scale wise, I d use my DC welder as a current source and cool the reactants
with coils of 8 or 10 mm stainless ste el tube and run water through them. If I d find that the voltage were much higher than
required, I d put two ban ks of electrode s in series.
Coincidentally, I was looking for THF myself some time back, if yo u d o n t buy it by the truckload, but from your local lab
supplier, it costs the earth.
My friendly supplier traced two 250 ml bottles of AR grade that went for a song.
I ll save this page, just in case, as I re ck on it s totally feasible and should I have no other source, I d whip up a going pilo t cell
in a matter of days, and then go the big Tupperware route. Without all the custom-made ground jointed stuff that I used at
the time.
Come to think of it, I was looking for a hypothetical source of 1,4-butanediol (even harder to get than THF), for some
hypothetical jet printer ink formulation; this OTC stuff is great!
FlaAlchemist January 31st, 2004, 07:20 PM

Did the grignard with the p-dichlorobenzene work?
Was it a traditional grignard rxn in ether solvent?
If so, what was the major product?
I'am curious because the p-dichlorobenzene is readily avalable as a starting material.
I have used p-dichlorobenzene by adding a NO2 in the ortho position to deactivate those chlorines on the ring.
megalomania January 28th, 2005, 12:33 AM

A little off topic, but I can't find a thread just for benzene, so... The Gringnard of p-dichlorobenzene did not proceed so well.
After several trials is is damn hard to initiate the reaction. The only reason I am back in this thread is because I am getting
ready to build myself a poor-man's hydrogenator that I hope will withstand a good deal of pressure. While refreshing myself
on hydrogenations last night I came accross a chapter about hydrogenolysis of aryl-halogen bonds. Apparently hydrogenolysis
of aryl halogens is quite easy under mild conditions (those conditions being a few atm's of pressure, nickel catalysts, and
about 100 C).
This is good news for the production of benzene from p-dichlorobenzene. The conditions required to completly hydrogenate
the benzene ring would require much higher pressures, or better still, precious metal catalysts. The order of reactivity is typical
of halogens, iodine > bromine > chlorine > fluorine. Apparently hydrogenolysis can even cleav fluorine, which is tough to do
most of the time (damn near impossible with a Grignard).
Halogen hydrogenolysis may also be a good way to make aniline from p-dichlorobenzene. p-DCB can be nitrated, and the
nitro group will actually make it easier for hydrogenolysis to occur. Under the same hydrogenation conditions for
hydrogenolysis of chlorine, the nitro group is hydrogenated to an amine, in this case aniline.
Experimantal conditions would consist of p-DCB dissolved in 95% ethanol with either sodium hydroxide or potassium acetate
as an acid scavenger. The presence of hydrochloric acid would poison the hydrogenation catalyst, hence the need for a base.
The reaction can be carried at room temperature and atmospheric pressure with precious metal catalysts. Since nickel catalysts
have less activity it would probably be best to heat the reaction and raise the hydrogen pressure a few atmospheres. One
should be careful because eventually you will hydrogenate the aromatic ring.

Mega maybe you could try one Grignard modification I read few years back. Instead of lightly heating the reaction to onset,
they just imerse the flask with reaction mixture in ultrasonic bath.
Maybe even electrolysing the benzoate solution or heating the sodium benzoate/sodium-carbonate mixture can get you some
benzene. Sorry I must ask, why? Just food for thought, real problem or what. I can't believe that you can't find available
benzene. Solution with hydrogenation is elegant you bring some of mine memories. Some parts of chemistry are acctually not
so easy. Most of reaction in organic chemistry are understandable and self-explicable but there are few areas that defies this
rule as catalytic hydrogenation and electroorganic reaction.
Rest of the thread is fine. For those who want to experiment little in toxicology I recomend to convert a 2-chloro-ethanol to
epoxide(carefull gas not to mention toxic one) and then heat that one with KSCN to replace O with S, you are now very close to
sulfur mustard gas...and man if this could work with epychlorohydrine it would make cheapest hell on earth ever.
megalomania February 8th, 2005, 09:37 AM

It seems the post I made about my experiment this past summer was deleted in the great crash. In particular nbk2000
described a method of making an improvised bubbler from Teflon tubing? Would you describe that process again nbk? I don't
remember the specifics.
I am going to try an build a high pressure hydrogenator using a "pipe bomb" design. The burst pressure of common steel
alloy is in excess of 7000 -1 3000 ps i for a 2 pipe, and the working pre ssure is half th at. A ma x pres sure o f 1500 ps i (100
atm) is quite sufficient. Apparently as the diameter of a steel vessel increases its max burst pressure drops. This explains
why air com pressor tank s have a ma x pres sure o f only 150 ps i, whereas a pipe has a min imum burst pressure of 1350 0-
17000 depending on wall thickness.
I was thinking of connecting two pipe sections together along with a U joint that includes a ball valve in between the parts. The
hydrogen can be generated chemically in one section of the pipe, while the hydrogenation reaction is held in the other. If extra
hydrogen is needed over the course of the reaction the valve can be closed, the hydrogen generator portion opened, and
additional chemical reactants added. The valve will keep the hydrogenation section from being depressurized.
I was also thinking about molding a loose fitting concrete shell for the pipe just for safety reasons. The concrete can be
reinforced with chicken wire so it does not crack and shatter should an explosion occur in the pipe. This may make it difficult
to ap ply heating and stirring to the pipe though. I cou ld rig up a ro ck er system like they h ave with Parr hydro genators
nbk2000 February 17th, 2005, 03:27 PM

Take a length of teflon tubing, clamp one end shut with Vise-Grips, leaving about a 1/8th inch sticking out, and use a low
flame on a lighter to melt the end. You may use a spoon to smooth the end while its still soft, and immerse it ASAP under
cold water to set it. :)
A hot needle makes the holes for the gas to bubble out through.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > OTC pyridine
production
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In the formaldehyde thread:
http://roguesci.org/theforum/showthread.php?s=&threadid=2089&highlight=pyridine
We touched upon some possibilities of obtaining pyridine from OTC sources such as extract of black pepper. Unfortunately that sources seems rather tedious and possibly
expensive. Some industrial type catalytic process may give results, but those are always difficult to reproduce. I cited a few patents in that thread.
I have found a chapter in a book that prepares pyridine derivatives through various condensation reactions and I would like some users input on the applicability of
these reactions. The specific information is a series of reactions called Hantzschs Collidine Synthesis originially published in 1882. Collidine for those who dont want to
look it up is trimethylpyridine. The reaction proceeds thusly:
Acetaldehyde and ammonia combine with 2 moles of ethyl acetoacetate (prep given on orgsyn) to form an alkylidene bis-acetoacetic ester which undergoes ring closure during
the reaction to form the cyclic pyridine derivative ethyl dihydrocollidinecarboxylate (rather like piperidine but with 2 double bonds). Subsequently the ring is made aromatic by
reacting with nitrous acid. The carboxylate portions are removed by neutralizing the compound to its potassium salt with KOH, and then heated with lime in the same way
benzene is made from benzoic acid.
Now then, collidine isnt exactly pyridine, but it is quite similar to trimethylbenzene (mesityline), of which I have been studying of late to convert to benzene.
Theoretically the mesitylene (or in this case collidine) can be oxidized to convert all those methyls into carboxylic acids, and they can be removed just like I said
above, by heating with lime. Of course there seems to be some disagreement in the literature I have read as to whether or not one can actually oxidize all 3 methyl groups at
the same time. It may take an additional step to oxidize any dimethyl or methylpyridine that remains. Also some stronger oxidizing agents other than potassium permanganate
may be needed.
Of course another alternative is to conduct this reaction using different starting materials. Ethyl acetoacetate could be replaced by something without the extra methyl
group. I dont know what this is called, its not in Merck, but it looks like this:
O=CH-CH2-COOR where R is the ethyl of ethyl acetoacetate hmm, why dont I just draw a diagram see attached image.
With all those double bonds shifting about it is quite possible those extra methyl groups are necessary for resonance :( so we may be unable to proceed directly to pyridine
using formaldehyde and ethyl-acetoacetate-less-a-methyl.
If anybody thinks Im on the right track here I will post the details of the collidine synth.
Marvin November 1st, 2003, 03:55 AM

I am interested in the synth, Id like you to post it though I dont consider it useful as an OTC method. Ive been after pyridine for some time, and done a fair bit of research.
Using formaldehyde instead of acetalydehyde will certainly work, and Vogels practical organic chemistry has this synthesis. Unfortunatly its in the 5th Ed, 1989, so I dont have
it. In removing the methyl group from ethylacetoacetate though you are turning a ketone (more properly a beta keto ester) into an aldehyde and I would expect this to mess
up the initial crossed aldol becuase self condensation is now more favoured.
Ethyl Acetoacetate can be made from Ethyl acetate by an ethoxide 'catalysed' reaction, but all the syntheses Ive seen end up using up large amounts of sodium metal.
Allthough 'in theory' you can make this by electrolysing molten sodium hydroxide its at this point the whole synthsis looks unfeasable to me for my pyridine requirements.
If you can find somewhere that will supply bulk B vitamins, you can always buy niacin and decarboxylate that to pyridine. Not the cheepest way, but certainly OTC, and about
as simple as its going to get. Note that the carboxyl group is on the beta carbon, and that these are more difficult to decarboxylate than alpha or gamma which go pretty
easily.
What software are you using to do the diagrams btw?
megalomania November 1st, 2003, 05:37 PM

I'll get the reference from Vogel's 5th edition Monday, it's at my library.
I have the distinct impression there is a way to make sodium ethoxide without using sodium metal, if that is the usage of sodium metal you were referring too. I can't
remember where I saw that info, i"ll have to check my stack of notes...
That niacin route sounds interesting, but probably not economical. I buy B vitamins for myself and they can get quite pricy. Of course the reaction does seem to be an
expediant OTC route if one does not require large quantities of pyridine. The decarboxylation of niacin does look pretty easy, and despite the function group of interest being on
the beta carbon, I would say it will snap off easy enough with a little extra reaction time. Have you ever tried the reaction?
Lets see, one could get 40 g of niacin for around $14.00 (400 100mg pills). That's only 0.325 moles, and even assuming 100% extraction from the pills and conversion to
pyridine that would only give us about 26 mL. The cheapest grade of pyridine in the Aldritch catalog is $31.80 for 500 mL.
I made the graphic in Chemwindow 6.
I am seriously considering setting all my other projects aside and concentrating on alkali metal production. It seems all roads lead to such metals when you try to synthesize
things. I tried to electrolyze some molten salts a few days ago and my metals just ignited as soon as they were formed, probably because of the magnesium in the mix.
Industry makes it look so easy... bastards.
Marvin November 2nd, 2003, 01:54 AM

You can make sodium ethoxide, and indeed sodium itself fairly easily if you can get magnesium metal. But its just another chemical that cant be recycled at home. My
intention is to try a few interesting reactions, make the odd interesting or useful chemical as and when I feel like it, rather than to try recreating the last 200 years of industrial
chemistry in my back garden.
Sodium can be made in quantity, but its a matter of buying the right bits and setting them up as if you were doing it industrially. Most people dont want to spend 6 months of
their life setting up the equipment and at the end just being able to produce 1 chemical. Unfortunatly this is the kind of dedication kg quantities of sodium require, though it
would be very cheep compaired to lab supply places. I would think a stainless steel pressure cooker would do quite well with nickel gauze diaphram and welding grade nitrogen
gas flushing. 25kg sacks of NaOH can be bought even here quite cheeply and the power amounts to less that this. Somewhere I have the estimated cost of sodium that I
worked out a while ago. The problem of a rigid insulator that will withstand attack by molten caustic soda rears its ugly head though and I wasnt able to solve that
satisfactorily. Ive made tiny amounts in a very simple setup, but nothing synthetically useful so far.
The collidine synthesis decarboxylates at the beta position, so Id expect conditions to be hopefully similar. I havnt tried the niacin route and I dont have specific conditions
which is one of the big reasons I'm interested in the synthesis you have and the similar synthesis in Vogels which may or may not include a decarboxylation in a later step. I
am still hoping to find someone that will just sell me pyridine, but in the event I cant niacin will probably be how I'll go. I want to do a coupling reaction that has to be done in
molten pyridine hydrochloride, but nothing most people on this forum would be interested in.
After doing a quick search on US sources for niacin a reasonable estimate would seem to be $35 for 500g of niacin. Tablets can be found that are 500mg up to 2g typically and
are only slightly above this price for 500g and 'bulk' powder prices similar for this amount. Its probably possible to buy it in multikilogram quantities and have the price fall much
furthur.

After reading about the Hantzsch pyridine synthesis in Vogels I have come to believe that this reaction can be done with an aldehyde rather than a ketone to get an
unmethylated version, aka pyridine itself. I believe the reaction proceeds via some sort of imine-enamie pathway that works with either aldehydes or ketones as it is the
carbonyl that is important, not that which may be attached to the carbonyl. The ester is still quite important to the reaction.
Instead of using ethyl acetoacetate as the starting material (giving us dimethyl pyridine) we can start with ethyl formylaldehyde. Ethyl formylaldehyde is just like ethyl
acetoacetate except its an aldehyde, not a ketone. Ethyl formylaldehyde should give us pyridine when reacted with formaldehyde.
I found 9 references for the synthesis of ethyl formylaldehyde, but none seemed all that good. The one patent there was is in Japanese. All I could find then is one tantalizing
scrap of information: the crossed Clasien condensation reaction of ethyl formate with ethyl acetate promoted by sodium ethoxide and subsequently quenched with acid.
Ethyl formate should be easy enough to make from formic acid and ethanol, same with ethyl acetate as it is just the ester of acetic acid and ethanol. Sodium ethoxide can be
made by adding sodium hydroxide to ethanol.
And now the part from Vogels 5th edition, which is so much better than the old version I have: Experiment 8.29 DIETHYL 2,6-DIMETHYLPYRIDINE-3,5-DICARBOXYLATE
AND 2,6-DIMETHYLPYRIDINE
Diethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate. Cool 52 g (51 mL, 0.4 mol) of ethyl acetoacetate to 0 degrees C and add 15 mL (0.2 mol) of 40% aqueous
formaldehyde solution, followed by a few drops of diethylamine as a catalyst. Keep the mixture at 0 degrees C for 6 hours and then at room temp for 40 hours. Separate the
lower organic layer, extract the aqueous phase with ether and dry the combined organic fractions over anhydrous calcium chloride. Remove the ether under reduced pressure
(rotary evap) and transfer the residue together with an equal volume of ethanol to a stout reagent bottle cooled in an ice bath. Pass a steady stream of ammonia gas (from a
cylinder) into the solution held at 0 degrees C for 1 hour, close the bottle with a bung securely attached with a wire and set the bottle and contents aside at room temp for 40
hours. Filter the resulting yellow solution to remove a small quantity of almost colorless material and heat the filtrate on a boiling water bath in an evaporating dish until most
of the ethanol has been removed, and then cool and crystallize the residue from about 400 mL of rectified spirit. The yield of the pale yellow crystalline dihydropyridine
derivative is 36 g (71%) mp 181-183 degrees C.
Diethyl 2,6-dimethylpyridine-3,5-dicarboxylate. Place 35.5 (0.14 mol) of the above dihydropyridine derivative in a 1-L round-bottomed flask and add carefully a cold mixture of
50 mL of water, 9 mL of concentrated nitric acid (d 1.42) and 7.5 mL of concentrated sulfuric acid. Swirl the mixture and heat it cautiously on a boiling water bath until a
vigorous reaction, accompanied by much foaming, sets in. When the reaction has moderated continue to heat cautiously for 15 minutes until oxidation is complete and a deep
red solution is obtained. Cool the solution, add 100 mL of water and 100 g of crushed ice, and make it distinctly alkaline with concentrated aqueous ammonia solution (d 0.88).
Filter off the solid product, wash it with a little cold water and recrystallise it from aqueous ethanol. The yield of colorless crystals of the pyridine derivative is 22.5 g (64%) mp
71-72 degrees C.
2,6-dimethylpyridine. Place an intimate mixture of 10 g (0.04 mol) of the above pyridine diester and 60 g of soda-lime (10-14 mesh) in a 100-mL round-bottomed flask fitted
with a still-head and condenser arranged for distillation. Heat the flask gradually in an oil bath to about 250 degrees C, and maintain this temperature until no further material
distills below 105 degrees C (about 2 hours may be required). Remove the oil bath, clean the outside of the flask and continue to heat more strongly with a Bunsen burner held
in the hand, keeping the flame moving over the surface of the flask. Collect the product which now distills, and continue to heat strongly until the flask reaches dull red heat
and nu further distillate is obtained. Treat the distillate with potassium hydroxide pellets so that the pyridine separates, and isolate the latter by extraction with ether. Dry the
ether extract over fresh potassium hydroxide pellets, and remove the ether and distill the residue at atmospheric pressure. Collect the dimethylpyridine as a fraction of bp 142-
145 degrees C; the yield is 2.8 g (65%).
Thats all folks. This procedure differs significantly from the old method I have, and not just because it uses aldehyde ammonia instead of formaldehyde. It forms the
aromatic ring by adding nitrous oxides formed by reacting nitric acid with arsenious oxide.
What do you think the chances of preparing pyridine from the variant of this method are, Marvin? One could prepare their formic acid from oxalic acid and glycerol,
then its a matter of combining the necessary alcohols and acetic acids to form the esters, and sodium ethoxide of course. Then all the other miscellaneous reagents,
none of which seem too far fetched. Some difference in solubilities of the intermediate product will have to be taken into account as we will no longer be preparing a
dimethyl dicarboxylate, just a dicarboxylate. Eh diethyl 1,4-dihydropyridine-3,5-dicarboxylate; and diethyl pyridine-3,5-dicarboxylate; and then pyridine of course. I
would think the major contaminate would be 4H-pyran if the aldehyde sections do their intramolecular inbreeding and the reaction with mixed acids does nothing to those
double bonds.
EDIT: Ahh, I see the rub here, if we use an aldehyde like ethyl formylaldehyde, what's to stop it from self condensing and forming some huge muto molecule rather than
condensing with formaldehyde? We could in theory apply an impromptu acetal protecting group to the aldehyde end of ethyl formylaldehyde with ethylene glycol. This would
allow the first part of the reaction to form. Then we add HCl to break the acetal, and subsequent addition of ammonia neutralizes any excess acid, and we continue where we
left off. I know, I know, what about the other carbonyl of the ester, won't it form an acetal too? Well, acetal formation dosen't do so good with things other than aldehydes or
ketones, but I don't know about esters. Hopefully it won't react.
knowledgehungry November 8th, 2003, 10:26 AM

You might be able to obtain pyridine from nicotine. For those of you who dont know nicotine is a pyridine ring with a 1-methyl azacyclopentane ring attached to it.
Mumble November 8th, 2003, 03:40 PM

You'd need a lot of nicotine to get an appreciable amount of Pyridine. This link (http://67.1911encyclopedia.org/P/PY/PYRIDINE.htm) shows several other ways to pyridine.
None of them are too viable for a decent level of production according to the site at least. It would be uneconomical as the amount of pyridine actually produced is small.
Perhaps a method or two, with further investigation, could yield a new more efficient proceedure.

I have been looking into some vitamin B3 sources (niacin) and it looks like most of the brands selling niacin are primarily niacinamide, or nicotinic acid-niacinamide mixes. It
looks like nicotinic acid is the stuff that causes "flush" when using niacin, and there are many flush free brands. Flush free probably means all niacinamide. The bulk niacin at
Wal-Mart is flush free.
Is there anything that can be done with niacinamide? It is just an amide after all. It would seem a trivial workup to hydrolyze the niacinamide by boiling with either sulfuric acid
or sodium hydroxide. In fact boiling with sodium hydroxide (or potassium hydroxide) leads to a sodium (or potassium) salt, and that is required anyway for the decarboxylation
step if it proceeds like the step in collidine synthesis.
Hmm, I guess I answered my own question. Any OTC niacin should be boiled with a strong base just in case it has any niacinamide. In fact there is a general procedure in
Vogel's... Amides may be hydrolysed by boiling with 10% sodium hydroxide solution to the corresponding acid (as the sodium salt). Lets see, it gives an example of another
compound which is basicially boiled for 3 hours to complete the reaction, during which ammonia is given off. Since sodium nicotinate is quite soluable in water it won't
precipitate, but we just boil off the water to obtain the crystals which will be mixed with NaOH, combine that with lime, mix, and heat to liberate pyridine. I am off to try that
right now. To the vitamin store!
EDIT: 1 hour later... Well it turns out Wal-Mart doesn't sell either nicotinic acid or nicotinamide, it sells niacin as inositol hexanicotinate. That stuff as it appears is the
predominant "no-flush" version. No matter, I went to another store and bought some niacin that is all nicotinic acid. A quick check of Merck shows inositol hexanicotinate is
quite the funny molecule, but would probably be convertable to nicotinic acid via acid or base hydrolysis anyway since it is an ester. The only downside is inositol hexanicotinate
is insoluable in water, so it may take awhile longer to react with an aqueous base. On the plus side digestion with water could remove some of the soluable components of the
pill beforehand.
thrall January 9th, 2004, 05:24 PM

Sorry to bring up an old topic,but what were your results megalomania! Looks like pyridine IS OTC;).

Darn, never noticed this thread..
I heard that ethoxide can be prepared by boiling ethanole with NaOH and destilling away water azeotropically with benzene. Any idea on other solvent than benzene? This
would be a fun project to investigate.. :)
We could in theory apply an impromptu acetal protecting group to the aldehyde end of ethyl formylaldehyde with ethylene glycol. This would allow the first part of the reaction
to form.
As far as I see, the carbonyl groups that will be protected suppose to take place in reaction by resonating.. When they're "fixed" by protective groups, enol will not form,
therefore, aldehyde will not connect to it. Though I'm just caviling to the details..
Btw, any idea where diethyl amine could be ubtained? Or, maby there can be used some other catalyst..

Due to the onset of colder weather I don't get much opportunity to do experimentation in my lab. We shall see in the spring. I am actually eager to attempt some of the old
19th century high temp catalytic reactions and see what kind of yields I can get.
snuk5 January 25th, 2004, 12:56 PM

Marvin,
__________________________________________________ ______________________________________
The problem of a rigid insulator that will withstand attack by molten caustic soda rears its ugly head
__________________________________________________ ______________________________________
I've also looked into the problem.

What do you think about somthing ceramic, possibly porcelain?
Does it have to be a nickel membrane, could stainless steel not work
(for at least a few runs)
Marvin January 27th, 2004, 04:26 AM

Ceramics seem to be mostly silicondioxide/silicate materials. These tend to dissolve/disintegrate in caustic soda. An experienced chemist has suggested magnesia mixed with a
tiny amount of sodium silicate solution, moulded and baked at about 1100C. This should only dissolve only very very slowly. I dont have a furnace so I wasnt able to try this, if
you can regulate that pet dragon of yours this might be an option. Steel or iron cage will probably work fine. There is quite a lot of info in threads here and on sciencemadness
about sodium manufacture youd do well to read as much as possible before doing a design. The major gotchas seem to be sodium metal shorting electrodes to eachother or
the diaphram, and the number 1, hydroxide too hot (25 degrees over melting point and no sodium forms).
FragmentedSanity January 27th, 2004, 11:14 PM

If someone wanted to make pyridine using OTC B vitamins, would they need a propper lab - or would it be possible to improvise? Is the synth simple enough for your average
Kitchen chemist to follow a "recipie". Id often wondered about such a process, so this topic got my attention when it first came up - but Ill freely admit that I dont have the
knowledge to devise a process by which one could achieve it. I had hoped to see something that would allow one to produce small quantities themselves; but as yet that hasnt
occured. Would anyone care to tackle the project of writing up a synth aimed at "kitchen chemists" - simplicity being the main objective along with ease of precursor
acquisition. The economics of the synth would be of far less importance.
I for one would be forever grateful - Im sure others would like access to small amounts of pyridine without the hassle of buying a watched chemical.

From niacin, yes, same basic reaction as the production of benzene from benzoic acid. Slightly harsher conditions required though I would think.

a n d I m provised C hemistry > Am m onium Nitrate Solubility in Methanol
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stanfield Novem ber 12th, 2003, 08:30 AM

did a search but nothing was returned... Both google & here.
So, anyone here has the solubility table of NH4 NO3 in (hot) m ethanol ?
thanx.
DBSP Novem ber 12th, 2003, 10:19 AM

C h e c k m e r c k ! s h o u l d h a v e s o m info on the solubility, I haven't got it installed right now so I can't check it m yself.
T h a n x i s s p e lled THANKS, use proper gram m ar in your posts (goes for all m e m bers!!).
Al Koholic Novem ber 12th, 2003, 11:07 AM

1 gram dissolves in 8 ml of m e t h a n o l .
stanfield Novem ber 12th, 2003, 12:40 PM

which tem perature ? hehe, this is what I need...
thanKS anyway ("thanx" is just shorter to write, sorry DBSP but I don't think it's worse than newbie who ask how to m a k e C 4 i n
the prim ary section...)
see you later !

a n d I m provised C hemistry > urea as a substiute?
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nanok66 Novem ber 18th, 2003, 05:56 PM

I h a v e f o u n d that pure am monium nitrate is very hard to find, for m e u r e a ( C H 4 N 2 O I t h i n k ) c a n b e o b t a i n e d m uch m ore
easily. Is it possible to substitute urea for use in anfo type explosives?
Or is there a way to convert urea into an am m onium nitrate substitute?
knowledgehungry Novem ber 18th, 2003, 07:37 PM

W ow this is the first g o o d p o s t a n e w b i e h a s m ade in a long tim e... O h wait no... no its no t at all, urea as a substitute for
NH4NO 3??? Just because they're both fertilizers doesn't mean they're both explosives:rolleyes:. W ho ever said there is no
such thing as a stupid questio n should b e s h o t .
Al Koholic Novem ber 19th, 2003, 12:08 AM

I suppose it couldn't hurt to m ention that he could make some urea nitrate if he has some nitric acid....oh wait....if you can't
get AN, I suppose it isn't worth the time anyway...
I just had to add...c'mon dude...if you reeeeee aaaaaaly wanted to find some AN you could without that much effort. W hy
should urea be easier to obtain? Cold paks...
jimmyboy Novem ber 19th, 2003, 01:07 AM

he is right though - am m on nitrate is alot harder to find these days -- urea definitely cannot substitute.. the only th ing i know
urea is good for is m aybe a cyanide synth
blindreeper Novem ber 19th, 2003, 03:40 AM

That is the stupidest thing I have heard all week. Can I substitue urea for am monium nitrate :rolleyes: Thats like saying can I
substitute KCl for KClO 4 in flash cause they both have potassium and chlorine in them . I can't see him /her around ehre to
m uch longer
zeocrash Novem ber 19th, 2003, 04:46 AM

you could substitute urea for AN, it would be utterly useless. but still while we're on the topic, chech out this (http://
www.roguesci.org/theforum /showthread.php?s=&threadid=1499) awesom e e x p l o s i v e
i really want to use th e forum f l a m e f o r m , but i'm not sure if this guy me rits a use.
Anthony Novem ber 19th, 2003, 03:15 PM

HED...:rolleyes:

and Improvised Chemistry > Setting up a lab
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vap0r December 6th, 2003, 04:05 AM

I've been into pyrotechnics on an amatuer level for 2 years now. I'm just getting into high explosives. I want to set up a sort
of "lab" for making them safely in my garage. Can anyone recommend what I should start off with? I've already got a couple
of beakers, a flask, a glass stirring rod, and some other accessories. What do all of you have, and what else are you going to
purchase to complete the setup of your lab?

I suggest a good spacey lab. Not cluttered. I personally have a wooden cupboard for my chemicals. It has 2 shelves, top for
small bottles and powders and the bottom for big things like 4L acetone, KNO3, acids bottles ect.
I also scored a metal, lockable metal cabinet which has all my glass, scale, gloves, glasses, respirator, matches/lighter, fuse
ect
A good solid desk/table is essiential for performing synthesis or whatever on.
I have a decent ammount of chems and rarely have to go out and get something new if I want to try a synthesis I "Just saw!"
I think you can;t buy everything you need in a lab at once, it kind of grows, like a garden :)
xyz December 6th, 2003, 09:12 AM

Now I wonder if we can get the people from one of those "garden makeover" shows like groundforce to start doing labs
instead...
flashpoint December 6th, 2003, 01:23 PM

I'm interested in getting a glassware set, I can get piece by piece at work, but I'd like a whole set, I wonder who sells them,
google time i guess...
Flake2m December 6th, 2003, 01:50 PM

I might setup a decent lab someday when I have enough money to. Labs themselves have also been known to be cash
cows...
Anyway as far as I know, make sure that the area your lab is setup is kept fairly clean. A dirty workplace can increase the
chance of bad accidents.
If you are really into seting up a lab it migh even be an idea to do a course at a TAFE (in Australia) on laboratory skills and
techniques, just so you have the basics.

I know its rather childish, but formally Edmund Scientific, has glassware sets...basic labware I do believe. Also I edited to add
this in, there is also labx.com that offers glassware I just found this today.
Anath December 6th, 2003, 08:16 PM

United Glass Tech (http://unitedglasstech.com/) has a nice distillation setup that's fairly cheap, I'd reccomend 24/40 joints.
SciPlus (www.sciplus.com ) also has some interesting stuff.
You can also put the word out if you know any schoolkids that you'll buy glassware for $20 or so, Sometimes it will
mysteriously 'appear' ;)
Don't bother buying beakers, I just buy pyrex measuring cups from Kmart, they are cheap and IMHO work better anyway.
Pick up flasks for cheap on eBay, keep an eye out for lab thermometers, a bag of rubber stoppers from a brewery supply shop
is always handy. check out the bins at the local Uni. Use an old electric frypan filled with 1" of sand as a cheap hotplate that
contains spills. Get a second-hand toaster oven to use as a dessicator. buy every cheap second-hand blender you see. A
cheap bar fridge is always handy.
You'll have a great lab in no time :)
megalomania December 6th, 2003, 08:20 PM

What kind of kit were you looking for, b ecause I h ave yet to see any seller offer more than a set of 10 beakers th at is
anywhere near economical? Places like Boreal Laboratories offer glassware setups meant to flesh out a complete school lab,
of course you have to be a teacher to get the catalog (but not to buy). If small quantities are your thing stay away from
Fisher or VWR, they have the cheapest prices only in mega case quantities. In small quantities you will pay through the
nose. Ebay or Labx.com would be the first place I wou ld lo ok to bu ild a lab on the cheap. You can t build a lab all at once
through the auction sites though, you have to wait and see what comes available over time.
It has taken me almost my entire life to build my lab. I find things at flea markets, garage sales, and local auctions. When
you can t find what you ne ed at the auction s then you can shop for things specifically at the glassware venders. I sug gest
www.elementalscientific.net for all your basic labware needs, they are the cheapest on average I have found and one of the
few who still sells chemicals to ordinary people. Now if it s real glass ware you want, and by that I mean a set of standard taper
glassware to do chemical reactions and distillations (ie. 90% of everything you would want to do) bite the bullet and make the
investment over at chemglass.com. Chemglass brand is top notch and the cheapest you can find. Order their free catalog or
read it online.
There is a damn good deal going on right now at labx here: http://www.labauction.com/v2/adsearch/Detail3.CFM?
adnumb=191416&CatID=165
Current bid is a mere $200 for a complete set, which is about half what I would expect to pay for such a set especially 24/40
taper. Ooh, even a three neck! (banned in California) If I only had the money :(
Now don t think yo u need to get all the profes sion al stuff, no indeed . The on ly th ing I would actua lly advise you to buy is the
standard taper kit. Otherwise you can use pickle jars as beakers, wine or beer bottles as flasks, Mason jars as beakers when
you need to heat stuff, measuring cups make good, if slightly inaccurate, graduated flasks (instead of a graduated cylinder).
You can use an ordinary blowtorch instead of a Bunsen burner. For lab stands you can get steel or aluminum rods at a
hardware store and either weld or solder them together. Things like clamps and rings you may be better of buying, and you
will need those sooner rather than later.
Save your money for the really important, but somewhat exotic equipment: magnetic stirrer, heating mantle, gram balance,
and possibly a pH meter.
Now then, it helps to know what kinds of chemistry you would like to do to choose what equipment you may need. Nothing
halts my experiments faster than lacking a bit of equipment.
Hang-Man December 6th, 2003, 08:23 PM

For those of you just setting up you're lab here are a few of the things I find most useful:
Small, 100 ml beakers
Pipettes (normal and micro)
Scale (0.01g)
Burner (butane rig i sort of made myself. works ok. I need a hot plate...)
Mortar and Pestle
Glass rod
High form, 500mL beakers
250 mL Erlenmeyer flasks for storing liquid chems (acids etc)
Wide mouthed jars for storing powders etc.
Thermometer
A few dozen large test tubes.
Latex gloves
PH strips, (or litmus or Phenolphthalein)
Once you have a lab you may want to check you're yellow pages for a hydroponics store and get some basic chemicals. I find I
run through HCl, H2O2, and KNO3 the most. Keep some baking soda on hand for acid spills (if your prone to accidents
:rolleyes:) and some salt if, like me, you often use electrolysis (you need to ionize the water) and for gods sake get some
decent goggles. Don't eat near you lab and ALLWAYS label your containers.
You may find the following site useful, good glassware kits.
www.thesciencefair.com/Merchant2/merchant.mvc?Screen=CTGY&Category_Code=gla
And for those Canadians, the only goo d store I ve found is http ://www.escience.ca/home.html the y have a large lo ca tion in
the Toronto area, but rather high pricing.
Hope that helps.
On an unrelated topic that does not merit its own post: Why is it that H2O2 accelerates the rate at which HCL eats metals?
I ve never figured it out.
T_Pyro December 7th, 2003, 02:23 AM

I think basic lab glassware (beakers/test-tubes/measuring cylinders, the works) is easiest to get through auctions/resales etc.
That way, you can also save your money for other exotic equipment like ball-mills, weighing scale etc. While just starting out,
it's a bit difficult to balance your funds between chemicals and equipment, so I'd suggest using makeshift utensils initially,
and slowly acquiring proper lab glassware as you progress.
Though not an integral part of the "laboratory", if you're going to spend most of your time conjuring pyrotechnic mixtures,
you'll find a sandbox/sandpit useful for testing out your pyrotechnics compositions safely, and close to your lab. It'll save you
the trouble of driving over to the nearest barren ground just to test a mixture.
Tuatara December 7th, 2003, 04:19 AM

Aside from glassware you'll need somewhere to do your stuff. Thats bench, sink, taps, drain, power, vents. Go scout your local
demolition yard for those sorts of things - I scored two proper lab taps for $NZ10 each (the sort with the tall up-and-over
standpipe, and a barbed hose fitting on the end). When I built my house I designed in a photo darkroom - it now doubles as
chem lab!
I got really lucky with the glassware - the med co my wife was working for decided to quit selling Schott - so I got three
carloads for FREE! :D :D :D Favourite pieces would be the 3l round vessel with the 5 hole clamp-on lid, and an all glass burette
with a fancy vacuum self-filling thingy designed to sit in a stock bottle. After browsing the online stores I've come to realise
I've walked away with about $3k worth of stuff.
Zeitgeist December 7th, 2003, 04:23 AM

Just don't make the same mistake as me, and assume a big Pyrex pot from the supermarket will survive being put on a gas
burner
frogfot December 7th, 2003, 04:24 AM

By things that you will need in your next experiment. That way you'll have a lab very soon..
On weighting scale subject.. recently got a broken scale for free: 6kg 0,01g. When it's turned on, it shows "overloaded", so I
gonna save it until I can fix it.. hope it's not the sensor.. maby somebody got a "magic" solution for this :)
Zeitgeist December 7th, 2003, 04:30 AM

Just noticed your unrelated topic Hang-Man
I think that the H2O2 is a stronger oxidant than the H+, and the dissolving of any metal is really just redox. I use H2O2/HCl
to etch printed circuit boards, but you can leave a board in conc. HCl for a week and nothing happens.
Once it's oxidised, the metal will happily dissolve in the aqueous HCl

I appreciate all the help and advice, I think I'm going to work slow, to get up to standard, like you said, I already have a .01g
scale, used for weighing something else ;) But I don't do that shit anymore so its free to use...anyhow I'll just check auctions
and slowly build from there. What about a good thermometer, I stole one from walmart in the food section, its digital, and I
calibrated it and everything but I read not to use those since the probe is metal...any suggestions on a good one? Possibly
digital...if not I'm making one at work
:D
Anthony December 7th, 2003, 02:28 PM

I think a probed thermometer will always be a problem considering the very corrosive chemicals that we usually work with. A
solution might be an infra-red electronic thermometer.
I don't see what's wrong with a traditional glass thermometer though. Alcohol filled ones are available from places that sell
home brewery equipment amongst other places, for a couple of dollars/pounds.
A hotplate is always useful, even just a kitchen one.

Anthony, I have one that uses infrared, I don't know why I didn't think to use it...How accurate are they? My dad uses them at
work and I have his at my place...let me know please :) Thanks

Those proper lab thermometers are very cheap, I have found them for $1.90 AU alcohol or mercury, they both cost the same.
But they break easy :(

I have a hard time reading regular thermometers though, that's why I like the digital ones :)
- Jared
Tuatara December 7th, 2003, 09:50 PM

The accuracy of IR thermometers is somewhat dependant on the material you are measuring. Obviously low emissivity
materials produce less IR than high emissivity ones - this is often solved by supplying black paint with the thermometer.
For a thermocouple meter there is no reason why one could not take a piece of 5mm glass tube, melt seal one end, then
insert the thermocouple, then seal around the thermocouple with silicone or epoxy. That way you get a nice , inert, accurate
digital thermometer.:) It is also possible to by stainless and inconel thermocouple probes.
Ordinary glass thermometers are plenty strong enough as long as you don't use them as stirring rods!:rolleyes: Though I will
concede they are hard to read when covered in condensation.

Tuatara
Are you talking about using a thermister to read the temperature?
Tuatara December 8th, 2003, 12:00 AM

No, I'm referring to a thermocouple, which is two dissimilar metal wires bonded together. Heating the bond creates a small
voltage between the two wires, dependent on the temperature. Search for 'Seebeck effect' (sp?). Most commonly used is the K
type thermocouple,. Thermometers using K type thermocouples are quite cheap.
Some thermocouples:
type T : copper / copper-nickel : up to 350 C
type J : iron / copper-nickel : up to 700C
type K : Nickel-chromium / nickel-aluminium : up to 1200C
type N : nickel -chromium/ nickel-silicon : up to 1250C
type S : platinum-10%rhodium / platinum : up to 1500C
type R : platinum-13%rhodium / platinum : up to 1600C
Thermistors can also be used, but tend to be non-linear, and need calibration as their response depends on their physical
dimensions as well as their material properties, whereas the Seebeck effect is only a function of the metals used.
Silicon sensors are also available, but can't be used much above 150C.
wrench352 December 8th, 2003, 03:39 PM
Heres a link to a great site:
International Order of Nitrogen (http://www.nitrogenorder.org/lessons/household.shtml)
Every thing you wanted to know about setting up the homelab but were afraid to ask ;)
Also odd lots of glassware, in various sizes, can be found on Ebay at sometimes good prices.Actually you really can by just
about anything on Ebay.I have a real human skull paper weight/candleholder I just got,really sets off the lab,you know.Im
hoping to get a hoplate stirrer for my Birthday.10x10 Corning
mmmmmmmmmmmmmmmmmmm,hotplate stirrer
(drools)
Skean Dhu December 8th, 2003, 06:32 PM

while searching for chems on eBay I stumbled across this
http://cgi.ebay.com/ws/eBayISAPI.dll?ViewItem&item=2578421348&category=11812
small setup but everyones gotta start somewhere, if I weren't saving up for a computer I'd consider buying one. the keywords
were'Laboratory equipment'
"seek and ye shall find"
vap0r December 8th, 2003, 06:39 PM

this seams like a nice set or starter glass as well. http://cgi.ebay.com/ws/eBayISAPI.dll?
ViewItem&item=2579328892&category=26406
Skean Dhu December 8th, 2003, 10:33 PM

good thing this guys isn't a chemist, otherwise the price would be considerably higher. you'd be lucky to find 30pcs for that
price. especially since most of its for distiilation
flashpoint December 9th, 2003, 02:25 AM

yeah tell me about it

Well..I stooped down and had my sniping ebay program snag it for me...at 148.50 total, I was pissed as it came from 38.00
to that :eek: Good find though, I appreciate it. Now just a few more pieces to collect.
Chemiboy December 15th, 2003, 11:35 PM

I totaly agree to blindreeper: "I think you cant buy everything you need in a lab at once, it kind of grows, like a garden"
in my country (Austraila) chemicals and equipment are hard to obtain. The chemicals comes slowly to u if u try to look for
them, but comes in small quanties and also not very pure.
So i just want to tell every one who is in other countries that u get many chemicals easily, always be against the people that
get themselves busted with explosives because, one day ur country will be like Australia.
Anath December 16th, 2003, 04:38 AM

I'd just like to point out that this statement..
"in my country (Austraila) chemicals and equipment are hard to obtain"
Is factually incorrect. I believe that what the original poster meant to say was.
"in my country (Austraila) chemicals and equipment are hard to obtain, if you are lazy, have a bmx as your sole means of
transport, and look 12 years old"
Australia is probably one of the -easiest- civilised countries to obtain OTC chemicals, Pyro supplies (second only to America),
and lab grade reagents, equipment & glassware in. It just takes a bit of know-how, (and know-who) and a willingness to get
off your arse and have a look around. See Blindreeper's excellent Australian OTC pdf for a (small) example of what you can
buy here easily.
Sometimes good suppliers just won't sell dangerous chemicals to little kids.. This is not a bad thing.

"in my country (Austraila) chemicals and equipment are hard to obtain, if you are lazy, have a bmx as your sole means of
transport, and look 12 years old"
That's got to be the funniest thing I've read, concerning little "KEWLZ". Out of all the Austrailian people on this board, it
seems, 99% of them don't have a hard time finding most chemcials...
metal dragon December 16th, 2003, 11:29 PM

As an Australian I sometimes have trouble finding chemicals but others are easily obtained so it really means where you live,
how much cash you got, etc. But some Australians over exaggerate about how hard it is.
Ammonal December 17th, 2003, 02:59 AM

Well I was nearly going to complain about certain things but since I just ordered a kilo of 98% purity KNO3, and some 50%
H2O2, I think living in Australia is tops! :D
And all it took to locate the source was a Google search, maybe I am giving away answers to KEWLS here, maybe not because
theyre too preoccupied with whatever it is they waste theyre time on to actually look beyond other peoples sources for things.
Look and ye shall find.

they beat off to much to do a search Ammonal :D
blindreeper December 22nd, 2003, 05:19 AM

Only one kg of KNO3? Thats not much, it will go fast!
Blackhawk December 22nd, 2003, 07:20 AM

I'd give my left testical for some KNO3, oh well time will yeild all :( I have ways of getting it, but I will wait, I have so much on
my plate ATM anyway, a little wait won't hurt and I learn more in the meantime.
blindreeper December 22nd, 2003, 08:08 AM

Blackhawk, contact me about KNO3 ;)
Ammonal December 22nd, 2003, 08:27 AM

A kg should be enough to do how much fuse? This is my only use for KNO3. Appart from terrorising mailboxes with KNO3/
Sugar :P And anyways this is the first place that sold me KNO3, 50% H2O2 (Thanks Blindreeper, I love the Aus OTC PDF) and
some Nitric acid no questions asked and I watched the guy burn the reciepts :D Gotta love the business weed growers make!!
Jackal919 December 25th, 2003, 06:34 PM

Here's a handy site for building your lab, http://www.geocities.com/capecanaveral/lab/4444/making_a_small_laboratory.html

On McMaster's (the university) site I found this:
http://www.science.mcmaster.ca/glass/
Basically the university sells glassware. They also make custom glassware. I don't know if their prices are intended to sell to
research labs, so if they are it might not be a feasible source of glassware. Otherwise it could be handy.
zeocrash January 8th, 2004, 06:53 PM

I'm still in dire need of a proper distillation set up.
I found ebay was not the place to look though as none of the quickfit pieces seem to fit each other. :( ah well if any of the UK
members are getting rid of a distillation setup tell me.
atlas#11 January 16th, 2004, 02:14 PM

http://www.freyscientific.com is a great company with a bad site. if you request the catalog you can get evry thing you need
except chems, that is unless your a teacher or something. their glass ware is quite cheap and they have it all distillation
apparatus, filtering flasks, tubing you name it. as for now i'm still saving up so i'm using one quart mason jars for everything.
tom haggen January 23rd, 2004, 01:07 AM

I'm looking for a complete vacum distillation setup. Included with a condenser, a proper vacum pump, a ring stand, some
hoses, and the proper fittings. does anyone know where to find something like this for sale that is fully assembled?
Mendeleev January 23rd, 2004, 09:27 PM

Tom hagen, www.unitedglasstech.com they have a 1 liter vacuum apparatus for $150, but no vacuum pump. I am hoping to
buy a 12 liter distillation apparatus from www.unitedglasstech.com with 2 12 liter flasks, a 600 mm Vigreux column, a three-
way adapter, thermometer adapter, vacuum adapter, and a 600 mm liebig condenser. This costs about $800 :(. If I decide
not to go this way I will place a $600 order at www.elementalscientific.com and have tons of beakers graduated cylinders,
meker burner, ringstands and clamps, hotplate/stirrer, and scale deliverd. Could anyone describe to me how effective are the
various condensers, like liebig, west, graham, and others? Also do I even need a 600 mm Vigreux column?

A vigreux column is useful if you're separating liquids which have close boiling points and are miscible with eachother. The
smaller the difference in boiling point, the longer the Vigreux column should be.
Cooling capacity only matters when doing reflux, to make sure nothing escapes out of your setup.
A liebig cooler is very ineffective, because of laminar flow. The "snake" cooler (alternating bubbles) is quite an effictive reflux
cooler. For substances with very low boiling points, Graham or Dimroth coolers should be used.
Xioa January 24th, 2004, 08:14 PM

Though this is slightly off subject, it's the only thread that i could find that would relate to my question. My lab is pretty ideal
for me, the only thing i need is running water in it. Is there a cheap way (installing plumbing is too damn expensive) to get
running water into my lab? The lab is seperate from my house and is a good 30 ft from it. Thanks.
SpiffyVision January 24th, 2004, 08:32 PM

This place also sells beakers and such for a good price http://www.enasco.com/prod/Home
Mendeleev January 24th, 2004, 11:05 PM

When you say low do you mean like ammonia gas low, nitric acid low, or need liquid nitrogen to make it liquid low? Just as an
example what would be the ideal condenser for say nitric acid (bet you never saw that coming ;))?
grendel23 January 25th, 2004, 03:43 AM

A retort can be used to distill nitric, so you don't need an ultra efficient condenser to get good results, I use a 300mm liebig
and it works fine.
If you are planning to distill more demanding substances, then a west, graham, or allihn may be a better choice.

You wouldnt happen to have a picture of your set up, would you grendel?
ossassin January 25th, 2004, 12:59 PM

Not much has been said about location. It would be hard for me to make a lab inside of my house. Would something in a little
shed work? How much ventilation should I have? How do those of you with parents manage to hide everything?

Xioa, how about leading some cheap garden hose from the house into your lab?
I was also thinking about homemade ventilation hoses made from polyethylene bags. They could be easily fused together by
an iron to any diameter..

I was also thinking about homemade ventilation hoses made from polyethylene bags. They could be easily fused together by
an iron to any diameter..
You're kidding, right? PE bags have virtually zero resistance against oxidizing acids, especially in vapour form.

No Vulture, he's not kidding... LETS JUST USE TEFLON BAGS!!!
T_Pyro January 25th, 2004, 11:19 PM

Then how about HDPE? I've seen some acid/alkali (including conc. acids) resistant HDPE measuring cylinders, but acids in
vapour form (especially at high temperatures) are quite different...
Mendeleev January 26th, 2004, 01:18 AM

Sorry, another sort of newbish question about distillation. See I've been using brainfever's ghetto set up with two beakers
which works just fine, but I know little about the real jointed glass set ups, so I was wondering what type of flasks would be
best for distilling: round bottom boiling, flat bottom boiling, erlenmeyer, or pear-shaped?

SpiffyVision,
Here are a couple of pictures of my setup, here (http://www.geocities.com/sulfuric23/glass.jpg) is the overall setup, here
(http://www.geocities.com/sulfuric23/head.jpg) is a closer view of the head end, and here (http://www.geocities.com/sulfuric23/
tail.jpg) is a closer view of the tail end. Cut and paste URL's into your browser.
What you are looking at is a 2000ml round bottom flask at the hot end, a distillation adaptor with a glass stopper in the
unused 24/40 opening at the top and a thermometer in the 10/30 port wrapped with Teflon tape to seal it. Then a 300mm
liebig condenser, a 105 degree vacuum adaptor, and a 1000ml flask at the cold end.
For clarity I am not showing some parts, I have a mantle on order to heat the large flask, I am tired of improvised heating
setups, I also use a ice water bath around the receiving flask, with a submersible fish tank pump to circulate cold water
through the condenser. I also use a piece of Teflon lined vinyl hose to attach the vacuum adaptor to a filter flask set up as a
water trap, also in the ice water, then to an old medical vacuum pump that will draw 20" of suck, just about right. I have spent
about 6 months collecting bits when I could get a good deal.
Mendeleev, If you are thinking of running vacuum you must use round bottom flasks in perfect condition, no cracks, chips or
heavy scratches.
Blackhawk January 26th, 2004, 06:17 AM

Your pictures don't work for me, not copy and pastable and the page has not exceded it's data limit.
frogfot January 26th, 2004, 08:27 AM

Vulture, can you define "zero resistance"? (thats sounds as if it was aluminium foil vs pure chlorine..)
We're talking about home lab that will output small ammounts of corrosive/poisonous crap, in small concentrations that is.
Most of it can be absorbed by washers/active carbon filters on exit from your apparatus, even in real labs they try to absorb
most of dangerous exhaust gases.
After all, who in your negborhood wants a half kg cloud of some toxic/corrosive byproduct gas from your reaction? :p
IMO, as long as PE pipe does not fall apart, it will be suitable for amateur lab.
Jacks Complete January 26th, 2004, 06:35 PM

frogfot,
he isn't talking about plastic pipe, he is talking about melting plastic bags together! I have no idea how you would ever get a
good seal over the dozens of joins you would need?
If you want to do that kind of thing, just buy tumble dryer ducting. At least that won't have holes when you start!
frogfot January 27th, 2004, 06:35 AM

Ofcaurse I meant bags, a 1 m PE pipe of that diameter would cost me 10-20$!!
Anyway, one can make segments by fusing big PE sheets with hot iron :) it's very easy to make good seal, just have to place
some paper between iron and PE, else it will be messy.
The segments can then be "mounted" together by some strong elastic tape..
Yeah.. I never said low-budget would give quality, well enough quality for less than 1$ :)
(gonna try this now..)
EDIT: hihi, that was fun.. :p I realised that tape is much better than iron..
Heres a pipe consisting of two segments:
http://www.geocities.com/frogfot/stuff/ventpipe.jpg
Gonna use it next time I melt candy propellant (paraffine stinks) together with homemade fumehood...

Blackhawk,
The links I posted work for me if I right click on the links and use "copy shortcut" then paste into the browser address bar. I
am using IE, are you using something else?
Is anyone else having problems with these?
SpiffyVision January 27th, 2004, 10:21 AM

Their working for me, where did you get that setup grendel?

I have access to a large supply of glassware, and since a few items disappear from the annual inventory anyway, I think I'll
add a few of them to my collection. :) Right now I have a 250 mL beaker, a 600 mL beaker, a 100 mL graduated cylinder, 2
glass stirring rods, and various bottles. What would you recommend grabbing? Thanks.
By the way, I'd rather it be something very common like a beaker or a flask. Things like condensing tubes would be missed.

If I had the choice to grab something common, given what you already have, it would either be a larger beaker such as 2-4L
or better yet a one liter erlenmeyer flask or one liter flat bottom boiling flask as they can be made into a pretty good distilling
apparatus using a rubber stopper and PVC pipe like here http://cavemanchemistry.com/cavebook/chalcohol3.html .

Good idea, I'll look for some. Any other suggestions? Can strong acids be stored in simple glass bottles? Should I grab a few
special ones?

Yeah, all acids except hydrofluoric can be stored in glass, and some in polyethylene coke bottles.
Bert January 28th, 2004, 01:54 PM

Will using a flat bottomed boiling flask under vacuum lead to an implosion?

What sort of top would be needed for the bottles? Would plastic be OK? It seems like strong acids would melt that. Some sort
of stopper, maybe?
EDIT:
I'm actually there right now, so if someone responds quickly, I'll grab it.
T_Pyro January 29th, 2004, 01:02 AM
"Plastic" is a very generic term. I've seen some HDPE stoppers which are used to seal 98% H2SO4 and 70% HNO3 bottles. On
the other hand, there have been reports by other members about 98% H2SO4 melting their plastic vessels. If you're going to
rely on plastic, I'd suggest leaving a small sample of the plastic submerged in a small quantity of the most corrosive (for
plastics) reagent you'll be using, for at last a week, and then checking for signs of disintegration.
On the other hand, if you're getting your concentrated acids from a laboratory supplier, you should get them in a glass bottle
with a stopper of its own. Why not use that itself? That's what I do.
ossassin January 29th, 2004, 01:49 AM

Just in case anyone is interested in a follow-up, I had another successful mission today. My haul consisted of a 1000 mL
beaker, another 250 mL beaker, an 80 mL beaker, a 40 mL beaker, a 1000 mL earlingmier flask, a 500 mL flask, a 250 mL
flask, a 25 mL graduated cylinder, a medium-sized bottle of 95% denatured ethanol (has not been measured yet), an alcohol
burner, and a small jar of powdered citric acid. There were plenty of these (http://roguesci.org/megalomania/equip/
glassware.html#flask) (#6), but I just didn't have any more room in my bag. What are they, and how valuable would one be
to me?
Bert January 29th, 2004, 02:09 AM

It's a distilling flask, and you wouldn't want one unless you were distilling nitric acid from sulfuric acid and nitrate. And no one
here would ever want to do something like THAT.
ossassin January 29th, 2004, 09:37 AM

:cool: Great! It's rounded at the bottom, so is it safe to heat it over an open flame? It looks like it would be hard to use a
hotplate. An oilbath maybe?
tom haggen January 31st, 2004, 10:59 PM

I just added on to my collection of goodies. To me this seems like an essential piece for my lab. I basically got this so I can
work around Nitrogen Dioxide in poorly ventilated areashttp://www.geocities.com/grandpa_jacob/night_vision.html?
1075603677388
tmp February 1st, 2004, 11:07 PM

Someone asked about venting fumes. I found that a window fan
works very well for my chlorate/perchlorate cells. I keep the cell
in front of the fan. The fan, of course, is set on reverse to draw
the air out.

I own a glass pitcher that is designed for holding extremely hot liquids. I'm kind of a poor guy so I use this instead of buying
nice glass ware. I also have one of those portable stoves with a heating element. I have set the glass directly on the heating
element before and it worked pretty good. I was just kind of nervous about setting my glass container directly on the heating
element. I could probably use a pot filled with sand instead of setting my glass container on the heating element. But does it
really matter since i'm only boiling off water at 100C, or is there a risk of my glass cracking? You would think that there would
be some danger when placing and removing the pitcher on and off the heating element, seeing as how glass an metal aren't
great friends. However, that's not my concern. My concern is the uneven amount of heat due to the spaces in between the
coils. Any advice would be greatly appreciated.
-Tom Hagen
wrench352 February 6th, 2004, 12:27 AM

Hmmm,this would be better in the purifiying sulfuric acid threads wouldnt it?But then youve worn out your welcome there
havent you. I had basically answered your question Tom when while searching on the subject so as to avoid giving you bad
info,I saw some of your other posts.
If you are too lazy to look this stuff up yourself(I found your answer on this site in about 15 minutes) then you are to lazy to
research the hazards associated with whatever it is your cooking up. Blindly endangering not only yourself but whomever is
nearby.Im through with you.Hey yall check out his posts here and sci mad. The scariest thing, it looks like he's wants to make
NG. :O
tom haggen February 6th, 2004, 12:49 AM

http://www.roguesci.org/theforum/showthread.php?threadid=1899&highlight=nitric+acid+synthesis Well wrench buddy, I
searched and found this post. It sure does talk a lot about what I am getting at, gee what do you know. But what I'm getting
at is that I have a glass pitcher, and I know for a fact that I could stick this son of a bitch in a 350F vat of oil with out any
problems. You see as I said it will with stand high temperatures. But no one really says anything about placing a glass beaker
on a heating element. I thought that thread I found was pretty damm close to figuring out my question too. By the way why
would this post belong in the purifying acids section? In my post before yours I said I wouldn't be above 100C, I thought most
acids have a much higher boiling point than 100C. Also, you are correct i have definitely worn out my welcome in that thread.

I did some research and boiling flasks are apparently the prefereed choice for distilling. I expected as much, but I am still
unclear, as to whether flat bottom flasks can be used for vacuum. I believe Bert also asked this question and did not have it
answered. For some reason most of the "ready to go" fully constructed distillation apparati sold from labware suppliers are
usually made with round bottom flasks, which in my opinion is a bit inconvenient due to the requirement of a heating mantle
as opposed to a hot plate and the inability to use a magnetic stirrer, so why are round bottom preffered? Is it because flat
bottom is incompatible in vacuum like Bert said?

Heres the flat bottom flask I have been talking about. www.geocities.com/grandpa_jacob/night_vision.html?1075604701466 I
found it in my kitchen its for holding extremely hot liquids. Putting it on a heating coil makes me nervous. I think i'm just
going to use oil baths with this flask. It can hold 1000ml.
grendel23 February 7th, 2004, 05:50 AM

I am not sure that a flat bottom flask would implode, but the results of such an event when distilling HNO3 under vacuum
would be so nasty that I cannot imagine why you wouldn't do everything you can to ensure a safe procedure. I might be willing
to try an less than optimum rig at ambient pressure, but not with vacuum.
By the way, they make stir bars for round bottom flasks, you can just put the mantle right on top of the stirrer.
A good distillation setup costs quite a bit, but if you are serious about this hobby, its worth every cent.

When it comes to a vacuum in a round bottom flask, The pressure is spread out evenly do to the geometery of the flask. The
right angle in a flat bottom flask does not have this same advantage. All of the force is directed right in the corner of the flat
bottom flask. Sorry if this is stating the obvious, but its what I do best.
atlas#11 February 11th, 2004, 10:34 PM

tom, If that beaker is pyrex then you shouldn't have to wory about it, if it was flint glass I would keep it under 100C. I use my
1L beakers on a hotplate at 1100 watts without problems when concentrating sulfuric, it all depends on what kind of glass it is.
As far as vaccum flasks are concerned, it depends on the thickness of the walls, the desisired pressure, the temperature, etc.
United glass tech( http://unitedglasstech.com/)sells there erlenmyer flasks with 24/40 joints for relativly cheap prices and they
are suposedly able to withstand quite a vaccume(did you mean flat bottom round flasks?). Currently I am working my ass off
to save up for a good distilation app. Think I'll go for the 600mm grahm condenser with 24/40jts. I will get the vaccume
adapter so I'll be shoveling horse shit for months to save up that kind of money :mad: .

The vacuum adapters are not at all that expensive, its that damn 12 liter three-neck flask that I'm saving up for.
tom haggen February 12th, 2004, 03:43 AM

atlas, I think my beaker is pyrex. However, it doesn't really say. I have boiled water with it a few times now just to make sure
it is not going to crack. I think its made out of the same glass that people make coffee pots out of.
atlas#11 February 14th, 2004, 11:51 AM

If it's for high temps then no doubt it's pyrex. Mendeleeve, what do you want a three necked flask for? Are you distilling 3
gallons of nitric at a time or what? And where on earth did you find one?
Jacob Kell April 8th, 2005, 09:10 PM

Can somebody tell me if there exists a simple distillation apparatus, just without a chance of anything getting out? I mean, no
holes for termometer, vacuum, with joints that can be hermetically sealed. I need something for concentrating sulphuric acid
and making nitric, and I am afraid of fumes, I dont want anything to get out of it. I also live in apartment. has anyone seen
such a thing somewhere for sale?


Aristocles December 25th, 2007, 11:20 PM

Allow me to resurrect this thread... hopefully it doesn't fall into the "necromancy" category ;)
Here's a copy and paste of what I tentatively plan to purchase tomorrow or the next day:
Flask, 3 neck, standard joint, 1000ml, 24/29x3

$29.95 $29.95
Teflon Joint Tape 1/2W x .003 x 260"
$1.50 $1.50
Simple Distillation Kit w/ 1000ml Flask & Hardware
$39.50 $39.50
SUPPORT STAND w/ ROD Cast iron 5" x 8"
$11.20 $11.20
SUPPORT RINGS w/ CLAMP Cast iron 3"
$5.60 $5.60
EXTENSION CLAMP w/ interlocking jaws
$6.31 $6.31
BURET CLAMP Rubber covered jaws One Buret
$4.60 $4.60
Allihn Condenser, 300mm jacket, 24/40 joints
$35.25 $35.25
Buret Class A Teflon Stopcock amber Straight 50ml
$27.95 $27.95
Does this look like a reasonable bare-bones beginning for someone interested in our hobby? I realize that to hyperbolically
generalize is silly but just give me your thoughts. I also, full well grasp that our experiments vary greatly but I'm just looking
for some rudimentary lab ware.
I have some glass vessels, scales, 'fridge', hotplate, thermometer, funnel, small oven, etc.
megalomania December 26th, 2007, 07:08 AM

Those prices are quite reasonable. It is hard to quantify what would be useful without knowing what kind of chemical
manipulations you intend to do, like you said. Personally I find 3-neck flasks to be of little utility; adapters can always add
additional functionality, and the extra openings can be inconvenient when you really need just the one. "Find the glass
stopper" is a terrible game we all are forced to play in the lab :(
I used to buy stuff that I thought I needed, but I ended up never using it. I like to ask myself a simple question, "do I have
a need for this, or do I just want it?" Do you really need 1000-mL flasks? Can you fit those with your heating mantles? Do you
want to make things on that scale? I used to love the big stuff, but now I embrace microchemistry. An experiment works just
as well (better usually) at 50 mL than it does at 1000.
I am not saying don't buy the stuff you want, just to stop and mentally picture what you will need. I always close my eyes and
try to imagine myself doing a reaction before I do it. I concentrate on the little details, bits of equipment, and reagents, that I
need so I can gather them up. If I don't have it, I can't do the reaction. It is better to realize this before you start something
than after a reaction is underway. If in your mind you do not use the stuff you want to buy, don't buy it.
Charles Owlen Picket December 26th, 2007, 10:00 AM

The first time I got a chance to get a decent distillation rig, I bought one that came in a briefcase. I wondered why they
thought it needed so much protection but was happy with the price. I realize that it was an attempt at portability but it was still
nice to have; in that glass is actually the largest expense of my lab. Although fairly cheap by today's standards; it was only
offered in a larger volume level for both receptacles. I thought that if offered between 500ml or a L that it's better to have
larger as I would always cut volume but not expand, if I didn't have the size to begin with.
Personally, I never had a big use for 3-neck flasks and since then I heard that a lot of cooks get them set up to speed-up a
synth and some jack-offs have put them on a "watch list" of glass materials... At the time I thought: "Good grief! They watch
fucking glass now." And bought up all the stuff I needed. I noticed at the time that the less expensive was in a 24/40 format
or I would also have bought on a smaller scale.
Aristocles December 26th, 2007, 05:47 PM

The three-necked flask has been shit canned. Thanks for the help.
I've tried to order but keep getting the answering machine... perhaps not everyone rushes back immediately following
Christmas.
To me, the dictum about mentally picturing picture the detailed setup has helped. (Truth be told, the three-necked flask
failed- actually it seems superfluous, for my purposes)

Indeed 3-necks are on the fedgov watch list for Kalifornia, and probably Texass (they watch almost everything now). The
strange thing is I don't recall any meth recipes on the Hive that actually used 3-necks, but trying to find logic from fedgov
motives is impossible.
I should say it is nice to have a large flask when you need it because it is better to do a reaction in an oversized flask. A flask
should be filled to no more than 50% of its capacity for safety reasons.
Personally, I prefer to use silicone grease to seal standard taper joints. It makes for a tighter seal, it helps keeps a joint from
getting frozen (stuck forever), and they tend to stay attached better. It also makes for a quicker setup and teardown of
glassware, but you will have to wash everything by soaking in a base bath after use. I do vacuum work, so grease is really a
requirement for that. I also like to keep a spool of wire and wirecutters handy for securing vacuum and water lines to the
appropriate ends. A squirt of acetone in the end of a rubber hose really helps get the sucker slip on (a condenser for
example). Keck clamps are also useful... These little incidentals should be factored into a setup because they can save you
from breaking expensive glassware.
Barnacles December 27th, 2007, 04:23 PM

I just ordered a distillation setup, this is what it came with!
I have a few questions! I wish I had thought of before. Is it common for these sets to come with all the stop cocks I will need?
And can I heat these flasks with a open flame? for non-flammable- non explosive reactions obviously? and mega maybe
there is no reason other than to test the waters of what they can and can't watch without raising a stink. and getting their foot
in the door.
1 x 2000ml Round bottom Flask
1 x 1000ml Round bottom Flask

1 x Vacuum (Bent, 105 degree) Adapter
Distilling 3-Way Adapter
1 x 300mm West Condenser
1 x Threaded Thermometer Adapter (w/Nylon bushing top)
1 1 x Full length -10C to +150C Thermometer
1 x Medium Size Kit Stand (5" x 8" Stand, Rod 20" high)
5 x 24/40 Plastic Keck Clamps (to hold together the different units)
1 x Metal Utility Clamp

You don't have anything on your list that would include a stopcock. They are typically included when a bit of glassware uses
them. Typically, but not always.
You can heat your flasks with an open flame, yes.

-> One note when distilling nitric acid; your "Threaded Thermometer Adapter (w/Nylon bushing top)" will go to shit from heat &
fumes. Most everyone's does after about half dozen distillations. When distilling nitric, remember the setting on your heat
source and replace the above with a plug of Teflon so it doesn't get messed up.
Most people think they won't distill nitric that often but when you can; you do....The first few months of "new glass" in the
period of most intensive use. have fun!
Barnacles December 28th, 2007, 04:47 PM

Thanks for that, dually( now how do I spell that word again always thought Duelly) noted.
I have a few questions sorry to bog up the thread.
Now that I know that, Wont that be a place that a stop cock could come in handy? Will the nylon melt into the acid causing
some unwanted reactions rendering the nitric acid useless for nitrations due to some ultra unstable nitro nylon or something?
Could I just wrap it in Teflon tape to stop that from happening ,but that may affect its temperature taking?\
Right about now I am wishing I spent a bit more time readingg about which would best suit me. But I had finally just put
together enough money that I was able to spend on such things for the first time in years so was pretty excited and went
ahead and bought it.
PS you must be psychic you read my mind about its purpose.(lol who would think a roguesci'er would want Nitric Acid JK)
PS2 I got it off of United Glass TECH. Gave me free shipping when I asked nice enough, I told them I would upgrade from the
1 literx500ml to the 2000x1000ml for free shipping. That was the setup I was going to buy anyway, but they are really nice
definately recommend them <no I am not UGT lackey, Mega can confirm my IP is not from the area of UGT.
Man Down Under December 29th, 2007, 06:21 AM

Why not replace the nylon with a teflon O-ring? They do make them.

United Glass are good people; I got some stuff from them also. You know that setting up your lab are YOUR lab concepts in
action; if you think a stop cock could be worth the expense rather than a plug or what-have-you, by all means do it. You will
know best what has utilitarian value.....to you! You may find that you do somethings on the cheap & others, you put some
dollars down to.
My method (which certainly doesn't mean it's a good one) was to get two of everything so if I had breakage, I wouldn't be
sidelined. My emphasis went into that concept. In other areas I went cheap. My condensers, let's say, I'd look at using a
cheap Clausen or some shit, rather than a high end big-boy. I bought used, a HELL of a lot of times! Any simple shit, I would
get those Chinese beakers and flasks; you know what I mean.

Where do you get your used stuff from, Charles?
I like to use Chemglass products, their prices are the best I have seen for standard taper glassware.

This is my technique: I have folks I know at the local university. I know students, I hang out in the lab, etc. I also know a guy
who is in the chemical business. I hit them up consistently for old stuff. You would possibly be shocked that salvageable glass
goes in the dumpster due to the need for spending; in and of itself.
A university (as you may know) has a budget that they MUST spend in order to get next year's at or above the previous level.
They NEED to have a need. The trick here is to get a connection.
I won't go into too much detail, but you get the idea. You must cultivate the local resources (even a "community college" - a
fucking secondary school) in a manner that allows them to use you as a way to get the stuff from their lab. It's an exercise in
creativity... But it can be done. You might even be impressed in the amount of stuff I have gotten. But you need to take the
shit with the gold in this as they want it OUT of the lab. Later you can sift through the goodies and keep what you want and
shit-can the rest. But you have to clean house for your source.
If you have a connection (close) with someone who either has a chemical business (let's say Water Treatment; that's a gold
mine) you let him or her know that you want the chemicals or stuff that they can get but have to order in large volumes. Then
you kick them down a few bucks so they can make a large order and save $.
I do the OEM thing a bit. I once got several air-bag units & salvaged about 800gr of azide from them, however it turned out
that a bio-lab uses NaN3 for cleaning up and they were getting it for $40 a pound at a purity level that was astounding....close
to the cost of an OEM source. But when I need glass there are so many ways to get used stuff that I have to make a decision
on what is WORTH buying new. I have a source for cheap (we're talking $8) sep-funnels. They ARE really cheap (Chinese) but
they work and have Teflon pet-cocks. A high-end funnel just ain't worth it (to me).
I can go on and on but it's better to PM me if any of you have more involved questions. I don't do anything inappropriate or
illegal but I do get some wonderful things that would cost a mint in this manner.
Aristocles January 2nd, 2008, 09:10 PM

Well, I recieved the UPS tracking number today... 'so I guess my shit is in the ether'
Man it was like trying to untie the Gordian Knot to get the stuff ordered from the original place.
I am an impatient bastard.
So I ordered from another place:
http://www.pelletlab.com/p_g_distillation.shtml
I purchased item LB120-1000K
http://www.pelletlab.com/p_g_burette.shtml
I purchased item LB74-50
http://www.pelletlab.com/p_l_support.shtml
I purchased item LB73-20C
http://www.pelletlab.com/p_l_clamps.shtml
I purchased item LB71-1
http://www.pelletlab.com/p_m_thermometer.shtml
The temporary goal will be to distill nitric acid. I am thinking I'll need an aspirator, also...
An interesting hobby... I'll be completely broke within two years from buying glass and chems, OCD does have it's bad side...
pyromaniac_guy January 2nd, 2008, 09:42 PM

did a quick search and haven't seen them mentioned in a while so i figured I'd make a little reminder post. When shopping
for new goodies dont forget to browse dovebid.com along with labx and ebay. you normally wont find any 5$ specials, but you
might pick up a perfectly good 500 MHz nmr set up for a thousand clams if no one is paying attention....
Charles Owlen Picket January 3rd, 2008, 08:55 AM

Aristocles:
That looks like a good start.
Everyone who spends $ for the glass portion of a lab faces choices as to where and how to spend the real money......What you
get from the vacuum is efficiency; that's certain. But it's not mandatory in all situations. An aspirator is cheap but can be a
hassle. The choice then becomes one of expense.
I had a chance to get a serious unit. A vacuum / pump that was a lab unit but would cost me 600 bucks. It sold new for over
twice that amount. It simply wasn't worth the expense to me. I like getting 1.52 HNO3 but I can live with a few hundred ml
here and there; I don't need to make a liter at once. That may be the core of the issue.
Aristocles January 4th, 2008, 02:46 PM

Well...
I just ordered:
24/40 Vacuum (105 degrees) Adapter - $29.99
24/40 200mm 3-Way Vigreux Distillation Head - $37.50
500ml Corning Brand Erlenmeyer Flask, w/ 24/40 Top - $14.99
Free Shipping...
I am assuming that I will be SOL on the Graham Condenser mentioned in my prior post, as it does not have a ground glass
joint at the bottom (where distillate exits). I am trying to figure a way to get a seal between the vacuum adapter and the
Graham, that won't be eaten by nitric acid .
Ideas?
Charles Owlen Picket January 7th, 2008, 11:11 AM

I would Teflon tape the thing to death and let it be. Because you are going to clean up your glass anyway use the Teflon tape
as it's cheap (plumbing supply shit) and you just take it apart. I know you want something that would look more professional
but whose going to see it? Use the wide stuff.
There ARE urethane stoppers that are acid resistant (not proof) that can work. They will stand up for a long time but the heat
gets to them after about a half-dozen distillations or more. You can use urethane for a lot of connections; what's more you
can wrap them in Teflon tape and they'll work QUITE well. I have a urethane connection that looks very professional that had
held up for a very long time. If you can't get a hold of the stoppers proper; don't fret. Get some skateboard wheels and trim
them to size.
Remember you're distilling at about 80-90 C so the glass won't be getting much hotter than that. That's important, as you can
use a whole lot of materials that can be covered in Teflon tape that won't melt at that temp. Condenser-wise you really don't
need a good one, most anything will do for HNO3. Once I broke a good one I had (don't ask) and I just got a shit-load of
sodium glass and made a spiral (like an old-time still!) and my level of efficiency was close to what I had! (I used 1/4" 48" @
4.5" dia.) Here is where creativity reigns supreme.... the lab layout.
Aristocles January 7th, 2008, 07:04 PM

Thanks, Charles.
Encouraging and positive... damned good qualities

There are certain kinds of tubing with excellent chemical resistance you may want to consider using to connect glassware when
distilling nitric acid. I just got a new tubing catalog today... Fluran F-5500, Tygon Inert SE - 200, Norprene Chemical Tubing,
Tygon Plasticizer Free Ultra Chemical Resistant Tubing, Chemfluor FEP, Chemfluor PFA are just a few that offer outstanding
chemical resistance. I saw one type of tubing actually recommend it be cleaned by boiling in nitric acid, but I can't find it now.
You will have to verify which type of tubing can handle hot concentrated nitric acid. I doubt these are hardware store tubings,
but an online search should yield some by-the-foot sources. You should not need that much tubing for connecting glassware,
keeping in mind these exotic type materials can cost $2-$3 a foot (for small diameter) and >$10/ft (large diameter).

a n d I m provised C hemistry > O T - Malonic Acid synthesis
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View Full Version : OT - Malonic Acid synthesis
jimmyboy D e c e m ber 13th, 2003, 11:28 PM

If anyone could help i would a ppreciate it - ive been poring over organic chem isty books for a good while now - the only
detailed reference I've found is from v o g e l a n d i dont relish the thought of toying with sodium cyanide and chloroacetic acid - i
f o u n d s o m e m ore useful hints here - http://4.1911encyclopedia.org/M/MA/MALO NIC_ACID.htm and here http://
77.1911encyclopedia.org/M/MA/MALIC_ACID.htm
(by the way 1911 is a wonderful place to find chemical info)
It still doesnt give enough details -- i have som e perm anganate and sulfuric around -- i wonder if they could perform the sam e
o x i d ation or if they would spoil the malic acid(e asy to acquire) - or maybe i could oxidize with a copper catalyst -- i want to p ost
this on hive/lycaeum but they require a waiting period - would love any ideas/leads - thanks
ShadowA lchemist January 5th, 2004, 05:08 AM

The reason i am writing here is because i unable to start a new thread.
So i hope som eone sees this and realizes what the fuck im talking about!
Right I'll get straight to the point, no point beating around the b ush is th ere.
I a m curious to know if anyone has ever attempted to perform 'research' experim ents specifically involving Electro-Catylitic
Hydrogenation, but not specifcally reacting any particula r solution.
If one was knowledgable in a particular elemen t of orga nic chem istry, involving a particular saturated solution and a very
specific conclusion, th e n o n e m a y b e a ble to co ntribute to the discussion. O f course not publically, because if anyone is on the
s a m e wavele ngth as m e, then you of course realize the m atter is best discussed "behind closed doors" So to speak ;)
You know before christm as i h eard a great word..Festerlytic..Seem s to ha ve stuck in my m ind ever since, although i cant
im agine why?!
If your switched on and you've got spa rk, you'd best give m e a b u z z ! !

If one was anything but cluele ss in the ways of the forum , one would not post a p oorly veiled attempt at a reply entirly
unrelated to a thread m ostly forgotten in a forum completely irrelevent a nd for purposes painfully transparent.
This is a forum for public discussion and m utual help, not a recruiting ground for second rate drug chem ists.
If you're switched on and you've got spark then better be careful with explosives and weapons to avoid a very specific
conclusion.
L i f e i s a g a m e with a very predictable ending.
ShadowA lchemist January 7th, 2004, 11:48 PM

For your information Marvin, I was/am not at all interested in trying to 'recruit second rate drug chemists', despite what you
m ay think.
W h a t m a k e s y o u s o d a m n sure that i want/ed to talk about som ething, that is outside the barriers of discussion and mutual
help . Which you yourself pointed out, is the way this forum conducts itself.
I m erely wish to talk to others who may or m ay not have experience in the field of organic chem istry, who may or m ay not be
able to contribute to a discussion!
As im sure everyone has discovered by now, there are not too m any places left, where people who share a com m o n i n t e r e s t ,
dare i say a love for chemistry, can talk openly without the fear of being a labeled a terroist or (the one i like) "Destroyer of
Innocence"
And Marvin, life IS a gam e and it ALW AYS ends! Believe it or not, crims may die young, but at least we die fucking rich!
Rhadon January 8th, 2004, 07:39 AM

Let's keep this on topic, guys...

a n d I m provised C hemistry > Detonator Capsule Materials & Reactivities
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View Full Version : Detonator Capsule Materials & Reactivities
Bert January 10th , 2004, 10:14 AM

Aside from such obvious thing s a s n o t u s i n g a m etal capsules with HMTD and avo iding any metal but Alum inum or Tin with
picric acid, are there any other com patibility issues between the m etal of detonator capsules and the com m on prim ary or base
charges, especially in longer term storage? Copper and brass in particula r are both som ewhat reactive towards oxidizers, and
Copper catalyzes m a n y d e c o m position reactions.
In the Blaste r's Handbook the re are several references to using one m aterial or another for the capsule and lead wires of
electric caps- But these are all from the point of view of what might be an unacceptable contam inant in the raw material bein g
blasted. There is one thread here (that is, in the forum ) that recomm e n d s C o p p e r for fulm inate ca ps and Alum inum for all
others, but n o specific reason is given.
Crazy Swede January 10th , 2 0 0 4 , 0 5 : 5 3 P M

Since lead azide was, and still is, very com m o n i n d i f f e r e n t k i n d s o f d e t o n a t o r s , I g u e s s t h e r e a s o n w h y t h e B l a s t e r ' s H a n d b o o k
recom m ends only using copper for fulminate caps is to avoid the possible form ation of copper azide.
Bert January 19th , 2 0 0 4 , 0 8 : 1 7 P M

O.K.- Starting to answer m y own question...
First piece of information: Lea d azide is not com patible with brass or C opper deto nator capsules? Would Silver azide be
sim ilarly inco m p a t i b l e ? H o w a b o u t L e a d s t y p h n a t e ?
That would be inconvenient. C opper is such a widely available material and so easy to form , as I've learned while m a k i n g m y
own 6mm be nchrest bullets.
I'm sure there are m ore prim aries and base charge materials that Copper is incom patible with besides picric acid or its salts,
HMT D a n d L e a d a z i d e - C o u l d s o m eone with a bit of experience in these m atters take a m inute to post that informa tion or
suggest where I might find it in one place, rather than piecem e a l ?
I have a fair grasp of the chem istry of high tem perature flam e s , b u t o n l y a s m u c h k n o w l e d g e o f s o l u t i o n c h e m i s t r y a s h a s
b e e n n e e d e d t o s a f e l y p r o c e s s w a t e r b o u n d c o m positions. Kind o f the reverse of most of you chemistry types-
Thanks in advance-
grendel23 January 21st, 2004, 08:01 AM

I have read that my favorite primary, azo-clatrate, does not react to copper. It contains lead azide, but it is locked into the
m atrix of the clatrate and is not free to react. I plan on testing this m yself before attem p t i n g a n y c o m p o u n d dets in a copper
casing.
If you wanted to use a incom patible m aterial, a coating of paint or wax could be used to protect the capsule. There would be
s o m e r i s k o f t h e c o a t i n g b e i n g d a m a g e d d u r i n g p r e s s i n g , s o a c o m patible case would be preferable.
I a m going to obtain a bag of those quite wonderful loo k i n g j a c k e t s a n d d o s o m e "bullet swaging" myself.
Bert January 21st, 2004, 11:27 AM

I've found several references to azo-clathrate (clatrate?) in the forum a n d o n g o o g l e . I ' v e b e e n u n a b l e t o l o c a t e t h e
preparation however- Could you direct me to th at?
Jacks Complete January 21st, 2004, 06:24 PM

Bert,
have you got any stuff on the process you are using to form your copper benchrest bullets? That sounds like it could be fun.
Bert January 21st, 2004, 06:34 PM

e-mail me. It's not really on topic- It might belong in the tools, techniques & plans? Or water cooler...
grendel23 January 22nd, 2004, 05:16 AM

Bert,
Here are the patent (http://patft.uspto.gov/netacgi/nph -Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=/netah tm l/
srchnum .htm &r=1&f=G&l=50&s1=3431156.WKU .&O S=PN/3431156&RS=PN/3431156) and the thread (http://
www.sciencem adness.org/talk/viewthread.php?tid=501) referring to the azo-clathrate prim ary. I love this stuff, high
p e r f o r m a n c e , s a f e , s t a b l e , a n d e a s y t o m ake. The only real concern is the toxicity of the precursors. The best part is you can
m a k e 2 4 g r a ms of azo-clathrate with only 5.3 gram s of NaN3.
Bert January 23rd , 2004, 02:18 AM

grendel23- T h a n k s !
I l o o k e d a t t h e p a t e n t inform ation. As they had m ixed 25% ground glass with the various products for testing, the sensitivity
information isn't too applicable to the straight product. Has anyone done drop ham mer and/or friction shoe tests of this stuff?
From practical experience, how does it com pare to Mercury fulm inate or Lead azid e in sensitivity to handling?
demo January 26th , 2 0 0 4 , 1 0 : 4 1 P M

Hey, why not just use plastic tubes for detonators, I dont think that any explosive will react with plastic.
knowledgehungry January 27th , 2 0 0 4 , 0 5 : 4 4 P M
U n l e s s y o u h ave an explosive such as MEKP wh ich is a solvent ^^ or nitrom e t h a n e .
demo January 27th , 2 0 0 4 , 1 1 : 4 4 P M

Oh shit why didnt i think of that. Sorry of that I dont have much of a brain.
W hats the VoD of MEKP? It is not a strong explosive right.?
Microtek January 28th , 2004, 09:41 AM

Detonators can be m ade with plastic casing or even caseless without too m uch tro u b l e . C a s e l e s s d e t o n a t o r s h a v e b e t t e r
initiation ability due to the m ore intim ate conta ct between donor and receiver charge, but the problem is that they a re
s o m ewhat less resistant to rough handling than the metal-cased variety.
knowledgehungry January 28th , 2 0 0 4 , 0 5 : 0 9 P M

MEKP is in the same range of VD as HMTD and AP around 3500-5000m /s
al93535 Novem ber 8th, 2008, 06:51 PM

I want to make a cap with .1 gram s of milled BP. That is kno3, sulfur, com mercial charcoal, and trace conta m i n a n t s o f l e a d
(from the m illing process). The BP will be the first fire com position, .1 or .05 gram s. Next I want to use .15 gram s o f d o u b l e
salts, and im mediately after that 1 gram of PETN. I was also thinking about using .5 gram PETN and .5 to .75 grams of picric
acid as well. I will do tests to see what is best.
I have some plastic casings but it just deforms all to he ll while p r e s s i n g . I a m g o i n g t o u s e s o m e p a p e r t u b e s , a s t h e s e a r e

actually stronger. After I can get into town, I will get some 1/4" ID aluminum tubing to use.
D o e s a n y o n e s e e a n y c h e m ical incom patibilities with m y s e t u p . I h a v e d o n e s o m e research, but another se t of eyes usually

c a n p i c k u p o n s o m ething that m ight be right in front of m e.
I will be doing tests a gainst 1/8" steel sheet, and I will have pics.
Setharier Novem ber 10th, 2008, 05:40 AM

I discovered the parfum e s a m ple capsules with volum e of about 0.25-1ccm are wonderful and quaranteed without suspicion
readily available small detona tor cap shells tha t do not pose shrapnel threat like rifle shells do. They're m a d e o u t o f h a r d
opaque plastic or eve n glass and can be pressed full with no fea r of defo rm i n g . P r o b a b l y o n e c a n o b t a i n h u n d r e d s o f t h e m b y
taking a single trip to nearest mall or shopping centre. Usually they've given off free of ch arge.

a n d I m provised C hemistry > Ion excha n g e a n d a c i d s
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O k , a t t h e m o m e n t m y chem istry course at college is covering the topic of ion exchange resins.
This got m e thinking about using An H+ ion exchange resins to produce various acids from various salts.
T h i s c o u l d b e u s e d a s a m ethod of producing HNO3.
I was also wondering whether an H+ ion exchange resin could be used to produce other m ore exotic acids, such as HClO3,
Hypochlorous acid and perm anganic acid.
Any thoughts??

W ell, every acid, including your resin, has it's pKa and I doubt it will be high enou gh to form strong acids.
It's useful though for reactions which call for m ildly acidic environment. The resin will also scavenge Na+, Mg2+ and Ca2+ from
your solution .

a n d I m provised C hemistry > Purification, stabilizatin and storage o f e x p l o s i v e s
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Bert February 6th, 2004, 03:07 PM

Conventional wisdom would be to never store a ny explo sive, ma k e i t a s n e e d e d a n d u s e i t i m mediately. Unfortunately, this
isn't always possible. Shit happens- If you m a k e s o m ething and can't use it up imm ediately for so m e r e a s o n , i t h a d b e t t e r b e
storable. I'd go so far as to say it would be foolish to m ake ANYTHING without knowing stability under stora g e c o n d i t i o n s a n d
applying any pertinent purifications or other stabilizing m e a s u r e s ( a s y o u m ay find out the hard way you've stored something
too long...)
If th is thread seem s worthy, I'd like those with both theoretical and PR ACTICAL experience to put down their thoughts on this
subject. There's a good bit of related inform ation scatte red throughout the forum piecem eal, I just think that assem bling as
m uch information on the subject in one place would be useful, and allow newbies to get a feel for the subje ct on an overall
basis.
Let's start at the beginning-
Black powder
Very stable if m a d e f r o m p u r e m aterials, kept cool & dry it can e asily last for centuries. Th e m ajor purification/storage issue
would be to assure th e P o t a s s i u m nitrate is pure, as Calcium , Amm onium or Sodium nitrates will render it hygroscopic. W ith
m odern Frasch process or refinery Sulfur there is no longer even a need to wash the Sulfur-
Take it away, guys! W ho wants to do n itroglycerine?
Pilathos October 10th , 2004, 01:00 AM

The following is general comm e n t s r e l a t i v e t o h a n d l i n g a n d s t o r a g e o f e x p l o s i v e s , o f a h a n d b o o k o f a m a n ufacturin g blastin g
caps com p a n y l o c a t e d a t P o m p t o m Lakes, USA.
D u s t C o n t a m ination. Every effort should be made to elim inate the possibility of dust contaminating the explosives. Insuring
that powdwer buggies are com pletely closed, covering the O BC round boxes, paving the roadway at locations where explosives
buggies will be traveling; providing filters for all blower m otor inlets; and considering use of som ething other than earth for
barricade m ounding (or covering earth mounde d barrica des to reduce dust from erosion).
H u m idificatio n. All operations involving l e a d s t y p h n a t e a n d b o r o n - r e d l e a d requiere a m inimun relative hum idity of 75%. All
operations involving pottasium chlorate, should be at a relative hum idity no greater than 50%. In addition, lead styphnate
m ust be preconditioned with h umidity for at lea s t o n e h o u r b e f o r e h a n d l i n g .
Electrical Faciliites. All electrica l instalations including lighting fixtures should be dust tight rather than explo sion-proof.
All m ootors in explosives buildings should be located outside of the barricade structure. Equipm ent drives should be connected
by long shafts and blowers should operate through long air ducts. All tem perature controls should be set to "fail-safe".
Conductive Floors. All m anufacturing building where exp l o s i v e s a r e h a n d l e d m ust have flooring of conductive linoleu m o r l e a d .
Grounding. All m anufacturing equipment and furniture must be grounded. Each building m ust have a single grounding rod, to
which all grounding will be done. Static grounding and power grounding m u s t n o t b e d o n e o n t h e s a m e rod. Surfaces or wooden
t a b l e s a n d b e n c h e s m ust be covered with conductive linoleum or lead and ground ed.
Personnel. All personel working with explosives must be provided with conductive soles and non-static gene rating clothing.
Preventive Measures.An instalation for detection of atmospheric static level advise when high levels be dangerous.

a n d I m provised C hemistry > Iodic acid & iodates
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T_Pyro February 13th, 2004, 02:40 PM

Iodic acid, unlike the other ha logen equivalents, is quite stable, and exists as a white crystalline solid. It is a strong oxidiser,
a n d d e c o m p o s e s i n t o I, HI an d O 2 o n h e a t i n g .
Iodine crysta ls can directly be oxidised to iodic acid, HIO3. The m ethod involves either oxidation of the iodine crystals by
fuming nitric acid, or by ozone. There is yet another me thod which I came across in som e laboratory procedure on the net:
" A d d 2 2 g o f p o t a s s i u m chlorate to 90 m l of boiling wate r in a conical flask, followed by 8 ml of concentrated hydrochloric acid.
Add, in sm all am ounts, 20g of powdered iodine over half an hour, with shaking after each addition. When solution of iodine is
complete, boil for a few minutes to destroy most of the yellow colour. Filter by suction while hot. Cool the filtrate, filter off the
product which separates, and recrystallise this solid two or three tim es. Dry in the oven at 100oC for half an hour. If the product
appears coloured, further recrystallisation is necessary."
The iodate thus formed could be converted into iodic acid by displacem ent by a stronger acid. The problem, howeve r, is to stop
the reaction at that stage and prevent the decomposition of the iodic acid into iodine due to the action of the acid.
I'm intereste d in the synthesis of Iodic acid for possible use as an oxidiser, as well as for further synthesis of other iodates
(and eventually per-iodic acid, som eday!). However, if the use of the iodic acid /iodate is to be as an oxidiser, it would not
m ake any sense to use chlorates (a better oxidiser) to m ake iodates. Nevertheless, I'm pursuing this method purely for
academic interest, an d I'll post the results soon. As for the other two methods, th ey're beyond my reach since I do not have
any fum ing nitric acid at the m o m ent... :( Has anyone tried either of the methods? if so, what were the yields like?
S o m e m ore info on iodic acid: It also has m edicinal uses, apparently: "used as an astring ent, caustic, disinfectant, deodorant,
and intestinal antiseptic". However, I h ave not com e across any reports of it having been used in pyrotechn ic com positions o f
any kind.
T_Pyro February 18th, 2004, 06:19 AM

Ok, I just com p l e t e d s o m e t e s t s u s i n g K H ( I O 3 ) 2 ( m ade by the chlorate process). A mixture of KH(IO 3)2, sucrose, and
Sr(C O3)2 in approx. 50:40:10 ratio ga ve a slow burning m ixture with minute lilac flames, and violet smoke (from the iodine
produced). An identical m ixture using KClO3 instead gave a bright crim s o n - r e d f l a m e . T h e i o d a t e , I g u e s s i s n ' t a n y g o o d a s a n
o x i d iser for coloured flam e com p o s i t i o n s . C o m parative videos of both are availab le here (http://m ercury.walagata.com /w/
joydeepb/T_Pyro/9875654.zip). A mixture of th e chlorate and iodate, on the othe r h a n d , i f u s e d a s t h e o x i d i s e r i n t h e a b o v e
composition, would be interesting, producing a red flame and violet sm o k e - m a y b e m y n e x t e x p e r i m ent when I have som e
tim e.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Phenole
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It seems like many fun experiments require phenole and it is quite unavailable, I can't even order it from chem supplyers... though thats not an important part, lets focus on it's
preparation.
Most organic books describes dangerous process w here they first sulfonates benzene with conc H2SO4 and then sulfonate group is substituted w ith hydroxide by melting together
sulfonate salt and NaOH at freaking 325*C!! (detailed procidure is described below )
I wouldn't do this even if phenole was really needed..
Another procidure seems a bit more friendly where they decompose diazonium salt of benzene in water.
First, they convert aniline to it's sulfate salt (w ith H2SO4):
C6H5-NH2 + H2SO4 --> [C6H6-NH3]SO4H
excess of H2SO4 makes nitrous acid required in diazotisation:

2NaNO2 + H2SO4 --> 2HNO2 + Na2SO4
diazonium salt forms (should not be that dangerous in proper conditions):

[C6H5-NH3]SO4H + HNO2 --> [C6H5-N2]SO4H + 2H2O
and finally, above salt is decomposed in water when heated:

[C6H5-N2]SO4H + H2O --> C6H5OH + N2 + H2SO4
(detailed procidure described below )
Now, second method sounds much more promicing, but aniline is nearly as hard to get as phenole. But, I'm quite sure it can be made easily, though I made only few tests and
only half way in.. All book methods I had recall for reduction of nitrobenzene, and there we'll need benzene again.. So, I thoat of another way..
First w e prepare benzamide from methyl benzoate and ammonia and then convert it to aniline by action of aqueous hypochlorite, heres overall path:
C6H5COOMe --> C6H5CONH2 --> C6H5NH2
First reaction is partially tested, where I used 25% aqueous ammonia, homemade methyl benzoate and ethanole as solvent. After reacting at room temp for a day, HPLC
showed presence of benzamide (several percent), however alot of the methyl benzoate had decomposed and there were also traces of ethyl benzoate. So, next try would be to
use methanole as solvent instead of ethanole and keep everything as dry as possible to prevent water catalysing decomposition of methyl benzoate.
All precursors sofar are easy to get/prepare/dry. Dry methyl alcohol can be ubtained even from pyro supplyer and methyl benzoate is easily prepared from benzoic acid:
C6H5COOH + MeOH -H2SO4-> C6H5COOMe + H2O (for example Vogel got the detailed procidure)
In next benzamide experiment I'll pass dry NH3 gas through a mixture of methyl benzoate and methanole. This should go nicely, though if not, it would be nice to hear other
ways to benzamide. I came to think of decomposition of ammonia benzoate by heat, it should work since the reaction mechanism is similar to decomposition of ammonia
acetate w hen we prepare acetamide..
Back to aniline. Second step to aniline is a bit more doubtful.. There I wanna act by hypochlorite on benzamide this should also work since reaction mechanism is also similar to
when we prepare methyl amine from acetamide. Heres the not so detailed mechanism (based on reaction w ith NaOBr instead of NaOCl):
first one H on amide is substituted by Cl:

R-CO-NH2 + NaOCl --> R-CO-NHCl + NaOH
the resulting partially acidic H is then removed by hydroxide:

R-CO-NHCl + NaOH --> R-CONa=NCl + H2O
R group jumps over to N (since NCl can leave easily):

R-CONa= NCl --> CO=N-R NaCl (draw this on paper to get better understanding)
and finally water attacks carbonyl:

R-N=C=O + H2O --> R-NH2 + CO2
This reaction path is mentioned with acetamide as example though I don't see why -R couldn't be -C6H5. -CH3 and -C6H5 seems also have quite similar electronegativity. I
suspect that amide of the later will give less yield since it's harder for big -R groups to make intermolecular "jumps" such that in third reaction (jump from C to N).
Well, if this works aniline could be simply converted to phenole as mentioned above. (and in detiled bookmethod below )
------------------------------ Procidures
Now, here are the two procidures I could leach from my books that I mentioned above:
Phenole from benzene (reference: Laboratory practicum of precursors and pigments, L.N.Nikolenko, 2:ed, 1965)
Sulfonating benzene
In 0,5 l iron pot with refluxer and dropping funnel place 220 g (120 ml) H2SO4*H2O. Add drop by drop 90 ml (78 g, or 1 mol) benzene in a period of 30-60 min. While adding
benzene make sure to keep temp below 70-75*C.
When all benzene is in, slowly raise temp to 105-110*C and w hile keeping it there stirr for 4 h. All benzene will react.
Reaction mixture is poured into 0,5 l water while stirred w ell. Solution is heated to boiling and neutrolised with CaCO3 until no CO2 is evolved (pH >5,5). Solution is filtered,
washed with 200 ml warm water 30-40*C.
Then, 110 g crystolline or 47 g anhydrous NaHSO4 is added followed by 18 g NaHCO3.
Solution is filtered from precipitated CaCO3, and evaporated preferrably under vacuum until solid salt shows up.
Precipitate is filtered and dryed at 100-105*C. Ubtained sodium benzosulfonate salt will contain 7 % sodium sulfate.
Phenole from sulfonate salt of benzene

Place 150 g NaOH and 50 ml w ater into 0,5 l iron pot. Pot is slowly heated on flame to 290-295*C, avoiding large foaming. While stirring, add in small portions, fine powder of
above prepared sulfonate salt. Addition speed is addjusted to not let temp drop below 290*C. When all salt is in, raise temp to 325*C during 30 min. Mixture is stirred at this
temp for 40 min.
While mix is hot, pour it out on an iron plate. When it cools down, crush it and dissolve in 1 liter water, w hile heating.
Solution is heated to boiling, neutrolised by 50% H2SO4 and filtered at 50-70*C. While filtrate is still hot, add conc HCl until pH is 2-3. Phenole is extracted 3 times with benzene
(200 ml benzene totally will be required).
Product is destilled at atmospheric pressure, fraction of 178-180*C is collected.
Yield is 70-75 g (75-80% from theoretical), freezing temp 38*C.
Phenole from aniline (reference: Practicum of organic chemistry, N.D.Prjanishnikov, 4:ed, 1956)
Place 50 ml w ater in 300-500 ml beaker and while stirring add 10 ml conc H2SO4 (0,18 mol). While solution is still hot, slow ly w hile stirring add 9,3 g (0,1 mol) of freshly
destilled aniline. Mix is cooled to room temp and 70 g crushed ice is added. On cooling, there will precipitate hydrogen sulfate salt of aniline, it w ill not affect next step of
synthesis.
To the cooled reaction mix that should be at about 0*C add slow ly, while stirring vigorously, a solution of 7,5 g (0,11 mol) NaNO2 in 30 ml water. When big ammount of nitrite
have been added, reaction mix is checked by a iodine/starch paper(Note1). If indicator show s blue after a w hile since the last addition of nitrite, reaction is compleate.
Ubtained solution of diazonium salt is transferred to 500 ml roundbottomed flask and heated at 40-50*C in w ater-bath until nitrogen stops evolving.
Phenole is then destilled w ith water steam.
Destillate is saturated by fine pow dered NaCl and phenole is extracted several times by diethyl ether. Organic phase is dryed by CaCl2 and solvent is destilled away. Phenole is
then destilles w ith short air destiller.
Yield is 6-7 g. mp 42,3*C: bp 182,1*C
Note1:
Iodine/starch paper
Heat a solution of 0,5 g starch in 100 ml w ater until it gets wallpaper glue consistency, add 1 g KI.
Soak filtering paper in prepared solution and dry it. After cut paper in strips and store in airtight jar.
------------------------------ Procidures end
Ok, diazotisation synthesis sounds to be very promicing, But steam destillation in the end sounds to be much of work, one could simply extract product w ith, say, ethylacetate or
other similar widely available solvent. That is if reaction mix is properly neutrolised..
Anyway, comments, suggestions are w elcome. Maby there are even simpler synthesis ways to phenole..
vulture February 16th, 2004, 11:46 AM

Ever thought of the decarboxyaltion of salicylic acid?
Check TNP aspirin process.

knowledgehungry February 16th, 2004, 12:33 PM
Using Conc H2SO4 on Aspirin gives you phenol IIRC.

I've seen that procidure, but for some reason they don't sell pure aspirin here (swe).. I have only access to those 500 mg tablets which are darn expencive.
Btw, I will try this to see the yields.. or maby someone have already measured theese (yields of phenole from aspirin)?
Also, maby there are different reaction conditions that will give better yields. For example, IMO, the acetyl group could be taken aw ay faster with an alkali..
Then I read in org chem book that some decarboxylations on aromatics is carried out on heating in presence of powdered Cu. I don't think that H2SO4 have any role in
decarboxylation (atleast w hen I tryed to draw mechanism), or?

The synthesis of aniline via Hofmann degradation of amide that you spoke of sounds ineresting (and promising). The last step, how ever, "and finally water attacks carbonyl",
IIRC, is actually:
R-N=C=O + 2OH- -> R-NH2 + CO32-
Another method of preparation of amiline would be the nitration of benzene to obtain nitrobenzene, and subsequent reduction using Sn + HCl to give aniline. I'm not sure of the
experimental conditions, though, apart from the fact that heating is required.
vulture February 17th, 2004, 12:38 PM

[QUOTE]For example, IMO, the acetyl group could be taken away faster with an alkali..
[QUOTE]
Quite the contrary, the acetyl function is hydrolized in water bij accepting H+ . Acid w ill make it go faster.
H2SO4 enormously speeds up decarboxylation. Otherw ise very strong heating is necessary which will often decompose the molecule.

I came across an interesting procedure for the preparation of phenol, which is supposed to be the method for the preparation of nearly all the phenol produced today. This
method starts with 2-phenylpropane (cumene). 2-phenylpropane is converted by air oxidation into 2-hydroperoxy-2-phenylpropane, which is converted by aqueous acid into
phenol and acetone.
http://ww w.che.rochester.edu/Courses/CHE286/cumene_rearrangement.gif
(Image from this page (http://www.che.rochester.edu/Courses/CHE286/bisphenol_a.htm))
Marvin February 18th, 2004, 07:09 AM

I would be bothered the conc acid might sulphonate the ring. I'm also a little bothered you arnt forming the acid itself w ith a seperate step, I'm not sure this will succeed.
I'd probably start with either asprin or methyl salicylate, add caustic soda to hydrolyse/form the salts, add HCl to ppt and distill the salicylic acid from powdered pumace,glass or
sand to produce phenol. Several older books recommend the distilling process to decarboxylate.

Quite the contrary, the acetyl function is hydrolized in water bij accepting H+ . Acid w ill make it go faster.
I assumed OH- catalysed "deacetylation" would go faster because it have less steps in mechanism than H+ catalysed, I dunno :rolleyes:
Thats a nice w ay, T_Pyro, I like idustrial process. On some search, cumene seems to be used as thinner for paints (maby as substitute/addition to toluene, which w ould be easy
to get/separate). Time to visit some stores :)
Btw, isn't lignine a cheap phenol derevative.. I got access to 23 books about wood processing, gonna check them out w hen there w ill be more free time..
Marvin, I checked bp of salicylic acid and it sublimes at 76*C, how can it then be thermally decomposed at atmospheric pressure. Do you mean that pumace/glass etc w ill
somehow prevent sublimation, or did I misunderstand something? (destill with excess HCl?)
I've checked Vogel for sulphonation of phenol where they place 2 -SO3H on a phenol. Reaction is carried out with conc H2SO4 at 100*C, so, now I'm also worrying about
sulphonation of final product :(
How about using catalytic ammounts of H2SO4, since sulphonation is reversible, there will be enough H2SO4 during w hole decarboxylation.
Or, how about refluxing w ith HCl, maby it will have same decarboxylation effect..
EDIT:
Attempt to make benzamide wasn't that good..
Ammonia gas was dryed by solid KOH and let through a mix of 9,5 ml methylbenzoate and 19 ml methanol. After about a day reacting at room temp, HPLC showed that there
was benzoic acid present... so, this means methyl benzoate decomposed because water was present :mad: dammit, thats probably air humidity.. I will not attemt same
experiment nearest time.. gonna test thermal decomposition of ammonia benzoate.
markgollum March 1st, 2004, 06:17 PM

How is this for the synthesis of phenol?.
React sodium salicylate, (an ingredient in whistle mix for pyrotechnics) w ith hydrochloric acid, (cheaper than H2SO4) to make sodium chloride, and salicylic acid. Next,
decarboxylate with sulfuric acid to make phenol.
Unless I am really missing something, this should be a good way to make your phenol.
(When last I checked, sodium salicylate was avalible from either pyroteck or firefox for about $15 a pound :))
Marvin March 2nd, 2004, 06:04 PM

I am uncertain how the decarboxylation happens, but I have several books that suggest this is how it can be done and nothing to suggest the acid process. I have read the
usual method of CaO/NaOH is too reactive and yeilds drop as a result and one verbal reference that the product is frequently an unapealiong tarry mass but that the yeild on
purification is high 80% + ish. Salycylic acid is made industrially from phenol by heating under pressure with carbon dioxide, which adds strength to the distilling method to my
mind.
mark, not a bad idea, but the bone of contention seems to be how to decarboxylate rather than where to get the salicylic acid from. A good tip though.
Lavoisier March 6th, 2004, 04:12 PM

Attempt to make benzamide wasn't that good..
Water usually dosen't interfere much in theses reactions, as ammonia is a better nucleophile than water and the resulting amide more stable than the acid... perhaps you rather
lost all your ammonia before it even reacted if your reaction vessel w as left wide open to atmospheric conditions? it could also been caused by some KOH that w ould have been
dragged into your mix...
I used to make acetamide this way :
I mixed ~50g ethyl acetate with ~ 100mL 28% aqueous ammonia under heavy stirring in a properly capped flask for 48h at room temperature. Then I distilled everything under
reduced pressure (painful...). Yield was about 30g.
Now for benzamide, I would probably keep using methanol as solvent.. but w ith 28% aqueous ammonia, which is w ay more convenient to handle than gaseous ammonia...
Btw, if theses are only small amounts of benzoic acid.. w hy don't you simply wash your benzamide with dilute aqueous NaOH? That would get you rid of it...
I hope this help you out somewhat...

Thanx. Though the only problem with water is that it decompose methylbenzoate.. You're right that aqueous ammonia is easier to handle, it was a pain in the ass to saturate
solution with ammonia (btw, finall concentration w as checked by titration, it had about equimolar ammount of NH3), and I've heard that this reaction should actually undergo
better in more polar solvent w hich justifyes to use aqueous ammonia again.
I have also noticed that formation of benzamide favors over decomposition of ester with increased temperature. So I'm going to test this out by filling a soda bottle with
aqueous reaction mix and monitor pressure with barometer, and heating it in water bath. Hope it wouldn't blow up :rolleyes:
Anyway, I found out that benzamide to aniline reaction can't go with help of hypochlorite :( either there are another way to drive this reaction, or, I'll just produce some
benzamide to occupy another bottle..

Oki, a new procidure got into my mind, w hich is more promicing.. again using benzoic acid.
To sum it up, we prepare meta-nitrobenzoic acid by simply nitrating it with H2SO4/KNO3 (btw , m-isomer is a probable mutagen, see MSDS). Then, it's decarboxylated by heat
(possibly w ith Cu/Cu(I) as catalyst) to form nitrobenzene (not that healthy eather), which is then reduced to aniline by Sn/HCl or in other reducing conditions, here I'll try to find
a method that uses zinc pellets (time of reaction is not critical).
Aniline is then converted to phenole as was mentioned in first post.
Everything seems to be simple to do, I've already carried out nitration successfully (yield is drying over CaCl2), but decarboxylation step is a bit critical..
However, I found some references about aromatic decarboxylations. Most usual procidure involves heating with copper powder and quinoline.
Quinoline
http://img37.photobucket.com/albums/v113/frogfot/stuff/quinoline.png
March mentions follow ing mechanism catalysed by an acid:
http://img37.photobucket.com/albums/v113/frogfot/stuff/decarboxylation.png
Another decarboxylation mechanism proceeds with a salt of the aromatic acid, first step is initiated by heat:
http://img37.photobucket.com/albums/v113/frogfot/stuff/decarboxylation2.png
Here, same catalysts can help reaction going. But I'm not sure yet which way would give better yields.
Now, to the catalysts.

Quinoline acts basically as H+ acceptor/donor and a solvent (since it have high boiling point).
March also tells that reaction is actually catalysed by copper (I) salts, where Cu+ stabilises the negative charge formed in second decarboxylation reaction above. Though I can't
see how copper(I) would catalyse the first reaction, where no negative charge forms..
Another source (Chemical abstracts 1947, 6223) tells that decarboxylation proceeds easier if aromatic acid is stronger, this is because stronger acid have more positive aromatic
ring and forming carbanion is more stabilised (one exception mentioned is chloro benzoic acid, which does not decarboxylate). Here, it pays off to decarboxylate nitrobenzene.
Reaction is also catalysed by compounds w ith -OH and -NH2 groups, which acts as H+ donors/acceptors in same way as N in quinoline.
"Chemical abstracts" mentions some experimental data, where 3 g o-nitrobenzoic acid, 3 g Cu bronze and 25 ml benzene is heated in an autoclave at 180*C (its decarb. temp)
for 4 h, this gave 90% PhNO2.
While similarly, m-isomer gave 92% at 238*C and p-isomer gave 62% at 240*C.
I have no clue why bronze is used instead of pure copper.
Procidure requires an autoclave which I'd be afraid to use, so, I've decided to go with simple heating and use acetamide as a solvent.. acetamide have bp of 222*C, it's very
stable and it's incredibly easy to prepare (in virtually any ammounts). Though it will not act as a catalyst as an amine would, though it have -NH2 group. Solvent w ould basically
act as an heat conductor w hich should decrease pain in the ass by giving an even heating of whole reaction mix :)
It's also good to mention their experimental results from decomposition of H2N-C6H4-COOH, since it gives good yields even without a catalyst:
o-isomer gave 89% PhNH2 at 145*C (205*C final temp) in 4 h. (97,7% with recovery of CO2)
p-isomer gave 75% PhNH2 at 187-210*C in 4 h. (81,8% with recovery of CO2)
I'm not really sure what "with recovery of CO2" means, but I think it's basically when they carry out reaction in open, to let CO2 escape. Here is another possibility, through
following path: toluene -(NO2+)-> o- and p-nitro toluene -(KMnO4)-> o- and p-nitrobenzoic acid -(Sn/HCl)-> o- and p-amino benzoic acid, and so on as in exp above. Thats
a long, but fun path, most probably w ith decent yields.
Oh, decomposition of salicylic acid was also mentioned:

3 g salicylic acid, 3 g Cu bronze and 25 ml benzene w as heated in an autoclave at 170*C for 3 h, this gave 93% PhOH. Acid alone w ould decompose at 205*C and at 170*C in
presence of aniline. This sounds promicing (if, again, we changed out the solvent to something more available), but again, here in Sweden aspirine seems to be hard to get
(anyone from swe cares to share a source?)
I got some more info about problem with sulfonation of phenole, apparently, sulpho groups can be simply removed by boiling w ith dilute H2SO4. So, procidure to get phenole
from aspirine should be pretty simple: boil with conc H2SO4 until CO2 evolution ceases, then dilute with w ater and boil some more..
As for cumene, I couldn't find any solvent that contained it. Most had toluene, different types of xylene and suchalike. Gotta search more..
Hope that next time I'll have some experimental results..
(heh, and I finally got an account on photobucket :) )
EDIT:
Dammit, on a bit rethinking, I checked MSDS sheets of nitrobenzene and aniline, both seems to be pretty evul compounds.. so theres the catch :(
Before attempting this experiment, one should probably make a fumehood and place where one can handle theese compounds and wash equipement (don't wanna do this in
kitchen..)
See MSDSs here:
http://ptcl.chem.ox.ac.uk/MSDS/NI/nitrobenzene.html
http://ptcl.chem.ox.ac.uk/MSDS/AN/aniline.html
Also any idea if nitrobenzene can explode on heating? They say "wide explosion limits"..
T_Pyro March 27th, 2004, 06:38 AM

I read the MSDS's you mentioned regarding nitrobenzene and aniline, but I really don't think it's as bad as the MSDS states. We use aniline for organic analysis in our college
chem lab, and I don't think they'd allow us to handle it if it w as so dangerous! One of my experiments in the lab also involved the nitration of benzene, and my teacher didn't
say anything when I took her permission... By saying "heating" of nitrobenzene, what temperature range are you talking about? I know that it's stable even at 70o - 80oC.
Regarding cumene:
Here's a hypothetical method for the preparation of cumene: http://img34.photobucket.com/albums/v104/T_Pyro/Cumene-preparation.gif
EDIT:
Sorry, the last diagram I'd posted was downright w rong. Anyway, here's the actual diagram. Only isopropyl alcohol is required, but the sulfuric acid w ill have to be concentrated
to produce the required secondary carbocation. No need for grignard reagent after all (phew!).
Just got another idea:

You could react aniline with NaNO2 and conc. HCl, and then add water to hydrolyse the diazo compound to get phenol.

Well, pretty high heating, I thoat if nitrobenzene could be destilled away from resulting goo after decarboxylation of nitrobenzoic acid. It have bp of 210,9*C.. it would probably
get much higher since I'm planning on using gas burner.
Anyway, on other thoat, nitrobenzene could be skipped if -NO2 was reduced while it is in nitrobenzoic acid, as mentioned preveously (w ahoo, so much possibilities!!)
Thats an interesting prep of cumene. And its sure much safer than melting sulfonated benzene w ith NaOH :)
As for grignard, I got pure Mg, and acetone could be easily dryed, methylchloride seems to be easily prepared (one book describes procidure that uses MeOH, conc. HCl and
ZnCl2). But preparing grignard of a gas seems to be a bit troublesome..
I think there should be isobutanole as solvent in usual stores.
frogfot April 23rd, 2004, 08:54 PM

While I was searching books for some info about reduction of nitrobenzoic acid, I found an interesting synth that basically makes phenole in one step by thermal decomposition
of copper benzoate.
This is apparently an industrial process where they use toluene as precursor and yield is above 73% with regard to toluene!!! (buts comes later) I checked out this closer, and
got two references to (Journal of Organic Chemistry 1961, 26, 3144) and a US patent 2,727,926. The first mentioned this method and the second reference basically tells
everything (patent is free on http://w ww.uspto.gov/patft/index.html).
Procidure sounds simple, they melt a mixture of benzoic acid (solvent/reactant) and copper benzoate ("catalyst"). Owing to patent, the ammount of copper should be from 1 to
5% from total weight. A stream of steam and air is bubbled through reaction mix and phenole is destilled aw ay. Some benzoic acid is destilled too, but in patent they use a
reflux column that separates benzoic acid and phenole, w hich lets the former to go back into reaction vessel. Actually, during experimenting, I found this refluxing column to be
the major problem, explained further.
Now, to the reactions that explain why air and steam is needed. First copper benzoate decomposes from heat, at 200-250*C:
2Cu(C6H5COO)2 --> C6H5COOC6H5 + 2CuC6H5OO + CO2
Formed copper(I)benzoate oxidises in presence of oxygene to regenerate copper(II)benzoate:
2CuC6H5OO + 2C6H5COOH + 1/2O2 --> 2Cu(C6H5COO)2 + H2O
The ester formed in first equation decomposes in presence of water:
C6H5COOC6H5 + H2O --> C6H5OH + C6H5COOH
Net reaction is following:
C6H5COOH + 1/2O2 --> C6H5OH + CO2
Since w ater formed in second equation w ill partially evaporate, external w ater is supplyed in form of steam to maintain full decomposition of phenyl benzoate ester.
I experimented a little with this myself. Apparatus used was a reaction flask w ith short air condencer and recieving flask, all in glass. A car tier pump was pumping air through
50-70*C water and produced "steam" was let by a copper pipe to the bottom of reaction flask where I melted 2 parts of benzoic acid and 1 part of copper salt. Heating was
done by a gas burner and in further tests by a heat gun (set at 300*C).
Reaction went nice though condencer stuffed up pretty fast by benzoic acid (heating reduction didn't help much). A product w as ubtained, that smelled phenole though most of it
was composed of benzoic acid and its phenolic ester. I guess that supplyed steam wasn't enough to break down the ester.
Here comes the main catch, even if temp of reaction is kept below bp of benzoic acid, it still destills over to some extent (prolly with water steam). In industry they solve this
easy by using a reflux column as mentioned previously. It basically returns all acid back into reaction vessel. But this does not sound simple at all... column temp must be
maintained at mp of acid and thats not the only problem. Screw the column..
One could alw ays extract phenol from the final solid desillate but main problem still remains: this destillate taps the condencer over short operation time.
Also, w hile experimenting I found out what phenol does on the skin.. :) Apparently, first, skin numbs and then appears a white burn.. Just in case I had tight goggles all the
time.
Anyway, patent mentions that reaction could be also done with sodium or potassium benzoates, preferrably with CuSO4 as catalyst in aqueous conditions. This process is
described in first reference I gave. Though there, they carry out reaction under pressure, which is tedious.. conversion is not full either.
One thoat was to decompose copper benzoate together w ith sodium benzoate as in method mentioned in beginning (with steam and air), but mp of benzoate salt is above
300*C which is kinda too high. Most probably, this will give low yield with alot of tar residue and probably higher benzene output. I've tryed to melt the salt and it started to
char over the time..
I beliave reaction w ould be a bit different, specially oxidation of copper(I) salt:
2CuC6H5OO + 2C6H5COONa + 1/2O2 + H2O --> 2Cu(C6H5COO)2 + 2NaOH
Together, giving follow ing net reaction:
C6H5COONa + 1/2O2 --> C6H5ONa + CO2
Sodium salt of phenoxide would remain in reaction mix, waiting to be extracted.. it would be probably partially decomposed, but still, we wouldn't need any reflux column nor
air condencer with funky glass equipement. But I'll currently stop experimenting w ith this process.
I still have a hope of the other 5 step process mentioned in previous posts, though some difficulties came up.. like, o-nitrobenzoic acid didn't want to be oxidised by KMnO4,
only p- isomer could :( However, the rest of steps have pretty good yields. Not looking on that darn oxidation, one could get up to 30% yield of phenol with regard to toluene.
One solution would be to separate the o- and p- nitrobenzoic acids, then oxidising only the p- isomer. But what the hell w ould I do with the o- isomer..?!?! (although it smells
funny :p it's toxic, I know)
Maby anyone know s some reaction conditions that would oxidise both isomers in the same batch? As I see it, the o- nitro isomer cann't be oxidised because the partially
negative nitro group doesn't let the oxidiser to come close to the methyl group. So, maby oxidiser should be small, neutral or positive charged and ofcaurse strong. (I have
currently a ready batch of nitrotoluene..)
Anyway, when I'm finished with all steps I'll present all procidures.
Btw, I have made a google search and found a phenol discussion on SciMad w here copper process was mentioned. Also, someone decarboxylated aspirine just by melting it,
ubtaining 77% yield. Though there was no further experimental data..

a n d I m provised C hemistry > C o n d e n s i n g O x y g e n o u t o f A i r
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View Full Version : Condensing Oxygen out of Air
YayItGoBoom! February 23rd, 2004, 04:42 PM

My friend came up with an interesting challenge for us to try: construct a device, sim ilar to the ones used in com mercial
indu stry, that is capable of condensing CO 2 and ultim ately LO X out of air. Theore tically, it is doable.
The aparatus is set up something like this. There is a m ain cylinder of aluminum pipe, probably 2-3 inches diameter and 5
feet long. Bo th ends are sealed with endcaps and tapped. 1/4 inch thread for the air com pressor (Sears tire pum p 130 psi - I
don't think this will cu t it but its all I have for the tim e b eing. The critical pressure of oxygen is 700 psi, but I am no t sure if
that matters if you ca n get it cold enough). An exhaust valve will protrude out of the botto m to dra in the liquid, and another
valve at the opposite end of the pipe will exhaust air into four copper tubes (1/8-1/4 inch) that will spiral around the cylinder.
Around this is an auxillary coo ling system (probably going to be ripped out of an old freezer or AC unit). The whole thing will
p r o b a b l y b e s u b m e r g e d i n s o m e sort of coolant to retain the cold during pressurization (water would be nice because of its h igh
specific heat, but it freezes, and freon isn't ava ilable).
T h e w h o l e i d e a i s b a s e d o n P V = n R T . W h e n t h e cylinder is pressurized, the tem perature is increased. The latent heat is tak e n
away by the cooling system. At first, th e air will be no where near cold enough to condense the gasses we want, so it will be
discharged. As it exhausts through the spiral coils, it 1) loses tem perature due to the pressure drop 2) carries away even m ore
latent heat 3 ) finally, I m ight just rout it to exh aust ove r the heat exchange pipes of the refrigerant system , as so to carry
away heat from the high pressure coolant (if not it will p rovide a nice cool breeze :p ).
O n c e w e g e t i n t h e r a n g e o f t h e p r e s s u r e / t e m p e r a t u r e t o c o n d e n s e C O 2, the com pressor will run, continually pressurizing as

t h e C O 2 c o n d e n s e s a nd the pressure drops, all the while the coolant kee ps the whole thing cool.
Then, if we're lucky, condense the oxygen. And if we get liquid n itrogen, well, I'll just have a headstart on the paten ts. ;)
Before we m ake our trip to Ho me Despot (typo intentional), I would like som e advice from people who have just a bit m o r e
experience with cryogenics than m e. Firstly, what coolant would be suitable? I believe the boiling point of oxygen is less than
100 K.
Second, would exhausting the pressurized gas inside the cylinde r do enough to actaully m ake a difference in getting the
temperature down in the first place? W ould a refridgeration coil alone be sufficient?
Thirdly, what would be the best kind of insulation to use? Som ething tells m e t h a t P i n k P a nther fiberglass isn't going to cut it.
Thanks a lot for your im put, p l e a s e n o flam es, yes I already know its going to be difficult, but I want to try it.
Tuatara February 23rd, 2004, 05:37 PM

Google for 'Linde'. Th is will get you to a descrip tion of the air liquifier he invented in 18xx.
Basically you compress the air, cool to RT, put it through a secondary heat exchanger, expand back to atmospheric, pass the
c o o l e d , e x p a nded air back through the secondary exchanger, further cooling the high pressure air just prior to expansion. Its
this regenerative cooling that gets you down to 70K.
I suggest you wreck a fridge: you'll get a compressor, p rimary heat exha nger, lots of stee l a n d c o p p e r t u b e , a n d a J o u l e -
Thom pson expansion valve.
Industrially this cryogenic process is not used m uch - PSA is m ore comm o n , u s i n g a z e o l i t e a d s o r b e r .
BTW the biggest problem you will have is with water in your intake air, which will condense and free ze way b efore anything else.
YayItGoBoom! February 24th, 2004, 06:50 PM

T h a n k s f o r t h e i n f o o n L i n d e , t h a t s o u n d s l i k e a m u c h b e t t e r i d e a than m y silly compression chamber.
I found a site on Linde, it has two grainy pictures and vaguely describes the process, but there is no schem atic for the exact
design. I dre w up my own design, but I'm not sure how accurate it is. If someone could post a link of a more exact description,
I would love that. Until then its Googling for m e.
Right now the largest problem for me is finding old freezers and AC units...
flashpoint March 4th, 2004, 01:53 AM

Are you referring to Low NOX, or LO X?

a n d I m provised C hemistry > AP dim er-trim er co nversion?
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View Full Version : AP dimer-trimer conversion?
me234 February 24th, 2004, 04:28 AM

Now I'm not sure exactly how to go about this thread, but I recently had a bad AP synth and I'm sure I've got m ostly the dimer
form sitting here, so I started thinking about possible ways to convert it to the trim er form , I ended up with m ostly bupkiss, so
I thought it might be nice if m embers could post there ideas here with re gards to the properties of the two, not really explosive
properties, but rather physical properties that m ight be useful to try out, I now ha ve a whole bunch of the d im er, and a bit of
the trimer elsewhere, I was thinking that I might try as m a n y o f t h e g o o d i d e a s t h a t h a p p e n t o c o m e u p h e r e o n s o m e A P a n d
compare the doctored dimer to the trimer. The only idea that m y mind could come up with was subjecting the dim er to a high
pressure (not too high of course) and leaving it for a while, perhaps in solution (be harder this way though), I thought that
perhaps in an effort to releave the pressure the dim er might convert to the trim er (though probably slowly) which (hopefully)
m ight have greater intermolecular forces which might bring the molecules closer together, even if only from an incre a s e d
m olecular we ight.Sorry if it sounds lam e but Le chatelier cam e to m ind, it was the only thing I could think of. It would be nice
f o r s o m e o n e w h o h a s a d o d g y s y n t h t o b e a b l e to do to up the trimer content.
Cyclonite February 24th, 2004, 11:50 AM

Its a waste o f time, you are also putting yourself at risk unnecessarily. W h e n y o u m ake it just chill the H2O 2 and acetone to
f r e e z e r t e m p . W h e n t h e t e m p i s r e a c h e d a d d t h e a c i d a nd put it back in the freezer. You m ay even need to put it in a
refrigerator for the reaction to happen in a decent am ount of tim e.
knowledgehungry February 24th, 2004, 09:18 PM

You can't change it from d i m e r to trim er without breaking peroxide bonds, breaking perox ide bonds is alwa ys bad.
me234 February 25th, 2004, 01:56 AM

Cyclonite, I know to keep it cold, I just tried adding the acid to the acetone first, it turned a little red and warmed up, I was in a
hurry so I didn't let it cool down enough before adding the H2O 2 (50%), when I a dded it the red colour went away first then it
heated up quite a bit, and stu pid me didn't think that m aybe I shouldn't make anything when in a hurry as this is when shit
happens, the final yield was actually pretty good though, besides this was mostly a pipedream , and I definately agree with
knowledgehungry, breaking O-O bonds is probably best left well the fuck alone, so I won't even bother. Thanks for the input
anyway.

I've read from a few (possible unreliable) sources that when you dissolve trimetric AP in acetone, and let it evaporate off at
r o o m t e m perature, it forms dim etric AP because of the higher te mperature it form s at. I was thinking that it could work the
other way around, you could chill a solution of dim etric AP in acetone, then use a vacuum to evapo rate the acetone. This would
l e a d to theoretical trim etric AP . F o r s o m e r e a s o n , t h i s s e e m s to good to be true to me. If anyone knows we ther this would work
or not, please say so. If it would work, I would be intere rsted in the results.
thelasttrueone Novem ber 11th, 2007, 03:49 PM

W hen you put the acid in first you m ost likely started m aking DDDP. See a thread on that for details
The_Duke Novem ber 11th, 2007, 09:41 PM

I think you m e a n D P P P : r o l l e y e s :
It cannot be made by the suggested route. If you would have re ad the thread you speak of then you would know th is...
megalomania Novem ber 13th, 2007, 06:21 AM

I don't think the DPPP thread was around 3.5 years ago when this thread was created, so you can hardly critize the guy,
thelasttrueone.

a n d I m provised C hemistry > W h i t e S m o k e P r o d uced by AN
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View Full Version : White Smoke Produced by AN
PIB March 1st, 2004, 03:53 PM

W hat is the white sm o k e p r o d u c c e d b y d e t o n a t i o n o f a m m noium nitrate?
vulture March 1st, 2004, 04:55 PM

A crosspost:
http://www.roguesci.org/theforum/showthread.php?t=3780&highlight=white+smoke
And a question that could have been answered by searching.
I'd say toodles to you...
Chemiboy March 5th, 2004, 09:58 PM

you will be lu cky if u dont get kicked out by tha t q u e s t i o n : e e k :

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > pH indicator
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I searched if there was already a topic on this, and I was surprised to discover there wasn't. This post deals with using red cabbage as a cheap and easily accessible pH
indicator. This method is pretty widely known but has not been discussed almost at all within this forum, even though it seems to be very useful.
The pH indicator is prepared by blending red cabbage in a blender, straining off the liquid, making sure there is no plant matter in it, then put it into your solution you are
testing the pH of. The red cabbage indicates at a pH range of 1 to 12. Here's a picture of the color range, from rhodium's site:
http://www.rhodium.ws/chemistry/equipment/pictures/ph-cabbage.jpg
I hope this helps some of you that are having trouble finding a good pH indicator.

Whow, that seems to be an accurate scale (except for pH 3-7), this is a very useful thing.
Any idea what is the active substance that changes color? Maby one could extract it and concentrate, to make it storageable since cabbage juice doesn't store well.
mongo blongo March 15th, 2004, 02:59 PM

IIRC you can make it with rose petals too.
Wild Catmage March 15th, 2004, 03:50 PM

http://home.howstuffworks.com/question439.htm - This site claims that the colour change is caused by one pigment contained in the red cabbage.
This site claims that the colour change is caused by two different pigments - http://www.penpages.psu.edu/penpages_reference/29503/29503200.HTML
For information on extracting anthocyanins, go to - http://www-saps.plantsci.cam.ac.uk/osmoweb/chloro1.htm
Tuatara March 15th, 2004, 05:58 PM

I've done quite a lot of messing with natural pH indicators (mostly to entertain the kids) and I've found practically any intensely coloured flower or berry will yield a useable
indicator. Even red wine works! Doubtless different sources will produce indicators for different pH ranges, sadly I have no calibrated pH meter to test them with.
The biggest drawback with red cabbage is the smell :D
Xioa March 15th, 2004, 06:50 PM

I've read that the red cabbage juice can be stored for 2 or 3 weeks if you refrigerate it. Heating the juice destroys the pigment, so if you plan on keeping it a while, dont put it
in the sun, keep it cool.
Also, Tuatara, you do not have to use a pH meter to measure the pH, just use a strong acid or base (weak ones are useable too, if you get the Ka/b of them) and then record
the moles you add until it turns color, then calculate the pH at which it changes color. It requires a bit of extra work though :rolleyes:
Tuatara March 15th, 2004, 09:11 PM

Heating didn't destroy my red cabbage - thats how I made the extract! Just boiled the stuff for 15mins (yech! what a stink). Boiling also kills off any bacteria, so the resulting
liquid should keep really well if covered and refrigerated.
T_Pyro March 16th, 2004, 04:24 AM

Anthocyanin is the water-soluble pigment that lends a red or purple colour to fruits. Since the active component of the indicator is the one that is coloured, it follows that any
fruit or flower having the same pigment will also act as an indicator. This (http://www.agsci.ubc.ca/courses/fnh/410/colour/3_22.htm) page has some more information
regarding the effects of change in Ph on Anthocyanins.

It showed to be very easy to extract pigment from red beet. I've chopped one beet in food processor and then extracted two times by boiling it with water. On addition of big
ammounts of alcohol (cheap denaturated), red goo precipitated (possibly with rest of inorganic salts). After filtering, solvent was slightly orange. Dryed product is noncrystalline
dark red solid (<1 g), which looks like somekind of rosin.
Now, I prepared a concentrated solution of this red solid, gonna see how well it stores..
Also, time to by some red cabbage ;)
vulture March 17th, 2004, 09:53 AM

Store it as a diluted solution, indicators are already effective in very low concentrations.
T_Pyro March 17th, 2004, 03:08 PM

I've been experimenting with black grapes (purple=anthocyanin most probably), and found that the indicator turns green in the presence of a base, and dark red, turning
orange in the presence of an acid.
Frogfot, is the "red goo" that precipitated a concentrated form of the pigment? I didn't understand how the substance precipitated out... The red dye from beetroot is water
soluble, as are the possible inorganic salts, so what was it that actually precipitated?
EDIT: Looking at the Ph chart above, it seems that the Ph range of the black grape would be more like 1-2=last 2 test tubes on the scale 3-14= first 12 test tubes. How this
shift in colour with Ph takes place, is a mystery!

I said it precipitated on addition of alcohol.. since anthocyanin is composed mainly of benzene rings, I assumed it would have bad solubility in cold alcohol. And I assumed that
nearly all pigment was precipitated since filtered solution became orange..
One might think that this pigment have different color in alcohol.. anyway, I tested to dilute the orange filtrate and the red color didn't come back, so I must've precipitated it
all.
As I understand from link you've posted before, pH indicator should contain a big conjugated double bond system, also conjugated with H+ donors/acceptors (like -OH and =O
respectively). So it seems that it should be pretty easy to produce own indicators.. we actually made one when some of us tryed to produce phorone, the byproducts that was
synthesized fall in the above-discribed creteria (with big conjugated doublebond system), this stuff was responcible in color change when acidic reaction mix was neutrolised.
Anyway, there should be other simple reactions that can produce similar complicated compounds..

I tried doing the same thing with the black grape extract, using isopropyl alcohol (Don't have any ethyl aclohol), but the solution just got diluted a bit. How much alcohol did
you have to add till the precipitation began?
The conjugated system with carbonyl carbons and hydroxy groups help to stabilise the carbocation by resonance (delocalisation of electrons). Ph indicators are generally buffer
solutions using alkali metal salts of weak acids, or salts of strong acids and weak bases which have a characteristic colour. Eg. In Mythyl orange:
http://img34.photobucket.com/albums/v104/T_Pyro/Methyl-Orange.gif
In the presence of a stronger acid, the -SO3- gets converted to -SO3H.

To this boiled down extract I added approx 10 volumes alcohol (maby more), try cooling to -20*C. There are possibility that grapes have other pigments..

A little OT, but... I don't think the product produced in the Phorone synthesis would fall into the category of "indicators". More likely, it was just a condensation product like:
http://img34.photobucket.com/albums/v104/T_Pyro/Reaction-scheme.gif
And so on, producing a polymeric chain.
The final product wouldn't be a salt of a strong acid+ weak base, or strong base+ weak acid, hence it can't act as an indicator. However, I agree with what you said about
producing other artificial indicators. Since an alkali metal salt of a coloured organic weak acid would act as an indicator, I was thinking maybe it could be possible to create other
indicators by coupling 2 or more benzene rings with a diazo bond (to provide the colour to the indicator), with a sulfonyl group on one of the rings to act as the weak acid. Or
else, the weak acid part could be a phenolic -OH bonded to a ring having strongly deactivating groups. Also, the compound would have to be soluble in water to act as an acid/
base indicator.
vulture March 18th, 2004, 05:58 PM

I've probably mentioned this before, but if you're titrating something with either NH3 or HCl, CuSO4 can be used as an indicator for neutral pH.
The smallest excess of NH3 will cause the solution to go to blue, a small excess of HCl will cause it to turn green. I've tried this and the transition is rather sharp and easily
detected by the naked eye.
A small amount of coppersulfate will do.

Thats a useful thing, with copper sulfate :)
T Pyro, it doesn't have to be a salt. The compound changes color because its double bonds change position. And this can happen simply if a carbonyl group takes an H+ (in
acidic medium), or as you said, hydroxyl group loses it's H+ in strong basic conditions. This affinity to H+ can vary greatly depending on how large is the conjugated system.
IIRC, absorbed light depends on total energy of doublebond system.
Oh, and ketone (or aldehyde) condensation mechanism is a bit different from that pic, because, in third step, the H+ will leave methyl group to form a double bond much
faster than that carbonyl oxygen would attack.

Using copper sulfate, shouldn't the end point be indicated by a pale blue ppt. due to the formation of copper hydroxide? The dark blue colouration appears only after there's
enough excess of ammonia for the entire copper to be precipitated out, and then dissolved as a complex. By that point, the ammonia would be in excess, beyond the
equivalence point. Nickel chloride, however, might work better because with ammonium hydroxide, it readily forms a blue complex, even before forming any ppt. The result is
a sharp green to dark blue transition.
Frogfot, what you're talking about seems a lot similar to the basis of infrared spectroscopy. So if we have a compound such as 2,4,6 unsaturated ketone (or aldehyde), would
it act as an indicator? It does sound a bit doubtful to me... :(
About the condensation mechanism, it's quite different from the condensation due to the presence of bases. However, if the H+ ion was extracted from the methyl group, due
to keto-enol tautomerism, it would speedily revert to acetone. On the other hand, in the presence of a concentrated, strong acid, the concentration of the carbocation species in
the third stage just might be high enough to promote the reaction.

a n d I m provised C hemistry > Household Film as Polym eric Binder
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Microtek March 21st, 2004, 02:09 PM

Most types of ordinary household film are simp ly sheets of low density polyethylene ( LDPE ). LDPE is basically chains of
(CH2)n with som e degree of branching in the chains, whereas HDPE has no branching but is otherwise similar. Both LDPE and
HDPE are therm o p l a s t s , m e a n ing that they soften when heated but LDPE, which the rest of this post will deal with, does not
m elt com pletely at sufficiently low temperatures. Instead, it softens at about 110 C much like hot-glue. This viscousity m a k e s
m ixing it with crystalline HE inconvenient though doable, but the HE can be sprinkled onto a sheet of LDPE which is then folded,
m ore HE is added, the sheet is folded again, and so on. At the end of this procedure a wa fer consisting of alternating layers of
LDPE and HE is obtained. This is then placed on a hotplate or in the oven and heated to a t e m p i n t h e 1 1 0 - 1 8 0 C r a n g e (
a s s u m i n g R DX or other high m elting HE ). This causes the LDPE to soften and flow together like hot glass. Then the m i x m u s t
be worked with a spoon or oth er utensil to form a h o m o g e n o u s m ix of LDPE and HE. This is effectively done by flattening the
m ass, and then folding it onto itself, then flattening again and so on. Ab out 10-2 0 tim es usually d oes it.
T h e s o f t m ass can now be cut up and packed into whatever shape is desired while m aintaing a tem p e r a t u r e o f 1 1 0 - 1 8 0 C .
A p p l y i n g a l i t t l e p r e s s u r e m a k e s t h e f l a k e s m e r g e s e a m lessly and on cooling, the product will be q uite strong and well suited
for machining.
I n t h i s m a n n er I easily produced a PBX consisting of 90.5 % RDX and 9.5 % LDPE. It had a density of about 1.5 g/cc and wa s
very strong.
Another useful property of polyethylene is the very high heat of com bustion; ca 42 KJ is released when one gram of PE is
burned in excess oxygen.
T h i s m akes it a suitable binder/fuel for rocket propellants as it gives a very robust grain with high chem ical stability in addition
to the high e nergy content.
Thus, a mix of 30 g LDPE and 200 g KClO4 makes for a slightly fuel rich mix which has an energy content of about 5000 J/g;
better than many other non-m etallized propellants.
Finally, LDPE is a useful material in the lab due to its ch emical resistance ( as evidenced by its successful use in HNO3
destillation ) so m any different types of labware can be made with a little creative thinking.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry >
Sodiumtripolyphosphate (Na5P3O10) as a dehydrator
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simply RED March 27th, 2004, 09:35 AM

The idea of using Na5P3O10 as a dehydrator was intriguing me for a while.
As its known polyphosphoric acids are anhydrides of the ortophosphoric acid, so they react with water to produce the H3PO4 like P2O5 does. Polyphopsphoric acids need higher
temperatures to react with water than acetic anhydride and P2O5.
Today i planned and carried out the next experiment :
In two separate beher glasses, 60 ml mixtures each one containing 30 ml H2SO4 (97%) and 30 ml HNO3 ( only 59% ) were introduced. In the first glass 15-20 grams
Na5P3O10 was added. The first glass was heat on boiling water bath for 10 minutes. Then the acid was decanted from the precipitate (the precipitate become one porous piece
and nearly all the acid decanted).
This mixed acid and the acid in glass 2 were cooled to 12-15 degrees celsius.
Samples cellulose were introduced in both cooled acids.

After 7 minutes the product was extracted, washed and tested.
The sample nitrated with Na5P3O10 dehydrated acid was nitrocellulose.

The sample "nitrated" with the acid in glass 2 was pure cellulose.
Na5P3O10 is sold here for 2 dolars the kilo...

Do Na+ ions inhibit the RDX synthesys?
p.s. Do the heating in jar with screwing cap, the watch glass is not enough to close the beher and the "lab" becomes full with fumes!
nbk2000 March 27th, 2004, 05:05 PM

Triclene is a trademark name for STPP, which is used in toothpaste as a whitening agent apparently.
The ratio of 1:1 of sulphuric/nitric is too low for proper nitration, but you are suggesting that using STPP allows you to use much less sulphuric, correct?

This could have many uses...
I can't see why it would interfere with making RDX, if it's a strong enough dehydrating agent. I'm also thinking it might help me make ethylene urea from urea and ethylene
glycol...
simply RED March 28th, 2004, 04:59 AM

Obviously with 59% HNO3 you can't nitrate cellulose no matter how much H2SO4 is used.
The ratio 1:1 in volume is okay if the acids are concentrated enough.
STPP dehydrates the nitrating mixture making it more concentrated. I don't know all the reactions that take place but obviously we have the fragment:
P-O-P + H2O = P-OH + P-OH
Chrystalohydrates with different percentage water may also form.
Na2HPO4.12H2O !!! :P
So the mixture is enriched in acids (the water reacts with the STPP and is no more presented)
Na+ ions are not wanted here as they are only balast and provoke side reactions (Na+ + HSO4- = NaHSO4associate) (not making problems but anyway).
If we find tripolyphosphoric acid (TPPA) it will be much better.
STPP will help making TNT in the last nitration, higher the yield of alcohol esters....
TPPA will be more effective and may fully replace acetic anhydride.
Polyphosphoric acid coresponding to 75% P2O5 maybe available. This voscous liquid is equivalent to acetic anhydride.
Marvin March 31st, 2004, 05:59 PM

If you strongly heat phosphoric acid, or any of the ammonium phosphates they will dehydrate/deammonate first to pyrophosphates and then to meta phosphates which Ive
mentioned before in the contexts of dehydration and phosphorous manufacture. Metaphosphoric acid is essentially the ultimate polymer of phosphoric acid. Glassy solid,
dissolves/rehydrates rather slowly in water. Corresponds to a polyphosphoric acid of very neerly 90% P2O5.
Using sodium salts is a problem for several reasons, major first being that it reduces the strength of the acid, because the free polyphosphoric acid is weaker as is the
secondary and tertiary orthophosporic hydrogens and major second that it effectivly prevents recovery of acids afterwards.
Nitrocellulose is very much a sliding scale as to success. If you wanted to more accuratly determine how well esterification went and you have access to the common lab
solvents, eg ether, alcohol, chloroform, acetone, possibly ethyl acetate, you can determine how much of a nitrocellulose sample dissolves in certain magic mixtures and work
out a rough N% from tables.
simply RED April 2nd, 2004, 02:32 PM

Do you have a recipe how to turn orto to meta?

a n d I m provised C hemistry > R ed Iron Oxide -> Black
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Cyclo_Knight April 4th, 2004, 12:08 AM

I currently have nearly 20 pou n d s o f r e d i r o n o x i d e ( F e 2 O 3) sitting in m y garage, however this is not optim al for thermite. My
therm ite burns much hotter when I use black iron oxide(Fe3O4), so I was wondering if the re is a way to turn Fe2O3 into Fe3O4.
I already trie d a d d i n g s o m e s t e e l - w o o l a n d p e r o x i d e t o t h e R e d o x i d e , b u t t h a t o n l y p r o d u c e d m o r e r e d o x i d e .
Is this reaction possible or do I have to waste m o r e m o n e y o n b lack?

A Google search turned up nothing relating to this :(
Mumble April 4th, 2004, 05:00 AM

T h e m e t h o d I h a v e f o r p r e p a r i n g I r o n ( I I , I I I ) O xide is pretty straight forward. Fuse equim o l a r a m o u n t s o f I r o n ( I I ) a n d I r o n
(III) Sulfates. They will give off SO3 and you will be left with Fe3 O4. Probably wont be m agnetic like the m ineral tho ugh.
My heating Iron (III) Oxide strongly, I believe it will red uce to Iron (II) O xide. It will be evident by an change from red to dark
brown/black. You could m a k e t h e s u l f a t e s f r o m here. If you want to try to just fuse the O x i d e s b e m y guest, but I can't
g u a r a n t e e s u c e s s . T h e Iron (III) m ay just be reduced to Iron (II) and you couldn 't tell them apart.

a n d I m provised C hemistry > Increasing fuel power.
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Wahur April 15th, 2004, 12:56 PM

Ok. If I mix NaNO 3 with fuel will it m ake it burn the fuel better so I could use it as a "turbo" mixture for m y car? I'm thinking
of an 1500cm3, carburator engine with a quite low com pression. Or could I use NH4NO3 with methanole? I'm guessing that the
NH4NO 3 with fuel will blow the hood off but m e t h a n o l e c o u l d h a n dle bigger com pression without pre-detonating.
Bert April 15th, 2004, 04:07 PM

Ok. If I mix NaNO 3 with fuel will it m ake it burn the fuel better so I could use it as a "turbo" mixture for m y car?
=========================<snip>========================
Or could I use NH4NO 3 with m e t h a n o l e ?
I don't think you'd get very much of either dissolved in gasoline or m e t h a n o l . Y o u ' r e n o t m u c h o f a m o t o r h e a d o r y o u ' d h a v e
heard of nitrom ethane (http://auto.howstuffworks.com/question642.htm ) which does, or can even be used by itself as a fuel...
A little searching would probably have found you this info. If you haven't read the Rules (http://www.roguesci.org/theforum /
faq.php?faq=vb_faq#faq_faq_therules), best do so.

Tolu ene or xylene are nice additives too, as their octane rating varies between 110 and 140 depending on the isom er.
kingspaz April 15th, 2004, 06:28 PM

bloo dy hell. you can't increase the power of a fuel. the same bonds get made overall (which gives the energy)
nitromethane is the highest energy fuel. raising octane will only improve power to a certain extent. in a low com p r e s s i o n e n g ine
the difference will not be that great. if you raises the com pression of the engine with perform a n c e h e a d g a s k e t s a n d b e t t e r
piston rings then it would benefit m ore from octane boo sters. this alone will not have that much effect as you must also
increase the amount of fuel burnt and hence the air it n eeds to burn. you could get N2O injection. it decomposes in the
cylin ders to release oxygen which goes on to react with the fuel. this would be useful in a low comp ression engine as it would
be able to ta k e a n N 2 O b o o s t a l o t m ore freque ntly. ultim ately though for good power gains the cylinder head must be ported
and flowed followed b y necessary upgrades in exhaust and airfilter design to allow more fuel to be burnt. twin carbs would also
benefit your engine a s m ore air can be taken in and m ixed with much more fuel to be burnt.
as far as i ca n s e e f u e l c h a n g e i s n o t g o i n g t o m ake a great deal of difference without heavy engine m odification. a lso, this
d i s c u s s i o n h a s n o p l a ce in this forum.
end of topic

a n d I m provised C hemistry > Thorium a n d U r a n i u m
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chemofun May 3rd, 2004, 11:05 PM

Does anybody here know how to separate Uranium from Thorium chem ically? I'm not sure how this would be done seeing as
how they both have 2 valence electrons. They are pretty close on the periodic table so i don't know if there is enoug h
difference in electronegativity to create differen t and easy to separate ionic compounds. Any im put from real chemisty buffs
would be greatly appreciated. Thanks.
Marvin May 4th, 2004, 05:27 AM

In terms of practical m ethods it usually depends on exactly what you have, the m etals, nitrates, sulphates etc, what relative
a m ounts of each and what impurities.
Specifically for thorium and uranium only and m acroscopic amou nts of each, thorium nitrate is m o r e s o l u a b le in water than
uranium nitrate so fractional crystalisation will seperate them . Uranium nitrate can be extracted from Aq solution to ethyl eth er,
leaving the thorium n itrate. Thorium can also b e precipitated as its sparingly soluable oxa late.
For m uch sm aller amounts of thorium in U solu tion, again for nitrates, adding am m o n i u m c a r b o n a t e i n l a r g e e x c e s s a n d
boiling will precipitate thorium as its hydroxide. This can be done fraction ally for other contaminants.
U/Th is a fairly easy case and things get more difficult for other m e m bers which a l l h a v e t h e s a m e p r o b l e m , s2 p0 outer she ll.
This is somewhat highlighted by the ra dioacitivty of this group which dem ands very high seperation often from a tiny
concentrations in one of the other m embers. Typically the best idea is to oxidise a solution with a m ixture of actinid e s t o
selectivly force som e o f t h e m a q u i r e u n u s u a l o x i d a t i o n s t a t e s ( + 3 , + 4 f o r e x a m p l e ) . D i f f e r e n c e s b e t w e e n s p e c i e s c a n t h e n b e
exploited, such as solubility in organic solvents, which can vary massivly m ore according to what oxidation state an ion is in
than between two different elements in the sam e oxidation state. In essence its forcing the f shell differences to com e into
p l a y b y g o i n g b e y o n d 2+. This is the b asis of the well known dibutyl ptha l l a t e b a s e d p l u t o n i u m e x t r a c t i o n s y s t e m .

a n d I m provised C hemistry > Lithium from Batte ries
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johnnycab May 6th, 2004, 12:26 PM

Hi. I am trying to find out how to extra ct eleme ntal lithium from lithium batteries (if it's possible). I am *not* trying to m a k e
drugs (since that is what seem s to com e up when I google this topic) or explosives; I want the lithium as part of a Table of
Elem ents I'm working on.
I u n d e r s t a n d the hazards of e lem ental lithium - s p o n t a n e o u s c o mbustion upon contact with m oisture, etc. - and realize it must
b e s t o r e d u n d e r m i n e r a l o i l o r n a p t h a . I f o u n d o n e s i t e w h e r e a g u y m e n tions getting lithium from batteries (http://
www.theodoregray.com/PeriodicTable/Elem e n t s / 0 0 3 / i n d e x . s 7 . h t m l ) , b u t h e d o e s n 't say ho w to do it. He also says that the
purity is < 5%, but I'm not sure if that means the whole battery or the actual lithium com pound in the battery or what.
Thanks.

The following thread already has details about lithium in batteries:
That thread is probably the best place to post if your questions are not a lready answered by it.
aikon May 6th, 2004, 06:33 PM

...I found one site wh ere a guy mentio ns getting lithium from batteries... ...but he doesn't say how to do it....
I just browsed the site and he gives detailed instructions for the procedure.
Go to www.theodoregray.com/PeriodicTable/Stories/003.2
Just one klick away of the url you posted. :)

In the interests of posterity I am reproducing the text o f that we bsite here:
Extracting lithium foil from a battery
Initially only used in fancy camera batteries, lithium is now available in AA and 9V batterie s for use in things like sm o k e
detectors and digital cam eras. They are m ore expensive than re gular batteries, b ut last a lot longer.
The great thing about disposable lithium cells is that the lithium exists in the form of a foil, not so me kind of powder you ca n't
separate. Note that this is only true of new, unused disposable lithium batteries. The reaction that powers the battery
c o n s u m e s a n d f r a g m e n t s t h e l i t h i u m , and you won't get a foil out of a used one. In fact, based on m y experience
d i s a s s e m bling a fully discharg ed lithium AA battery, it's not something you would want to do. Shortly after unrolling the coil
(see below for m ore details) the thing actually spontaneously ignited in front of m y eyes. Seriously, I opened it up, it started
feeling warm, and seconds later the paper towel it was on burst into flames. I've never really had that happen before in quite
s o s p o n t a n e o u s a w a y , i n m y 30-odd years of taking things apart and so metim es trying to make them burn. (I picked up th e
paper towel from the sides, which were not burning yet, and set it on the concrete floor of the shop for safe burning out.)
I'm not really sure whether this was a unique event (it was extrem ely hum id at the tim e, which may have contributed). I've
never had it happen with a fre sh battery, and I'm not planning to repeat the used battery experiment, except m aybe to film it
s o m e tim e.
Anyway, back to fresh batterie s. To get pure metallic lithium , a l l y o u h a v e t o d o i s d i s s e m b l e t h e b attery and unroll it.
Of course, th is is som ewhat like saying all you have to do to save the wo rld is clip the righ t wire on the tim e b o m b .
Disa s s e m bling a AA lithium battery is not som ething to be done lightly: It can be quite da ngerous. The chemicals inside will
b u r n e x p o s e d s k i n a n d e y e s , a n d a s I c a n t e l l y o u f r o m personal experience, it's entirely possible for it to catch fire completely
unprovoked. Eye protection is absolutely, positively required for any experim ent involving alkali m e t a l s , a n d y o u s h o u l d a l s o
work in an area where things can burn them selves out harm lessly. A concrete floo r (withou t spilled oil) is good, or I like to use
a cast-iron welding table I got at an auction.
O n e p r o b l e m is short circuits. If you short out the term inals of a lithium battery, it will heat up quite rapidly (a second or two),
a n d c a n b e c o m e d a n g e r o u s l y h o t . Y o u m a y h a v e r e a d a b o u t p e o p l e w h o s e p o c k e ts caught fire when they carried these things
loose with so m e c h a n g e o r k e y s .
The trouble is that when you use diagonal cutters to clip away the fairly tough metal casing, you'll almost certainly m a k e
contact with the positive term inal, because that's the on ly place you can start cutting. The key is to cut away the top as quickly
as you can, removing any internal shorts you've created before it blows up in your hands.
Once you've started the cut at the top rim, rem oved the various disks an d rings you'll find at the top, and m a d e s u r e t h e r e a r e
no shorts (as evidenced by the fact that it's not continuing to get hotter), the casing can b e p e e l e d b a c k u s i n g d i a g o n a l c u t t e r s
or som e pliers, until you've exposed enough of the coiled core to pull it out of the casing. Be careful not to puncture the plastic
inside, or you'll create more short circu its. If you're foolish enough to have gotten this far, be warned that from here on out,
y o u s h o u l d d efinitely be wearing non-flamm able gloves. You do not want to touch elemental lithium with your bare hands,
especially if you're nervous. (It reacts strongly with moisture, liberating hydrogen gas. On the plus side, this gas will usually not
spontaneously catch fire.)
If you clip away the plastic wrap or tape holding the coil together, you can then sim ply unroll the th ing, which will separate into
several layers. O ne is a shiny metal fo il that looks a lot like alum inum foil. It is, in fact, aluminum foil, so discard it. Another
layer is a bla ck flaky/powdery substance that sm ells bad. This is the electrolyte, which you should wrap in a plastic bag and
discard in a fire-safe way. The re are also some plastic layers that are of no intere st. W hat you're a fter is the dull, soft foil that
is probably d ark brown by the time you see it. This is th e lithium .
D e p e n d i n g o n t h e h u m idity level, it is almost certainly oxidizing before your very eyes. O n a m o i s t m idwestern night, the foil
will actually stay com fortably warm , sim ply by the continuous rea ction with water in the air. In any case, it will not last long,
certainly not a whole day, in the open air.
You could try to preserve it un der oil, but what's the fun in that?
Or you could throw a sm all patch of it into a bowl of water, but of course that would cause it to disintegrate almost instantly in a
froth of bubbles, which there is small but real d anger co uld ignite spontaneously. (The reactivity of alkali m etals increases as
you go down the periodic table. If you throw sodium or potassium into water, the gas most likely will ignite, but with lithium,
the reaction usually isn't hot enough to light the gas. At least not in my experience: This could be your chance to m a k e
e m ergency room history.)
A fellow experimenter, Gill, reports his techniqu e for extracting lithium foil intact:
Get a container of dried liquid paraffin ready.
Dism antle battery. In the process you will inevitably crush the foils thus short circuiting the battery and causing a fire. W ait until
it su bsides and carry on. You will only have burnt about a 50th o f the Li.
O n c e d i s m antled, put the foil as quickly as possible into the liqu id paraffin and separate from any rem aining waxed p a p e r
strip s or other battery content under liquid paraffin.
It's not as difficult as the first attempt misleads you. Don't be put off by sm all fires. Short circuiting the insides of the battery,
thus igniting it is inevitable, but happe ns at the early stages when the Li is still well enoug h covered by battery case to run out
of oxygen before burning away.
Personally, I haven't had that much problem with them catching fire from short circuits. It probably depends a lot on the brand
of battery you're using.
nbk2000 May 8th, 2004, 06:16 PM

W h y n o t s i m p l y d i s s a s s e m ble the batteries under the kerosene in the first place, obviating the fire , as it ca n't ignite the oil
from underneath the surface, as there's a lack of oxygen. :)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Benzaldehyde
(missing thread)
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Marvin August 19th, 2004, 08:15 AM

There are 2 good threads missing from this section I think, one is benzaldehyde and I'm dammed if I can remeber the other.
The gist of the thread was,
Turn toluene into benzyl chloride using the hypochlorite route.
Hydrolysis of benzyl chloride would normally get us only benzyl alcohol, so instead use the Sommelet Reaction. The benzyl chloride is reacted with hexamine, forming a
quaterary salt, and then this can be hydrolysed under mild conditions to benzaldehyde.
Description of the Sommelet Reaction here,

http://themerckindex.cambridgesoft.com/TheMerckIndex/NameReactions/ONR373.htm
I dont remeber who started the thread and my apologies if they were planning to restart it, but as memory serves they stopped posting only a few days after starting the
thread and didnt reply to any of the questions as to specific conditions.
A tentitive suggestion is 42g of benzyl chloride to be added dropwise into a boiling suspension of hexamine 48g in water (unknown, enough to dissolve the salt - all the
hexamine should dissolve after addition of the chloride) and the mixture refluxed for 2 hours. Alternativly the benzyl chloride can be simply added to the hexamine in water and
then refluxed for a slightly lower yeild. A small amount of HCl solution is added to prevent Schiffs bases in the condensate, and the mixture steam distilled until the condensate
is nolonger cloudy, or stops smelling of benzaldehyde. Method reconstructed from fragments of related methods. Yeilds of 80% should be achieveable based on benzyl chloride.
akinrog August 19th, 2004, 06:51 PM

Dear Marvin,
I found the reference you requsted at the hive.
Here is the link (https://www.the-hive.ws/forum/showflat.pl?Cat=&Number=519043&page=&view=&sb=&part=1&vc=1).

Post number is 515478 I believe.
HTH.
P.S. It might be necessary to become a member to view this thread.

P.S. 2 Funny thing the poster made reference to mega's synthesis and another guy says the method is not correct.
P.S. 3. In the post there is a patent (no 431412) which describes entire process (starting from toluene to Benzaldehyde).
Bugger August 20th, 2004, 08:41 PM

Or you can hydrolyze the benzyl chloride to benzyl alcohol with a strong alkali, and then oxidize the alcohol to benzaldehyde, preferably using CrO3-pyridine complex in
dichloromethane solvent.
It is difficult to go directly from toluene to benzaldehyde, because oxidation of the CH3 in toluene by the usual reagents like hot alkaline KMnO4 (followed by
acidification)results in further oxidation to benzoic acid instead.
Bugger.
Mr Cool August 21st, 2004, 09:21 AM

Damn, I'm out of CrO3 and pyridine at the moment. But I have a few kilo's of hexamine....
I prefer the Sommelet rxn ;).
Marvin August 21st, 2004, 09:28 AM

akinrog,
Thats a good reference. The essential differences are, the benzyl chloride contains considerable toluene, which helps to extract the benzaldehyde into the organic phase
afterwards, this can be seperated and fractionated, avoiding a steam distillation. (The patent talks about tolualdehyde but this is an exact analog of the process). Its possible
since no water miscable organic solvent is used the steam distillation can be dispensed with even if no toluene is present. Much more HCl, reducing the pH to 3-4, this prevents
amines in the organic phase (I assume). In the information I've read adding HCl was optional before the steam distillation to prevent a cloudy condensate masking the end
point of the benzaldehyde coming off.
Being able to use the result of the chlorination directly when using chlorine gas is useful, as it reduces contact with the very toxic benzyl chloride, I have a feeling this is as
broad as its long though as venting large amounts of chlorine gas contaminated with toluene and benzyl chloride might turn out to be just as nasty. The hypochlorite/toluene
method looks a easier on the face of it.
My references are all 60 years old or more. Interestingly the actual yeild, 80%ish hasnt changed in 40 years and the only innovation is the use of crude benzyl chloride! Maybe
BASF had other reasons for trying to reestablish rights to such an old process.
The only possible thing I can see with the Benzal chloride method mentioned, is that hydrolysis is normally done with calcium hydroxide. Maybe the method was adapted from
a working benzyl chloride method (to benzyl alcohol) that would be easily hydrolysed by water/CaCO3 or maybe it really does work. I respect Organikum on most matters but
from experience on sciencemadness the less sure he is the less likley he is to give a reason for his opinion. I'm sure his ratio for hexamine to benzyl chloride works and its close
enough to what I calculated, being a little high on the hexamine.
JohnW,
I'm unsure if the usual safe bets like PCC in aprotic solvents will work for benzaldehyde, regardless, its expensive and unsubtle. The founding principle for those that dont know
is that oxidising an acetaldehyde itself is much harder than oxidising the diol it forms in water. If you are doing a complicated molecule and need a high yeild of the aldehyde
from the alcohol, PCC and its cohorts are doubtless the way to go. Conversely though, if you need acetaldehyde you can distill it out of a mixture as it forms and get a
reasonable yeild from a more convensional oxidising agent at much less cost/complexity. Ethanol is cheap. We cant distill benzaldehyde out of the mixture but we do have
more leeway than with aliphatics. Benzaldehyde is a tad harder to oxidise than most aldehydes and this gives us a wider range of reagents and processes. The other key
difference is that its not possible to generate the aldehyde from the ammonia addition product, so bisulphite compounds have to be used instead if this level of purification is
required.
In the vapour phase we could catalytically oxidise toluene with air/MnO2 at 500C and the product is supposed to be very pure. Out of easy reach as a lab method though.
A mixture of MnO2/Copper sulphate/Sulphuric acid will oxidise toluene to benzaldehyde but its easy to take this too far and get benzoic acid. I'd like a reliable method for this
but the only reference Ive found is a passing mention in Karrer. frogfot found a version optimised for a continuous extraction, US1302273, it looks like a lot more experiments
need to be done before we have a halfdecent method though. His thread is on sciencemadness here,
http://www.sciencemadness.org/talk/viewthread.php?tid=2223
Chromyl Chloride CrO2Cl2 will take toluene to benzaldehyde and stop. (Karrer)
2-nitropropane will oxidise benzyl bromide (and probably chloride) under strong alkaline conditions (ethoxide) to benzaldehyde but this is another one of rather limited
application only. (Organic syntheses)
Copper nitrate will oxidise benzyl alcohol or benzyl chloride to benzaldehyde and stop. I think this has potential.
The method for benzyl chloride is,
250ml flask reflux setup equipped to bubble CO2. Through the condensor is poured 23ml of benzyl chloride and then a solution of 20grams copper nitrate in 125 ml water. CO2
is used to sweap out the oxides of nitrogen and the mixture is refluxed for 8 hours keeping a steady current of CO2. Benzaldehyde is extracted with several small portions of
ether in a seperating funnel.
The ether extract is then purified by the sodium hydrogen sulphite addition compound. Most of the ether is removed by heating in a water bath and excess saturated solution of
sodium hydrogen sulphite is added. The crystals are rapidly filtered and treated with a slight excess of sodium carbonate solution and the benzaldehyde is extracted with ether,
dried over anhydrous CaCl2, ether boiled off and the remainder distilled keeping the fraction between 178 and 180C. Method from Organic chemistry, 3rd Ed, by Stokes. How
or if the method needs to be altered for benzyl alcohol isnt stated.
It should be possible to generate the copper nitrate solution in situ, so if a replacement for ether can be found, or the product purified via a different method I think this is a
reasonable contender to the Sommelet reaction. Purification of the ether extract is clearly a generic method for benzaldehyde.
Bugger August 22nd, 2004, 01:53 AM

Thanks for your possible alternatives for benzaldehyde. Because of the use of benzaldehyde as a food flavor (oil of bitter almonds), as well as for further organic syntheses
where it is desired to introduce benzyl groups or else further groups to the benzene ring, I would be most interested in which method is best for large-scale industrial use -
which do you think is most suitable?
BTW Can Organic Chemistry, 3rd Ed., by Stokes, be downloaded from anywhere? Otherwise, do you think you could email it to me?
Bugger.
organikum August 25th, 2004, 04:51 PM

The Sommelet reference at the HIVE is from me and also mine is the opinion that this sentence:
"The crude benzaldehyde oil is treated with a concentrated solution of sodium bisulfite, after shaking for a long time the oil should have dissolved into solution. If any crystals
happen to form during the shaking, add water until they dissolve."
is plain nonsense, may it come from incorrect citation or whatever.

It was asked if this is correct. The answer was and is: NO.
Megalomania or not.
Benzaldehyde is supposed to precipitate as sodium-bisulfite addittion product. "Crude" benzaldehyde wont easily precipitate, if at all - the bisulfute purification works only on
fairly clean substrates.
The patent I presented works perfectly well - its tried and true.
Benzalchloride hydrolysis:
The benzalchloride is SLOWLY run INTO a SLURRY of water/calcium-carbonate under STRONG STIRRING, some added calcium hydroxide doesnt hurt but may be helpful. Then
the broth is refluxed for some hours water added and steamdistilled.
If you just add water/hydroxide/carbonate and reflux you will not need 2 hours, not 4 not 10, but some days.
Benzalchloride synthesis: DONT try to make banzalchloride by the LOOMIS patent method, heating hypochlorite and toluene. There is a high probability that you will get an
explosion. Thats just because so much hypochlorite is needed that the toluene will not cover it completely all time. And thats NOT GOOD, believe me.
Abigail September 14th, 2006, 03:09 PM

Hey, i have no reference but benzalbromide is a alternative to the chlorine method and bezahl chloride. Dryed bromine is bubbled through boiling toluene, i belive that will do
the same.
100 ml toluene to 271,3 g benzalbromide by weight.
I think it is correct when bromine is dropped into boiling toluene to get benzalbromide. You need no chlorine or bromine generator.
I`m not shure you can get benzaldehyde at the same conditions with calcium carbonate.

a n d I m provised C hemistry > O n-line chemistry courses
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lumberjack S e p t e m b e r 5 th, 2004, 09:23 AM

D o e s a n y o n e k n o w o f a r e a l l y g o o d o n - l i n e c h e m istry course? Are there any free courses? I would really like to find an
intermediate, self-paced course that is thorough and easy to understand. I know this m ight be a tall order to fill. There is so
m uch on the web, I was just wondering if any of you guys had fo u n d s o m e real good stuff amongst all the clatter.
Real_Wrestler October 3rd, 2004, 05:02 PM

I g o o g l e d " C h e m istry courses" and came up with what seem ed like a good site.Here (http://www.in d i a n a . e d u / ~ c h e m info/
c_course.htm l)
I'm not a big fan of online course, i had a frien d who took highschool chem istry o nline, to make a long story short, He went
i n t o A P C h e m istry not knowing what a m ole was.....
Marvin October 4th, 2004, 02:52 AM

I simply dont bilieve that its p ossible to teach chemistry without giving th e s t u d e n t h a n d s o n e x p e r i e n c e .
I also think that a nice energetic redox reaction perform ed by a teacher, eg a the rm ite, is one of the best ways to convince a
class that they want to know what a m ole is and how to calculate the right am ounts for the m ost spectacular reaction.
C h e m istry has a lot o f very dull aspects that arnt any use until m uch late r on.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Freebase Nicotine
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A2675770 September 6th, 2004, 04:57 PM

I've been researching the possibility of turning Freebase Nicotine into a gas form which could be contained.
I have the properties, Melting, boiling, flash, ect, points, But I'm frustrated with the process, I can't seem to find a method that is logical and sufficient,
Any recomondations? Ideas? Exp?
-A26

Nicotine has a boiling pt. of 246C at 730 mm Hg, and melts at under -80C. That is a reasonably high temperature to try to get it into the gas phase,but it is attained in
smoking cigarettes. It would probably decompose at significantly higher temperatures. It is very soluble in a wide range of solvents. Why do you want to vaporize it?
Bugger
festergrump September 7th, 2004, 02:54 AM

Perhaps he wants to end his life for not reading the rules before the Mods get to him? It IS a strong poison.
A26, Just what are those melting, boiling, flash, ect. points you found? (DAMN Bugger "buggered me"...) :p It doesn't happen to say on MY cigar box, anyw ay.
Anyone else noticing a major increase in newbies starting new threads w ith interesting ideas, yet not going into detail about what they may have already learned from their
OWN expirience (or telling what they might have found in their own searches). Call it paranoia or call it careful, I smell idefense and it's fucking foul...
(EDIT: I had mind to delete the latter half of this post but thought better of it. I AM w ondering about the newbies, but also wondering where A26 might be going w ith this.)
#1-N-B-killer September 7th, 2004, 05:39 AM

Thats a new one, well I do know how to extract it into a betw een a liquid and gaseous state, but I dont know how to turn it into a true gas . Nicotine is isolated from tobacco by a variety
of methods; some of the most recent include supercritical CO2 extraction, where carbon dioxide is compressed to a supercritical state (betw een a liquid and a gas) under high
pressure, thus becoming a non-polar solvent. When the extraction is done, the CO2 evaporates leaving behind nicotine.
Assume you have a chamber full with tobacco leaves, and connected to it you have another chamber. You fill the empty space of both chambers w ith CO2, Keeping the
temperature slightly above Tc, and you carry on pumping in CO2 to a high pressure.
At a certain point the gaseous CO2 acquires the density of liquid CO2, and is
capable of dissolving some of the constituents of tobacco, e.g., nicotine. If
you w ait enough time or if you impose a forced circulation between the tw o
chambers, after a while, you'll have the same concentrations of solutes all
over the place. If you close the connection between the chambers, the amount of gaseous solution of the tobacco chamber will be smaller than that of the other chamber.
The solutes dissolved in the gaseous CO2 because at that density its action
is like that of a liquid solvent.
What do you do now to recover the solutes you have in the second chamber? You can either slightly cool the gas below Tc, and get some CO2 condensation, w hich will dissolve
the solute, or perhaps better, you can reduce the pressure, remaining supercritical, and the solute will condense out of the gas as a liquid or solid, as the case might be.
Take out the precipitate from the second chamber and repeat the operation as necessary, until you extracted whatever is extractable under these
conditions. You'll also get denicotinized tobacco. ""I m not sure if there is a way to make nicotine gas but I will research some more. Dos e anyone know how much nicotine m olecules
weigh?
FU TI September 7th, 2004, 02:13 PM

Supercritical extraction is fine...but almost unattainable to us mortals. Anyway that funny named new bie is undereducated p*nk that will be sp*nk by the mods for asking stupid
questions...nicotine free base is vaporised only through w ater destilation, its boiling point is to high and it would start to decompose if you try normal destilation, maybe vacuum
destilation can work, but I doubt. Best purification is through extraction and salt making recristalisation method (from tobacco), but you want free base. Grade please! above
90% or 99,9% by HPLC? What for? Poisoning your grandmother or just plant bugs? Not for E&W I'm sure. If you are trying some junk drug synthesis look some other forum
please. And have always in mind that you had been warned few times before you start stupid experiment with substance and matter of whom you obviously have unsufficient
knowledge so it is not our fault if you poision yourself.
A2675770 September 7th, 2004, 04:05 PM

The free base is extracted by ether and fractionated in a current of hydrogen and cannot be extracted from tabbaco.
Nicotine has a molecular mass of 162.23.
A ambitious attempt of aprox. 95% -99.95. My intrest in this is Stricktly hypothetical and a question of possibility.
Melting Point: -80 degrees Celsius
Boiling Point: 247 degrees Celsius
Flash Point: 95 degrees Celsius
Auto-Ignition Temperature: 240 degrees Celsius
Explosive Limits: 0.7 - 4 percent, by volume, in air
Vapor Pressure at Room Temperature: 0.006 kPa (as some were specified by Bugger)
Because of the ignition temperature, This is a learge obstacle.
NICOTINOIDS
The nicotinoids are a new er class of insecticides with a new mode of action.
They have been previously referred to as nitro-quanidines,neonicotinyls, neonicotinoids, chloronicotines, and more recently as the chloronicotinyls.
Just as the synthetic pyrethroids are similar to and modeled after
the natural pyrethrins, so too, are the nicotinoids similar to and
modeled after the natural nicotine . Imidacloprid w as introduced in Europe and
Japan in 1990 and first registered in the U.S. in 1992. It is currently
marketed as several proprietary products worldwide, e.g., Admire, Confidor,
Gaucho, Merit, Premier, Premise and Provado. Very possibly it is used in
the greatest volume globally of all insecticides.
Imidacloprid is a systemic insecticide, having good root-systemic
characteristics and notable contact and stomach action. It is used as a soil, seed or foliar treatment in cotton, rice cereals, peanuts, potatoes,
vegetables, pome fruits, pecans and turf, for the control of sucking
insects, soil insects, w hiteflies, termites, turf insects and the
Colorado potato beetle, w ith long residual control. Imidacloprid has no effect
on mites or nematodes.
Other nicotinoids include acetamiprid (Assail), thiamethoxam (Actara, Platinum), nitenpyram (Bestguard), clothianidin (Poncho,dinotefuran (Starke) and thiacloprid.
U.S. registrations for acetamiprid, thiamethoxam
and thiacloprid were granted in 2002 and clothianidin in 2003.
Mode of action--The nicotinoids act on the central nervous system of
insects, causing irreversible blockage of postsynaptic nicotinergic
acetylcholine receptors (See also Nicotine under the Botanicals).
Idefence!! How dare you fester? I started this thread because theres not to
many subjects left,the guys here have so exquisitely coved the facts I dont
dare argue with them, I started to wonder if I could make nicotine gas
because Im curious to see if its poss ible
Fester why would you post if you have nothing to contribute to the
discussion?
Anyone else notice a major increase in post w hores lately???
Why don t you let the mods deal with that,and unless you have a
theory for
making nicotine gas stay out of it please.
-A26
#1-N-B-killer September 8th, 2004, 01:10 AM

Yes you re right, nic otine has been and is used in many pesticides for aw hile, as well as other chemic al agents, but you really need to be c learer in youre posts. And in youre research,
what research have you done on this?
Could it be possible to maybe bind the nicotine with some other substance, like with other gases? Maybe it could somehow be binded or altered with a lighter than air molecule, I cannot
see an answer to this question until you do som e serious tes ts of your ow n, Im p retty sure no one has ever tried this one before. It w ill be a lot of work though, and probably a
consumption of time and money, but it is a cool thought!
FU TI September 8th, 2004, 11:32 AM

I must disapoint you man...mine grandmother used the some kind of boiling tobacco extraction procedure to obtain insecticidal solution for her roses...reading what you had
posted makes me very proud to be her grandson, she was a women ahead of her time beating two great scientific forces as US and Japan:). Can you post a some paper or
work where it is stated that you can't obtain nicotine free base from tabacco? You have mine full attention now.
festergrump September 8th, 2004, 02:20 PM

How dare you fester?
How dare I? I dare because I care about this forum and hate to see know -it-all newbs thinking rules don't apply to them and posting their first post ever as a new thread with
very little to explain w hat ground they have covered in their own studies on the topic they deem fit to bring to light. A search found 18 threads besides this one somehow
relating to nicotine (at least five of which it w as mentioned for it's principals as a deadly poison. It took me all of two seconds to search for and moments to scan the searched
threads for those five). So, if you happened to take offense at my previous post, good. Moderators aren't the only ones who sick at the blatant disregard for rules. You're
subject to all the rules just like everyone else no matter w hat you know or can bring forth.
The iDefense thing was a bit much and you have my apology for that. You w ere not the only one that was directed to, how ever.
I'm highly attracted to and motivated by this site because of just what it is: A haven for practical knowledge pertaining to explosives and weapons. As our rights diminish the
need for such know ledge increases.
With that said, I will leave your discussion alone after asking you one question: What would you plan to do with nicotine in a gaseous form? I realize your thoughts on this are
purely hypothetical, but as a weapon would it be practical, implementable, and somewhat expedient (at least in the sense that it can be created and packaged in the privacy of
ones own home, shop, or workplace)? Don't let the title of this section fool you. It's chemistry related to E+W, as is the whole forum. The Water Cooler is w here nonchalant
questions are posted and fit.
BTW, your implication that I am a post whore was kind of funny. I post here very little compared to most. You have my attention, also.
A2675770 September 8th, 2004, 02:46 PM

Thank you Futi, I stand corrected, you cannot extract Freebase nicotine from Cigarettes, Tabacco or the plant itself is deffinatly possible.
Fester I agree with you, This site is w ithout a doubt a great source of knowledge, from w hat I see, the best and brightest. As that said, You do have the right to defend it.
My first post was lacking, too much, and I regret not writing dow n the information I had.... I have no excuse for such ignorance.
My use?... The procedure seems difficult and I challenge it, opening possibility for other experiments with the obstacle of a lower ignition temperature then the boiling
temperature. I do believe that it could be a practical, cheap, and efficient small chemical weapon.
James September 8th, 2004, 03:43 PM

After a quick search of tw o webpages, I found the following. A) appearently Nicotone will explode (http://193.78.190.200/smokersclub/nicotine.html) before it boils. B) freebase
Nicotine is only absorbed (http://www .quit.org.au/quit/FandI/fandi/c11s2.htm) through the lining of the mouth. Note however that the sites refferenced are not impartial.
I think if I were going to try something similar, I w ould aerosolize a Nicotine salt. Probably Nicotine HCl (H2SO4 is a reccomended salt). I think that freebase Nicotine w ould shift
the PH of w hoever happened to breathe it in (barring the omnipresent buffers). I also recall that we have discussed Nicotine before (http://ww w.roguesci.org/theforum/
showthread.php?t=2568).
[edit: added thoughts fixed a bug]
FU TI September 9th, 2004, 08:59 AM

In theory you could kill a man with nicotin content of one cigarette since that molecule bind to a neuron and muscle receptors so it act similar to chemical weapons. I think that
extraction and litle pH adjusting and playing around with extraction again can give you very good result for a home made product. If you use some of the info posted here and
play w ith cristalisation and water destilation you could make veeeery pure compound. Free base form is highly impractical since most amine are easily oxidated in this form so
the shelf-life of it is sh*t (that is why hydrogen in the post you mentioned I think incorrectly since it is not the other partitioning phase but oxidation preventioning aid - usable
only to large scale). That is one of the reason why most of this compounds come as salt solution for inhalation or injection (depending of the activity). If it come as salt it
penetrate in body slow er through mucous membrane but it will make a balance that will enable it's absorption (it will work for nicotine since it has high activity). If you take
some other low er activity substance you w ill have to inject it to w ork. Still there is no link or work that I asked you for.

The Hive bees have supposedly been dinking around with fluorination of cocaine alkaloids, to greatly increase the potency, 40x or more.
Nicotine is an alkaloid, though a different type, and could perhaps be amiable to such molecular tweaking.
As the lethal dose of nicotine is ~ 3mg, if you made it 10x more toxic, that'd be .3mg per adult, which is on order of VX. :)

http://ww w.toxicology.lsuhsc.edu/clinphar/din/nicotine.htm
http://physchem.ox.ac.uk/MSDS/NI/nicotine.html
http://ww w.fullersysteminc.com/products/fulex_nicotine.htm
I thought 3mg wasn't quite right after remembering the approximate amount in cigarettes.
The above links provide some information as to nicotines toxicity. If it could be made 10x more toxic, as nbk said, it would still be a cunt of a poison!
FU TI September 11th, 2004, 07:07 PM

Thanks for a details kingspaz!
Well you see that mine memory is not that badly damaged. And you are right it is not such a strong poison because it w ork as competitive ligand with other neurotransmitters,
not like sarin and other holinesterase inhibiting substance. Rest of my story is about spreading the substance. I think some of those smoke-prevetioning patches that suppose to
help you abandon that bad habit contain the nicotine (you now one step at the time) so penetration is posible through skin. I w onder does some of those tricks to make your
subtance lipid soluble through (don't shot me if I made mistake) pamoic (or w as it pamidronic?) acid salt formation can improve its skin/mucous membrane penetration? In case
you A26 have wish (in your dreams of course) to kill some one with this substance you will have to go to injex thread:). And you can be sure this is not undetectable way of
killing someone that is not an insect.

a n d I m provised C hemistry > Making AN.
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anchorpad S e p t e m b e r 8 th, 2004, 07:54 AM

This is my first own thread, so I hope i dont get banned now. :(
I have searched on the forum after "Making AN" and couldnt find anythin g so I ask in a new thread insted.
For a while ago I m ixed Ca(NO 3 ) 2 + NH3.

This should become AN.
Anyway, I dissolved the calcium nitrate in the NH3 and stirred for a while.
After about 15 m inutes I filtered it. The liquid I had left I poured it into a saucepan and boiled away the NH3.
W hen no NH3 was left I had powder left which should be AN.
The thing is that the powder d oesnt dissolvs in water that easy it should do and when the powder finally has dissolwed the
water doesnt get cold.
I find this very strang e and wonder what I have m ake wrong?
C a n y o u m ake AN with this m ethod att all?
//An chorpad
( e x c u s e m y bad english, i work on it ;) )
Marvin S e p t e m b e r 9 th, 2004, 02:38 AM

Essentially adding stoichiom etric amm onium sulphate should work, and filtering o ut the CaSO4. You will need a lot of water
and filtering will be a right pain. Am m onium com p o u n d s t e n d t o m a k e c a l c i u m com p o u n d s m ore soluable, so this m ay still be
contam inated with calcium nitrate. For m ost people working hard er on finding a source of AN will pay out m any tim es what
tryin g to m ake AN will cost you in effort.
I f y o u d o n t g e t b a n n e d f o r m aking your first real post a new topic on a subject that allready exists, good lu ck and let us know
how well it works.

and Improvised Chemistry > Hydrazine preparation: anhydrous processes
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Well... this is my first new thread, please be patient with this enthusiastic little n00b :o .
I've been interested in hydrazine for a long time. Please, don't tell me "astrolite is for kewls" or "it causes cancer", I've read
up thoroughly about this and I understand the pro's and con's.
Now, every preparation method I've read includes the reaction of either ammonia or urea with a hyochlorite. I've never tried
this method, and probably never will for many reasons, but most important of all is that you gotta seperate the hydrazine
from water, and because using jello just sounds like a Mickey-Mouse operation to me. Also a waste of chlorine, and very little
end hydrazine for the liters of fluid you deal with.
The only other method I found was this:
H2NCl + H3N --> H4N2 + HCl
I haven't toyed with this either, because the result is hydrazine chloride. To get pure hydrazine, you'll need to mix it with a
hydroxide, which means more water, which means (getting monotonous?) a nerve killing distillation.
Also, how do you make chloramine without making nitrogen trichloride?
But today, I was searching info about hydrazine, and this came up:
http://www.booksmatter.com/b0471415537.htm
It'a 2000+ page exclusively about hydrazine. The price is 425$, I found used books cheaper, but still way out of what I'd pay.
But anyway, that link lists the table of contents, and this little bit is VERY interesting:
Preparation of Hydrazine from Ammonia

Preparation of Hydrazine by Photolysis of Ammonia
Preparation of Hydrazine by -Radiolysis of Ammonia
Preparation of Hydrazine by Glow Discharge in Ammonia
Preparation of Hydrazine in an Electric Arc Plasma and Other Hot Flames
Preparation of Hydrazine by Electrolysis of Ammonia
Preparation of Hydrazine from Ammonia by Chemonuclear Processes
Preparation of Hydrazine by Chemical Oxidation of Ammonia
Preparation of Hydrazine from Urea
Preparation of Hydrazine from Compounds with A Nitrogen-Nitrogen Bond
Preparation of Hydrazine from Semicarbazide
Preparation from Nitramide
Preparation of Hydrazine from Nitrosamine Derivatives and Nitroso Compounds
Preparation of Hydrazine from Nitrogen Oxides
Preparation of Hydrazine from Azo and Diazo Compounds
Preparation of Hydrazine from Inorganic Nitrides and Azides
Of particular interest to me are:

Photolysis of Ammonia
Glow Discharge in Ammonia
Electrolysis of Ammonia
Nitrogen Oxides
I've searched about all of these, and here are my schittey findings:
Photolysis of Ammonia
http://newjournal.kcsnet.or.kr/main/j_search/j_bkcs_archives_view2.htm?code=B960909&qpage=j_bkcs&spage=j_bkcs_01
(make sure you download the pdf)
Basically, it says that aqueos ammonia exposed to UV but sealed from oxygen will turn into hydrazine.
It's aqueos, but still interesting... it'd be incredible if you could just leave ammonia outside in glass with a relief valve (for the
hydrogen) and end up with hydrazine solution a month later.
Glow Discharge in Ammonia
I read up a bit on glow discharge. It seems to be something like a low temperature plasma caused by 2000 V in low pressure
(around 150 torr).
These are conditions which I can attain, but this is of concern:
http://www-2.cs.cmu.edu/afs/cs.cmu.edu/user/mnr/st/std091
It makes it sound like it's a difficult process. This isn't suprising: since hydrazine is used a monopropellant, I can't imagine
how it would survive a 2000v spark... also that text states it must be highly turbulent flow, I imagine that the whole setup
would be complicated to make.
Also, just as in NOx fixation, you probably won't get near 100% yield, meaning you'd have to recycle the ammonia, making
things even more complicated.
Electrolysis of Ammonia
This I'm very, very interested in. I must've spent 2 hrs googling earlier today... found nothing, except that electrolysis of
ammonia yields hydrogen and nitrogen, which apparently is an idea for fuel cell hydrogen source (sounds severly backward to
me: using electricity to make a chemical to make electricity).
I'm kinda poor with electrochemistry, does anybody have any info on this? I'm guessing that at a certain voltage you get
hydrogen plus nitrogen, but at another voltage you'd get hydrogen plus hydrazine. Anybody have a clue to what the voltages
might be? Can they be calculated?
Also, what's the smartest electolyte (pure ammonia wouldn't conduct)? A bit of water, maybe? Some salt that can in the end be
removed with some sort of voodoo?
Would this work for some good old 30% ammonia solution? But then you got the water problem...
Nitrogen Oxides
This is intersting to me mostly because I can probably make nitrogen tetroxide very cheaply (I'm working on it with
confidence, might post about this if I can refine it). It almost definitely would produce water, but that's an OK compromise if
the process is simple.
I found absolutely no info about this.
Well, that's all. I've called every freaking library and bookstore within a 200 km radius asking if they had that book, all came
negative.
Does anyone have any info to contribute? Or by any chance access to that book?
I might experiment in a month or so, if I find anything I'll post.
Marvin September 9th, 2004, 02:11 AM

There is a fair amount of general information in this thread on wet processes,
As for use of gelatine being a mikey-mouse process, its purpose is fairly simple. Lock up any copper ions in solution to
prevent a very fast side reaction that produces nitrogen instead. Tap water for example contains enough copper ions to make
the reaction fail almost completely. Glue or EDTA will work, but less well. NH2Cl + NH3 is part of the standard Rashig synthesis
I would have doubts about feasabilty outside of aq solution.
If you want hydrazine for astrolite, I suggest you forget it. Astrolite is only feasable if you can just buy the stuff. If you want it
for something else small amounts are possible but one hell of a chore and you may have no choice but to go via a wet
method and several distillations.
The urea process has a major advantage over ammonia - you dont need a massive excess to get decent yeilds. Several
methods are around including a good one by Mr Anonymous together with slightly over emphatic directions and this may be
the best option. Urea, bleach and sulphuric acid are cheap, the yeilds are reasonable and we know this works. From the
hydrazine sulphate produced the steps are very well documented and silvering glassware might not protect it completely. I also
think this is one of the compounds that can explode on contact with ground glass joints (Detail needs cheking but watch out
anyway anyone trying this). you will also lose product every step of the process.
"but most important of all is that you gotta seperate the hydrazine from water"
The vast majority of the water is removed by the formation of the hydrazine sulphate salt. Reaction of this with a strong base
gets you strong hydrazine hydrate or better (meaning mixture of the hydrate and anhydrous) which can be distilled off, from
there its 1 more distillation also with silver or silver coated equipment. If you can make the hydrate or even a weak solution in
water, it is possible to make hydrazinium borate from which the anhydrous hydrazine can just be distilled off directly after
dehydration. Somewhere also there is mentioned an entraining method for dehydrating hydrazine hydrate to anhydrous.
Possibly megalomanias website, but discussed here also with some corrections.
Glow discharge I would think would be a major feat of engineering. What might work instead, and I'd put my money on for an
easy route to (very) small amounts is a silent discharge in the same equipment we'd use to make ozone.
Electrolysis is new to me, but I'd bet sizable money the electrolyte is sodium amide in anhydrous ammonia, and that the
primary hydrazine forming reaction is NH2- => NH2. + e at the anode followed by 2NH2. => N2H4.
If you are willing and able to handle liquid ammonia, making a hydrazine salt is not so far from anhydrous ammonia, as
ammonolysis will turn it into hydrazine and an ammonium salt (which ppts), decanting and a fairly easy distillation of the
ammonia gets you anhydrous hydrazine.
There is an alternative method to one step anhydrous hydrazine based on an old patent, but it has 2 major disadvantages.
1, The byproduces are ungodly toxic,
2, it doesnt actually seem to work.
Depending on how desperate you are you may want to look this up and try it at considerable risk to your helth if you succeed.
After some very heavy research on this whole hydrazine topic during the last 10 years Ive found no easy answers, very few
sneaky shortcuts and substatially inorganic processes dont seem to have changed in the past 50 years.
kurtz September 9th, 2004, 03:46 AM

Photodecomposition of NH3:
JCS 1160-1169, 1932
JACS 55, 1754-1766, 1933
JACS 54, 1806-1820, 1932
JACS 56, 318-323, 1934
JACS 49, 2438-2456, 1927
JACS 58, 2462-2467, 1936
J Phys Chem 42, 783-788, 1938
Nature, 142, 1080, 1938
JACS 59, 827-830, 1937
JACS 51, 2059-2082, 1929
They obtained a 57% yield (based on decomposed ammonia) in the JCS article.
Unfortunately only .1% of the NH3 reacts. So 1 ton NH3 = 1 lb. hydrazine. Hydrazine is also photosensitive.
Electron Bombardment:
Proc. Roy. Soc. 130A, 346-366, 1931
Electrolysis:
Nature 125, 709, 1930
Trans Faraday Soc 31, 792-797, 1935
Nature 119, 235-236, 1927
Trans Faraday Soc 39, 234-237, 1943
Only traces of hydrazine can be obtained through electrolysis of aq. ammonia, at least with the (1915) ref that I was able to
find.
As for NxOx, perhaps the involvment of these is to form intermediates, rather than being a reactant itself?
And you said nitramide was useless! Probably not as useless as the above. It seems that research did not continue for long.
No one in industry, anywhere, uses such processes. Of all the Bizzaro ways to make hydrazine, you seem to have picked the
least practical ones.:) So you'll really be needing those refs.
Microtek September 9th, 2004, 01:00 PM

For sodium azide production I use a method which gives hydrazine in alcohol ( from hydrazine sulfate ) with little or no water:
- 1 mol dry HS is placed in a flask along with a suitable amount of anhydrous isopropanol.
- 1 mol of NaOH pellets are added and the contents are triturated with a glass rod until they begin to react, forming a slurry of
hydrazine hydrate and NaHSO4. This doesn't mix with the iPrOH, but forms a sticky goo on the glass.
- Another 1 mol NaOH is added which converts the NaHSO4 to Na2SO4 ( and forms a mol of water ) which separates cleanly as
a white powder.
I would think that the Na2SO4 is a good enough dessicant to dry out the solution which can then be decanted.
- Another extraction or two with dry iPrOH recovers most of the hydrazine.
This alcoholic solution of hydrazine works well for producing sodium azide with isopropyl nitrite.

As for use of gelatine being a mikey-mouse process, its purpose is fairly simple. Lock up any copper ions in solution to
prevent a very fast side reaction that produces nitrogen instead. Tap water for example contains enough copper ions to make
the reaction fail almost completely. Glue or EDTA will work, but less well. NH2Cl + NH3 is part of the standard Rashig synthesis
I would have doubts about feasabilty outside of aq solution.
Would that mean they have chelating properties as well? That would make alot more sense...
If you want hydrazine for astrolite, I suggest you forget it. Astrolite is only feasable if you can just buy the stuff. If you want it
for something else small amounts are possible but one hell of a chore and you may have no choice but to go via a wet
method and several distillations.
Not exactly astrolite. I want to see if I can make azides with it (maybe even hydrazine azide?), and see what'd happen if I mix
it with some certain oxidizers I have in mind...
Reaction of this with a strong base gets you strong hydrazine hydrate or better
That's exactly why I don't want a wet process: hydrazine free of water is tough to make. For many reactions the hydrate is fine,
but if the hydrazine is used directly it's a bad idea thanks to it's negative heat of formation. Pure hydrazine is much better.
Glow discharge I would think would be a major feat of engineering. What might work instead, and I'd put my money on for an
easy route to (very) small amounts is a silent discharge in the same equipment we'd use to make ozone.
I don't think an ozonater would work since ozone's formation is more endothermic and since ozone is less sensitive in some
ways.
Electrolysis is new to me, but I'd bet sizable money the electrolyte is sodium amide in anhydrous ammonia, and that the
primary hydrazine forming reaction is NH2- => NH2. + e at the anode followed by 2NH2. => N2H4.
If you are willing and able to handle liquid ammonia, making a hydrazine salt is not so far from anhydrous ammonia, as
ammonolysis will turn it into hydrazine and an ammonium salt (which ppts), decanting and a fairly easy distillation of the
ammonia gets you anhydrous hydrazine.
I don't think anhydrous ammonia is too much trouble, I was planning on making some later on for different needs. The fact
that none of the reactants contain oxygen is very attractive to me :)... I also think this method has hope because you say
you've been at it for 10 years but haven't toyed with electrolysis much.
Only traces of hydrazine can be obtained through electrolysis of aq. ammonia, at least with the (1915) ref that I was able to
find.
Well, I won't even try that then. But I'm still most interested in dry ammonia electrolysis.
And you said nitramide was useless! Probably not as useless as the above.
I didn't say it was useless... but nitramide is hard to make and hard to work with. I haven't found any easy synthesis', if you
have one, can you state it?
Of all the Bizzaro ways to make hydrazine, you seem to have picked the least practical ones.
I personally think that's likely, but there's a slight chance that we might come up with something anyway...
No one in industry, anywhere, uses such processes.
Did you know that you can make sulfuric acid by boiling sulfur with nitric acid, and then collect NO2 vapor to recycle the nitric
acid? That's easy, right? So why doesn't the industry use it? Because it's very easy for them to pass sulfur dioxide and oxygen
through near molten catalysts.
The industry uses the method most practical for them, and the professional chemists use methods that yield very pure
products with minimum hazard. Us home improvisationist-chemists are left in the middle to fend for ourselves, and often we'll
use something that seems like a miracle to use but severly impractical for everyone else.
Rosco Bodine September 9th, 2004, 07:34 PM

The value of hydrazine for our purposes is limited to the usefulness
of hydrazine as a precursor in the synthesis of several different types
of primary explosives . Such a need is satisfied by the use of
hydrazine sulfate directly in some reactions . Other reactions require
the hydrazine hydrate freebase which may be obtained from the hydrazine sulfate
by reaction of the solid with solid sodium hydroxide , and the absolute minimum
of added water to form a thick slurry of sodium sulfate crystals in hydrazine hydrate ,
which is taken up in successive portions of methanol . Proper technique and glassware
is needed for reactions involving the freebase hydrazine since it is destroyed
fairly rapidly by exposure to oxygen of the air .
For lab scale synthesis of hydrazine sulfate , the reaction of urea and
sodium hypochlorite is the best method . There is an extensive detailed
description at the Hive . That process is superior to any other published
method for lab scale synthesis of hydrazine from common materials .
The reaction of a slight excess of isopropyl nitrite with a cold methanol solution
of hydrazine hydrate and slight excess of sodium hydroxide , in a slightly pressurized
reaction flask produces a solid precipitate of pure sodium azide crystals in pretty good yield .
A pressure relieved , sealed glass and teflon reaction flask and addition funnel ,
with magnetic stirrer and an ice water bath is needed for performing the synthesis .
Regarding isopropyl nitrite ,
The isopropyl nitrite needed for the synthesis of sodium azide may be prepared
in advance and kept cold in the freezer , stored in a glass bottle having a teflon gasketed
threaded closure . The isopropyl nitrite may be made at salted ice bath temperature ,
by fairly rapid addition of a freezing cold mixed solution of aqueous 31.45% HCl and
a slight excess of theory of 70% isopropanol , to a well stirred freezing cold aqueous solution
of sodium nitrite in slight excess of theory which has been dumped onto twice its volume
of ice cubes in a flask which is cooled by a salted ice bath . The HCl in isopropanol should
be introduced through a small bore teflon tube extending downward to near the bottom
of the stirred mixture of ice cubes and sodium nitrite solution , or else it will decompose
the isopropyl nitrite which rises to the surface as it forms , if the acid mixture drops onto the
surface and contacts the free ester . It is very important for this reason to introduce the HCl in
isopropanol , near the bottom of the flask to avoid the decomposition of the product .
When all the HCl isopropanol has been added , the stirring is stopped and the isopropyl nitrite
top layer along with some of the lower layer of byproduct salt water is quickly decanted into a
prechilled separatory funnel , and the lower layer drawn off and discarded . The oily ,
bright yellow isopropyl nitrite layer is drained into a prechilled glass bottle having a
teflon gasketed closure , sealed only moderately tight to allow for a bit of overpressure relief
if needed , and stored in a freezer . The storage bottle and cap should be preweighed
so that the added weight of the isopropyl nitrite product can be determined , and it will be known
what molar amount is available for use of this precursor in further reactions . The isopropyl nitrite
fumes freely in the air , producing nitrous fumes from decomposition , as well as fumes from
the intact ester which has a volatility similar to ether . These fumes are highly toxic and physiologically active ,
as is the liquid ester itself so due caution should be observed to avoid inhalation or skin contact .

Well... thanks for the info but I've searched this forum already and the internet in general, and I'm well aware of those
methodes.
Concerning the azide, that's a very nice procedure. I'd read about it here and there on this forum but not in such detail.
Thanks :D.
Concerning electrolysis, I found this (from a chemistry book genuisly titled 'Chemistry'):
N2(g) + 5H+(aq) + 4e- <> N2H5+(aq)

E0 (V) = -0.23
Obviously the part about (aq) has been ruled out, but could this bit of info be useful otherwise? Like I said, I suck at
electrochemistry...
Pb1 September 9th, 2004, 09:43 PM

I just had a thought on the NH3 + NH2Cl method. NH2Cl is one of the intermediate chems involved in the synthesis of NCl3,
which doesn't react to form NHCl2 and NCl3 at a certain pH. Is there any chance of synthesizing it by passing Cl2 into an
ammonia solution at a carefully-controlled pH?
There is really no need for producing hydrazine in anhydrous condition
for use in syntheses where hydrazine is used as a precursor for explosives .
Hydrazine hydrate and its methanol solution with sodium hydroxide does
not attack the unground surfaces of borosilicate glass , and only very slightly
clouds the surface of ground joints , which may be protected from such
slight attack by a film of Halocarbon grease or even Dow Corning High Vacuum
Silicone grease . There is no explosion hazard for the ground joints in
contact with hydrazine hydrate vapors , as is a concern for diazomethane .
Rocket propellants and some pharmaceutical syntheses are places where

the anhydrous hydrazine may be needed , and the expense and hazard
justified . With regards to astrolite , well there are cheaper and safer and
more powerful explosives which don't require hydrazine in any form .
Electrochemical methods are generally less desirable than direct chemical methods
for small scale production .

Hmnn... ok I'll put electrolysis on hold (sorry, but I'm doomed to try it one day).
What about the ordeal with nitrogen oxides? Anyone have a clue how'd they work? It makes no sense to me since NOx +
hydrazine = hypergolic propellant.
Edit:
Concerning the glass, Merck says:
For hydrazine: Can be stored for years if sealed in glass and kept in a cool, dark place.
For hydrazine hydrate: Strong base, very corrosive, attacks glass...
I don't plan to make astrolite ever but I'd prefer anhydrous because you can do more with it I guess.
Rosco Bodine September 10th, 2004, 12:25 AM

Those Merck references or their quoting are exactly backwards .
Unless there is some truly exceptional specific requirement for the

anhydrous form of hydrazine , the pursuit of making and storing it
is not justified because of the costs , difficulties , and the hazards .

Now why doesnt it surprise me Rosco would rave about the Urea process :D
I agree with him completely though, if you want azides anhydrous hydrazine is not a logical intermediate. Ive read it doesnt
attack glass much, but the hydrate does, so I'd follow Merck on that one.
I'm not sure if I missed kurtz's post acceidentally, but it might be becuase it took a while for a mod to authorize it. Either way
I'd sure like to see any scanned versions of those references.
"Of all the Bizzaro ways to make hydrazine, you seem to have picked the least practical ones."
This made me laugh. Why is it with hydrazine the wierd and low yeilding ones are the most attractive looking yet the ones that
are long, dull, well tested and OTC trivial we avoid like plauge victims.
I'm working on a a simpler way to sodium azide from OTCs that bypasses hydrazine entirley. More information when
apropriate. For the time being going with a basic alcoholic extraction of a hydrazine salt sounds like a good process. There are
some tricks with magnesium metal, producing the alkoxide that can remove water completely if needed for other experiments.

The urea process was simply the method which appeared to be
most promising for a lab scale approach to producing usable yields
with economy , easily available precursors , and minimal equipment ,
while still being a relatively clean and safe process . I did look at
alternative methods , but the urea method became the clear preference
after all the factors were considered . The urea method works so
well that the synthesis should be confirmed and a technical writer
should do a proper writeup and have it added to the four volume Wiley
Organic Syntheses as an improvement over the older method , whenever
they next update their publication .
Azides were the principal reason for my interest in devising a good method
for lab scale production of hydrazine . And the first order of business
there was to devise a method for producing pure sodium azide directly
without any need for distillation of hydrazine . The freebasing and
methanol extraction of the hydrazine hydrate , followed by reaction in
the cold with isopropyl nitrite , satisfied the goal of producing pure
sodium azide in good yield by the most direct approach found to work .
The alternative Hodgkinson patent process looks to be so simple that

I tried to replicate that reported work , but even after literally two dozen
experiments using the same or slightly varying conditions from those
reported by Hodgkinson , there was ZERO success in producing azides
by Hodgkinsons method , which I quite frankly believe to be fraudulent .
I even tried some significant variations applying my own ideas of how
to troubleshoot and modify the reaction conditions to achieve the desired
results , but nothing I tried worked , even when extremely close control
of pH , temperature , reaction concentrations and mixing parameters were
applied , negative results became the predictable outcome .
On paper and in theory the reactions work beautifully , but in the

reaction vessels , everything else but what you expect should happen
was the rule for "Hodgkinson type" hydrazine sulfate / sodium nitrite
reaction scenarios . Anyone who can make such a reaction produce
azides , should declare how the matter is accomplished , and take a
bow for discovering and sharing the secret . This puzzle has already
stumped and thoroughly humiliated both Rosco and Philou , so Marvin
you are invited and welcome to solve this enigma of molecule crafting ,
and please teach us what we want to know :D
kurtz September 13th, 2004, 02:31 AM

May I get a little off the anhydrous part of the original post and more towards the alternative syntheses part?
Marvin, you may want to see scans of those articles, but I doubt that the Administration would want even a pittance of their
bandwidth used for them. I read every one of them, and all seem impractical. Hydrazine or its salts were not actually isolated
in any of them, determinations were spectral and sometimes chemical.
One article that did have isolation of the pure sulfate, JACS 55, 1968-1974 (1933), used NH3/.05mm tungsten filaments to
produce 380 mg./kWh. These filaments were heated to 3000C.
It would be interesting to see if the Preparation of...'s in that book actually presented full experimental details. Something like
what follows at the end of this post, for example of what I'm looking for. Especially of the older methods - I'd love to know
exactly what's in all those old German and French articles that use hyponitrous acid/Na bisulfite/Zn/acetic acid, nitramide/Zn/
H+, nitrourea, nitroguanidine, diazo- aldehyde ammonia or hexamine/Zn, Fe, Al, or Mg, and the original ethyl diazoacetate/
NaOH/H+ route. All of these articles (at least 24) sit in the library mocking my 1 year of high school German. I've no idea just
how practical these methods are if one happens to have these precursors.
I was able to find an English article, JCS 69, 1610-1620 (1896) that deals with the Na/Hg reduction of K nitrosulfate (NO, KOH,
K2SO3). That's what they call it, I think its KSO3N(NO)OK. And I think that the Germans got this to work with alkaline Zn
instead of the amalgam. Something similar in choice of reductants, acetone/NO/NaOH in EtOH. This may work with alkaline
aluminum. Also found JACS 54, 1530-1538 (1932) which used methyl isopropyl ketone and ethyl nitrite, which I will paraphrase
even though this is, um, off the anhydrous hydrazine process topic:
125 g methyl isopropyl ketone and 6.7 ml conc. HCl was kept at 45-55C as the theoretical amount (1.45 moles) of gaseous
ethyl nitrite (OS X, 22) was added over 2 hrs. The product was put in the freezer and then cooled more with a freezing mixture.
The crystals were washed with ether giving nearly pure bis- methyl nitrosoisopropyl ketone in 24% yield, 40g.
17.25 g (.15 mole) of this (finely ground) was slowly added to a stirred solution of 84.5 g SnCl22H2O (.375 mole) in 123 ml
conc HCl. The temp was kept below 25C during addition, but was allowed to warm and stir until the reaction became
homogenous, 5 hours. 190 ml H2O was added and methyl isopropyl ketone was distilled off. The Sn was precipitated with H2S.
What liquid remained was evaporated nearly to dryness, and EtOH was added precipitating the hydrazine dihydrochloride. This
was washed with ether giving a 40% yield of nearly pure N2H42HCl.
As impractical as this or the other methods above may be compared to urea or aq. ammonia, these are far better than the old
methods in my earlier post. I wonder if any improvements have been made to the anhydrous processes, but not enough to
buy the book.
meselfs- Of course you're right, you said not especially useful, not useless - I apologize. I will make up for it by looking up
the Inorg Syn ref for it. However, there was no need for the industry lecture, I was simply stating an FYI fact.
OK - Inorganic Syntheses 1, 68-74 (Nitramide) does not fit meselfs request for an "easy" synthesis of nitramide, for most
people here. It starts with urethane, H2SO4, ethyl nitrate, Et2O, and NH4OH to give ammonium nitrourethane (47-55% yield).
This yields K nitrocarbamate on treatment with KOH/MeOH (65-80% yield). Finally, this is added to dilute H2SO4 to give
nitramide (75-85%yield). I left a lot out, the authors give much detail and say that such detail is necessary. I don't think that
anyone here wants nitramide that badly. For hydrazine, it hardly seems worth the trouble.

meselfs,
"Would that mean they have chelating properties as well? "

Yes, that exactly.
"I don't think anhydrous ammonia is too much trouble, "

I do, its not meerly the low temperature, dry ice isnt that hard to find, its what happens if you run out....
Aq ammonia produces wet ammonia, which you can breathe in and it can cause short term diaphram paralysis. Ive had this
(from an unlucky lungful following a spillage of 880) and its somewhat scarey, but I read that dry ammonia is much much
worse. Pulmonary edaema territory.
N2(g) + 5H+(aq) + 4e- <> N2H5+(aq)
This is only valid for the destruction of hydrazine, it doesnt imply you can make it.
"I don't think an ozonater would work since ozone's formation is more endothermic and since ozone is less sensitive in some
ways."
Maybe I can convince you. Ozoniser is basically a very low density glow discharge, broken molecules, but without any thermal
problems. Ozone forms by oxygen being broken up into O. radicals, I'm thinking hydrazine would form from NH2. radicals. Its
possible that radical density is a critical factor though.
kurtz,
For me this thread is a patchwork and the intention it seems was only to make azides anyway. If the mods object it can always
be merged with the existing hydrazine thread. If those articles are in easy reach I'd still like to see them, you could upload to
the forum FTP, if they arnt dont bother the effort is better spent on things that will produce decent yeilds. Having spent so long
in libraries looking up weird methods I have a slant in that direction. I recall one method that involved nitrosating hexamine
and then reducing.
I'm fairly sure the nitrourea method will involve reduction to semicarbazide and Ive been wondering about the production of
azides this way. What with the reduction it doesnt seem easier than the urea/hyperchlorite method but I'm still after a process
for the final azide step. If hydrazine can by obtained fro semicarbazide thats also useful. There is a nitrourea to
semicarbazide prep in detail on SM, goes via acetone semicarbazide though so it looks a little messy.
http://www.sciencemadness.org/talk/viewthread.php?tid=253
The Tungstun wire method is a possible OTC method, you can buy 2 mil wire at magic shops as one of the grades of 'invisible
wire'. By my math that would be pretty close to 0.05mm. If its possible to freeze out anhydrous hydrazine it could be useful. I
wonder how much ammonia it turns into N2 and H2 in the process. I'm also quite surprised actually the wire wasnt destroyed
rather rapidly. Hot ammonia is really unfriendly to most metals. I read a really dull article on it once purely because it was
next to a fantastic article in the same journal and I was bored.
Ok, I'm done with this post because its late and my first attempt was eaten by a power cut. Some days things are just uphill
both ways.

I do, its not meerly the low temperature, dry ice isnt that hard to find, its what happens if you run out....
No problem if you store it under pressure. A coke bottle will work surpisingly well.
Those bottles have a design pressure of around 200 psi. If propane at room temprature makes around 50 psi, then ammonia
shouldn't be too difficult; and I've worked with propane before, it's not a great challenge.
I tried making some a few days ago via distillation under pressure, but the pressure caused the ammonia to dissolve in large
amounts into the reaction jar. I tried to put as little water as possible but that happened anyway. To solve this I'll probably
have to get my hands on either dry ice or a pump...
Maybe I can convince you. Ozoniser is basically a very low density glow discharge, broken molecules, but without any thermal
problems. Ozone forms by oxygen being broken up into O. radicals, I'm thinking hydrazine would form from NH2. radicals. Its
possible that radical density is a critical factor though.
Hmnn... I just might be convinced.
I recall one method that involved nitrosating hexamine and then reducing.
An explosive called CTMTNA is bassically RDX except nitroso instead of nitro. It's very easy to make but generally has 40%
yield. Reduction would probably be aqueos so I imagine that this is impractical, since the yield would be better with the good
old urea methode.
I just had a thought on the NH3 + NH2Cl method. NH2Cl is one of the intermediate chems involved in the synthesis of NCl3,
which doesn't react to form NHCl2 and NCl3 at a certain pH. Is there any chance of synthesizing it by passing Cl2 into an
ammonia solution at a carefully-controlled pH?
Sorry for missing this...

I read somewhere that the reaction must be dry, although the reaction between ammonia and chloramine must be in the jello
solution.
It would be interesting to see if the Preparation of...'s in that book actually presented full experimental details. Something like
what follows at the end of this post, for example of what I'm looking for.
It'd better... the whole book is over 2000 pages long.
However, there was no need for the industry lecture
Sorry :D
meselfs March 28th, 2005, 05:42 PM

I read "Comprehensive Inorganic Chemistry" at a newfound library. Some items of interest:
Urea -----Ni, 60-7 C-----> CO + Hydrazine
Now that seems exceedingly ideal. What's the catch? If it takes weeks to proceed, that's fine by me... I heard that factories
never use slow processes so maybe that's why it's never used (I'm such a stupid optimist).
Also:
NO2 + NH3 ----> HNO2 + NH2
I've read that NH2 readily dimerizes into hydrazine.

This method isn't very attractive to me, since I'm pretty sure the HNO2 will cause a mess, to say the least.
But the first method... any thoughts? That 60 - 70 C is way below the melting point, so how would the urea contact the Ni? Aq
soln, maybe (heaven forbid!)?
Also:
NO2 + NH3 ----> HNO2 + NH2


Also:
NO2 + NH3 ----> HNO2 + NH2


The procedure is not exactly new since it has been around for 50 years... Ullmann's does not mention it, so that should tell
you right there it is not "economicially" viable. I happen to have a patent in my collection, let's see... Ahh yes, US patent
2,717,201 the Production of Hydrazine details this very procedure.
The jist of the reaction is that you mix powdered urea with powdered nickel at around 70 C and stir. The hydrazine along with
carbon monoxide are emmitted and should be collected. The reaction can also use iron as a catalyst, although the
temperature should be nearer the melting point of urea then, around 130 C. In fact at around 60-70 C there may be very little
hydrazine given off. You can end up with a slurry of hydrazine and unreacted urea with nickel.
Sounds too good to be true... Naturally this procedure is probably dangerous and nickel carbonyl (the byproduct of this
reaction) is rather toxic. Merck also says it explodes at 60 C, but I would hope it is diluted enough in the reaction for it to just
decompose as it is formed.


cutefix April 6th, 2005, 02:40 AM

reaction) i.
The main concern there with such form of vapor phase synthesis...is it had many toxic products emanated.
I was wondering who among the forum members would give it a try? :cool:
Besides Semicarbazide is one by product which can be converted to hydrochloride and then will become the base ingredient for
the synthesis of nitrotriazolone, a powerful but insenstive high explosive which is likely to replace TATB.
Meanwhile the standard form of hydrazine synthesis was proposed by german chemist Freidrich Raschig in the US patent
910858 titled : Synthesis of hydrazine. It is simple and can be made with OtC ingredient but unfortunately will end in
hydrazine suflate which is difficult to extract the anhydrous hydrazine :(

reaction) i.

reaction) i.
meselfs April 8th, 2005, 07:27 PM

I'd love to know why Kellog needs hydrazine (they own the patent) :-S
The carbonyl should decompose as soon as it forms, even in the absence of oxygen. I don't think there's an explosion risk.
I got an idea: what if this is done in boiling methanol? Urea will dissolve in it (1:6 at STP), and the methonal boils at an ideal
temperature: 65 C. Hot methanol shouldn't react with hydrazine...
...right?
Just reflux the mix a few hours, I don't see a problem, except the possibility that the reaction is incomplete, as mega hinted.
Still, I think a liquid medium is a good idea, and methanol is fine choice.

...right?

...right?

This came up a year or so ago at science madness, it was tried by BromicAcid and produced no distillate at all well beyond the
temperature mentioned in the patent. He used nickel powder produced by thermal decomposition of the oxalate too, which
should have been the most active. Its a little disturbing to think how many patents simply arn't true. Maybe important details
are missing or maybe its based on the expectation of certain reactions of hydrazine and metal carbonyls going backwards
under the same conditions they go forwards.
I cant find the reference where hydrazine and a metal carbonyl go to urea and I wonder if I'm mistaken on that, but I can find
one where iron carbonyl and hydrazine go to 'a complex mixture of semicarbazide, iron carbonyl and hydrazine'.
The relavent thread is currently located,

http://67.15.145.24/~sciencem/talk/viewthread.php?tid=1128
Interesting idea to try boiling methanol but it could react with the urea producing ammonia and a urethane.





Thanks alot, Marvin. Methanol seems to fit all of the points needed in that thread.
Here's how I'd do it:
Mix urea and methanol, 10 g or so methanol to 1 g urea (beyond STP saturation). Put this in a beaker, not a flask. Add some
chunks of nickel, free of copper. Put all this in a convinient location.
Setup another beaker with boiling water, have this placed not too close to the first beaker, since hydrazine's flash point is near
50 C.
Setup a steel pipe, going first into the boiling water, then into the methanol beaker. In the methanol beaker, the pipe should
have lots of tiny holes in it, as to aerate the mix.
Pass air dessicated with CaCl2 through the pipe.
If that fails, I'd then try:

Make or obtain a refulxing setup, reflux the appropriate mix for a while with air entering the mix through a steel tube.
In any case:
If the nickel doesn't dissolve, simply spoon it out & boil off the methanol. If it does, you'll probably have to do a nerve
wrecking distillation.
Some things to note:
Methanol boils around 65 C and dissolves urea in 6:1.
Do not add H2S (suggested in that thread)!!! It's a fact that urea can be made by combination of ammonia and CO in
methanol in the presence of sulfur...
Metal ions aren't a huge problem, in the Raschig method they are problematic only because the nascent chlorine/oxygen will
attack the hydrazine, catalyzed by the ions. Since in this process doesn't rely on oxygen/chlorine attacking anything, the metal
ions shouldn't matter. So, don't add any chelate.
If there's a reaction between the steel pipe and hot soln, use PTFE.
Merck says that methanol and hydrazine are miscible, which must indicate that they don't react. I really hope this is still true
when the methanol boils.
My question, and this may sound really, really silly to some of you veterans: will the hot air (~65 C) react with the hydrazine?
The point is for it to react with the carbonyl. Such reaction is basically guarunteed.
If several hours of unattended refulxing produce > 20% yeild, I think this'd be well worth it.

50 C.

In any case:

50 C.

In any case:
Rosco Bodine April 10th, 2005, 01:32 AM

Hydrazine is a highly air sensitive , oxygen sensitive material , and it is destroyed

rapidly by exposure to air , or even to dissolved air or dissolved oxygen in water
or other liquids . Hydrazine is an effective " getter " for oxygen and it is for that reason that hydrazine is added to the boiler
water in steam heating systems .
A certain level of hydrazine in the water used in a closed loop system will prevent
corrosion of the pipes and the boiler , by reacting with and removing any
dissolved oxygen .


dissolved oxygen .


dissolved oxygen .

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Explosives
fromTerephthalic acid ?
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View Full Version : Explosives fromTerephthalic acid ?
qashimalik September 12th, 2004, 11:44 AM

hi frends!
its my first thread .
Is there anyway to make explosive compounds from terephthalic acid?Any of its derivatives as explosives...?

You could try nitrating it (terephthalic acid = para-benzenedicarboxylic acid) , in the usual way for an aromatic. Or you could decarboxylate it first, or reduce it to p-xylene,
then nitrate, which would be preferable. It is usually used for copolymerization, to make polyester fibers especially (with ethylene glycol) Dacron/Terylene/Mylar.
Bugger.

I welcome ur suggestions.But i need a well detailed and exact info.i want to know the procedure,parameters and quantities of the reagents etc.
Ok...
Let me say, i want to procure picric acid using terephthalic acid as a starting material and want a detailed method of its preparation.Will someone guide me?
FUTI September 13th, 2004, 10:44 AM

wrong path! Yield sucks...multiple products...most of them bad explosive caracteristics. Try salicylic acid it is easy to find and give better results in picric acid production. And
watch your face I saw a face of a man who didn't make that experiment go well. In best case you will stain yourself and be visible to police like chained jail-bird dressed in
black and white stripes, and in worst you wouldn't like to look yourself in the mirror. You know little of organic chemistry or else you wouldn't ask that question. Maybe you
could obtain trough that procedure trinitro-benzene which is strong explosive as I heard but also a hard one to make. You can make picric through terephtalic acid but it is to
much steps and trouble for a simple molecule.
bobo September 13th, 2004, 02:47 PM

I welcome ur suggestions.But i need a well detailed and exact info.i want to know the procedure,parameters and quantities of the reagents etc.
watch your tone dude, demanding to be spoonfed like that is not done here. Still, the topic is interesting enough.
Carboxyl group in the benzene ring (as in benzoic acid, easily obtained) is not much good, let alone two of them, since COOH is already a deactivating group (but NO2 is that
too). I think Urbanski does not ever mention explosive compounds with a carboxyl group (it is not in my memory at least). Which basically comes down to it is either not
working or very unlikely to succeed unless you're an experienced amateur who wants to synthesize a crazy chemical just for fun.
Benzene nitroderivatives are harder to get than toluene derivatives. SInce all you're going to get from this chemical is benzene based nitro products, this is why I think you
better buy a batch of aspirin :D
Benzene is more resilient to nitration than toluene because it lacks an activating methylene group. This is all well if you want to nitrate it to mononitrobenzene for making
aniline. Dinitrobenzene is much more toxic than it's toluene-based cousins, and why bother. The best route to manufacture TNB for educational purposes seems to start out with
TNT :rolleyes:
And Bugger, does that actually work, reducing a COOH on a ring to a CH3? I think, oxidizing anything to COOH is easy enough but how exactly would you reverse the
oxidation?

qashimalik,
How difficult is it to follow the rules?
You may not start a thread with your first post, your first post may not be a question and when we look at the question its completely clueless. Its broken logic that you tell us
what you can get and expect us to provide something fun to do with it. Read the forum, find out what you need to do what we do, or read the books and add a new
suggestion based on what you can get.
Hey guys I can get water and soil and rocks and stuff how can I make an explosive?!?!?
You see how this sounds to us?
COOH groups are electron withdrawing, which makes nitrating a ring with one on more difficult than without, it also makes it meta directing, which is bad in itself. Compound
has 2 on oppasite sides, which is also bad, as soon as you add a nitro group the thing is going to want to decarboxylate even assuming it survives the first nitration.
Reduction of COOH on a ring is possible, but a lousey synthetic method by any way I know. To take it back to benzaldehyde youd make an acid chloride, say with PCl5, and
then reduce this with zinc dust. Hydrazine reduction may or may not reduce this back to the CH3 group as it would with an aliphatic aldehyde. Its essentially not a useful
method synthetically and if you do manage it, you end up with para xylene, which are electron donating groups, but in the wrong place, so theyre fighting eachother and
blocking the production of a trinitro compound.
The synthesis is going nowhere because its based on a starting material chosen almost randomly. Picric acid is possible, but youd end up going through chemicals the hard way
you can get to easily from other widely available materials.
kurtz September 14th, 2004, 02:55 PM

Fedoroff mentions the azide and peroxide. Usefulness, and qashimalik's ability to make them, well, that wasn't the question.

:D Sorry Guys! there's some misunderstanding here.
I didn't asked about the direct nitration of terephthalic acid(p-phthalic acid).I just asked to know whether there's any other possible way to convert that into any trinitro
derivative say tri-nitro-resorcinol(styphnic acid) or picric acid etc.
I m wonder why my question seem to be clueless.There are many examples that early explosives where made from non-explosive and even incombustible materials.
Gunpowder exported to America by Mexico in 18th century was made from Bat excretes. :cool:
Picric acid was first made using "Indigo" as a raw material. :p
I think it would have made my question more clear.
Suppose you have no other option but to use terephthalic acid to make an explosive,what would be your strategy.I guess this will make you think again and again,eventually
you will come up with a new idea :D .

"Sorry Guys! there's some misunderstanding here."
Yes, but not by us.
"I m wonder why my question seem to be clueless."
It lacks understanding of chemistry, it lacks understanding of explosives, it lacks understanding about the forum and its rules. Did I say clueless? I meant clueless.
"Gunpowder exported to America by Mexico in 18th century was made from Bat excretes. "
We know this. Potassium nitrate was made from animal dung and urine for over a thousand years, it would not be surprising even if we didnt know it.
"Picric acid was first made using "Indigo" as a raw material. "
We know this, the end point of treating most organic matter containing benzene rings with conc nitric is picric acid anyway.
"I think it would have made my question more clear."

It is clear. You can get terepthallic acid, you want to make an explosive out of it, but dont know what explosive or how and you argue that its in our best interests to work it
out and tell you. We arnt that stupid and we also know the best option is to move over to other things.
Is it impossible? No, but if it was a choice between using that or making one from air and water, Id opt for air and water and we have thousands of possible precursors before
I'd have to sink that low.
"I guess this will make you think again and again,eventually you will come up with a new idea"
Grow up.
Dave Angel September 19th, 2004, 10:58 PM

It is good to see someone speaking sense Marvin.
qashimalik: This thread should have been made in the water cooler, but even more preferably made as a post to an existing thread on phenol. The very first post itself should
not have been made as it is. You should have done as much research as possible on it before making the post and included your research in it.
As Marvin pointed out, it's pretty damn obvious that you have just found a chemical you can lay your hands on and want us to work out how to make it into an explosive.
Having read the rules, you should have fully expected to have been banned outright for posting that first post you made. The second one isn't any better. Even after recieving
information about possible routes you still demanded exact details, rather than going off to read up on decarboxylation methods etc. to work it out yourself.
And you used "ur" rather than your! :rolleyes:
Whilst I'm at it, Bugger may want to read the bit in the rules that goes:
You will not use your username as your signature as well. If your username is "HAL9000", then you will NOT use "HAL9000" anywhere in your signature, nor at the bottom of
every post. It's redundant since your username is always included next to your posts anyways.
It irks me for some reason, but importantly, it irks whoever wrote the rule!
Apologies to other members if this came off as a rant, I usually try to restrict most of my postings to results of my practical work, or discussion of useful information. The only
useful information worth giving to make this post somewhat on-topic is to reiterate that it is so much easier to make TNP from ASA than to try to find a route from terepthallic
acid. I'm all for a bit of originality in synths, but such novel routes are usually better recieved at MSDB, though vulture didn't seem to agree with your 'spoonfeed me' style post
either.
In typing this reply, I am considering whether it is even worth posting and may be objectionable to the mods; an attitude a few others seem to need to adopt. Despite it not
being quite on-topic, I will post, as I wish to add to the concerns I have seen others raising over the quality of some postings recently.

a n d I m provised C hemistry > Destruction of Aluminum via Mercury Amalgamation
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nbk2000 October 15th , 2 0 0 4 , 0 6 : 5 8 P M

An idea I've been kicking around for a while cam e to me when I saw an article in the septem ber '04 issue of Popula r Science,
where they showed an alum inum I-beam 'rusting' into dust after contact with a sm all amount of mercury.
From New Scientist (http://www.newscie ntist.com /lastword/article.jsp?id=lw547)
P l a n es are largely m a d e f r o m a l u m inium and, surprisingly, a very sm all am ount of m ercury can de stroy a large am o u n t o f
alum inium . Despite its apparently inert behaviour, alum inium is actually a rather reactive m etal wh ich will com bine violently with
oxygen in air. However, this reaction quickly produces a thin, tough oxide layer which stops further attack. The process of
a n o d i s i n g t h e a l u m inium thickens this layer to give better protection.
Mercury has the ability to disrupt this protective oxide layer, and the results can b e spectacular. It can dissolve alum inium to
form a n a m a l g a m which m a y b r e a k u p the oxide layer from below--presumably the initial attack occurs through tiny faults in
the oxide.
Many years ago a technician working for m e spilled a few drops of m ercury on his wooden bench, which had heavy aluminium
angles screwed round the edges to protect it. Next morning large holes were eaten through the alu minium , the wood nearby
was deeply charred, and large fragile towers of friable aluminium o x i d e h ad grown like strange corals.
This used to provide a fine chem istry experime nt but it is now frowned upon because of the toxicity of the m ercury.
O n o n e o c c a s i o n a p a s s e n g e r i n f r o n t o f m e wa s preven ted from carrying a barom eter onto an aircraft because it wa s on the
list of prohibited articles, even though this particular barometer was empty. With difficulty I persuaded the staff that it was
harmless. They did not realise it was the mercury that was dangerous, they thoug ht it was just barom eters per se. I wonder
what they thought an altim ete r measures . . .
Harvey Rutt , Department of Electronics and Com puter Science U niversity of Southampton
=======================
Give n the m obility of liquid m ercury, the corrosive am a l g a m m ay form deep within the structure. An aircraft in which mercury
h a s b e e n s p i l l e d m ust be put into quarantine u n t i l t h e a m a l g a m m akes its presence known. Ultim ately, the aircraft is likely to
b e s c r a p p e d b e c a u s e t h e e n g i n e e r i n g t e x t b o o k s state that the amalgam slowly spreads like wood rot to adjacent areas.
Rod Paris , Air Medical Lim ited O xford Airport Kidlington Oxfordshire
Hm m m m ....destroy a irplanes with m ercury? My, oh m y.
My concerns were more m u n d a n e , t h a t b e i n g t h e d e s t r u ction of the com m o n e s t p u c k l o c k f o u n d o n v e n d i n g m achines, the

Am erican Lock Com p a n y S e r i e s 2 0 0 0 .
US Patents 5 1 2 7 2 4 4 a n d 5 3 4 5 7 9 4
Since these locks are 'com posite', m e a n i n g a m ostly alum inum body with som e steel inserts for strength, it seem s logical to
think that, if you sm e a r e d s o m e m ercury on the lock early in the night that, by dawn, that it would have disintegrated into a
loose collection of parts that would no longer constitute anything close to a lock.
This wouldn't affect m y lock, a 2010, a s it's solid steel and not cheap-ass alum inum . :p
S e e m s to m e like a project about to happen, as mercury switche s are dirt cheap to buy, and series 2000 locks are free for the
destroying on vending machin es. ;)
T h o u g h I ' v e a l r e a d y o r d e r e d a s e r i e s 2 0 0 0 l o c k f o r u s e t o m a k e a d r i l l i n g t e m plate for the purpose of bypass, so perhaps I'll

wait till after I'm done using it for that purpose and test this idea on that lock instead.
Suggestions on how to keep the mercury on target? I'm thinking of m ixing it up well with m elted vaseline a n d s m earing that
on. O r perhaps a m ercury salt like corrosive sublim inate would work?
This is a SW idea, because if it works, it's too valuable to give away for free to an y o n e r u n n i n g a g o o g l e s e a r c h . ; ) T h a t , a n d
I'd like to avoid giving away the game prem aturely.

a n d I m provised C hemistry > tetranitromethane synth???
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me234 Novem ber 9th, 2004, 01:33 AM

O K l a d i e s a n d g e n t l e m en.
Nitromethane is m anufactured by the industrial CH4 + HNO3 method, or by the la b o r a t o r y m e a n s o f C H 3 C l + AgNO 2 -->
CH3NO 2 + AgCl
So, would the sam e lab method hold true and work for:
CCl4 + 4AgNO 2 --> C (NO 2)4 + 4AgCl
I'm thinking that this might be some what useful. I haven't worked out a nything like heats of form ation or shit like that, I was
just inspired by the idea.
A n y t h o u g h t s o n w h e r e o n e m i g h t h a p p e n a c r o s s l a r g e ( o r s m a l l , I ' m n o t g r e e d y ) a m ounts of silve r nitrite.
Any references to literature would be wonderful.
Marvin Novem ber 9th, 2004, 07:25 AM

W ont work, read Urbanski for working m e t h o d s , v o l u m e 1 I I R C . I t s e x t r e mely toxic. I was under the impression we had a TNM
thread allready so try some searching.
Silver nitrite you would have to make, and the sane che mist recycles the silver an yway. Th ere is a m ethod in inorganic
syntheses, but I dont have access to them .
Microtek Novem ber 9th, 2004, 01:40 PM

In m y opinion, trinitromethane is more interesting anyway. There are m ethods described here or o n the ftp which involves
reacting isopropanol or acetone with strong ( 95+ % ) nitric acid at elevated temperatures. I have carried out one of these
s y n t h e s i s e s a n d m a n a g e d t o p r o d u c e s o m e trinitromethane which I used for hydrazinium nitroform a t e a n d a m i n o t e t r a z o l e
nitroformate. The pro cedure is pretty unnerving; the acid m a k e s s m all cracks and pops and evolves NOx when you add the
substrate. The yields are not particularly impressive either.

a n d I m provised C hemistry > M a k i n g a m m onium p e r s u l f a t e
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The_Rsert Novem ber 28th, 2004, 05:45 PM

Hello,
Has somebody inform ation about amm onium persulfate?
I h a v e s o m e s o d i u m perulfate, am m o n i u m n i t r a t e , N H 4 O H a n d a m m onium chloride.
Is possible to synth. it with the chem icals?
I n e e d s o m e am m o n i u m p e r s u l f a t e , b e c a u s e I w a n t t o m a k e s o m e c o p p er persulfate(neutralising amm onium persulfate with

copper carbonate) to synth. tetraamincopper(2)persulfate.
Mumble Novem ber 28th, 2004, 06:12 PM

W ell, amm onium persulfate is a comm on etchant of circut board s. It is used as an alternitive to FeCl3 and Sodium Persulfate.
I ' v e h e a r d o f p e o p l e m aking it from th e interation of so lutions o f a n a l k a l i p e r s u l f a t e a n d A m m onium Chloride. I never heard
the results of the proceedure though. I imagine that you could possibly crystalize the persulfate out with low tem ps as NaCl
doesn't change in solubility much. Am m onium Persulfate decomposes in water so you may want to wash with alcoho l or
acetone.
The other wa y to do it is electrolysis of am monium sulfate in dilute sulfuric acid. That is all the detail I have about that
m ethod.
hereno Novem ber 28th, 2004, 06:36 PM

Acco rding to here http://www.sciencem a d n e s s . o rg/talk/viewthread.php?tid=1778&page=1
Cupric persulphate has not be en isolated, but its tetram i no - a nd t et ra pyri di ne deri va t i ves , [Cu,4 ba s e]S 2O8, ha ve b een
prepared (Barbieri and Calzolari, Z. anorg. Chem ., 1911, 71, 347).
Thus, you can't m a k e C u S 2 O 8 by precipitating from amm onium p e r s u l f a t e , o n l y s e e m s i s o l a t a b l e a s i t s c o m p l e x . T h e r e s n o

need at all to convert the Na2S2O 8 t o t h e a m m onium salt anyway! Use it as is, Na2S2O 8 solubility = 55g/1 00ml @ 20C.

But m aybe they m a d e s o m e p r o g r e s s s i n c e 1 9 1 1 .
nbk2000 Novem ber 28th, 2004, 09:54 PM

I ' d h o p e c h e m ical science has advanced at least just a little in the last century! :p

Im quite sure that in 1911 they knew how to precipitate salts from solution :rolleyes: If it were as sim p l e a s m i x i n g a m m onium
persulfate with copper carbonate (<-Is THAT even isolatable!) it would be well known. Anyway the point is that there is no need
to isolate it anyway, if your aim ing for the com p l e x .
FUTI Novem ber 29th, 2004, 08:21 AM

I t h o u g h t t h a t C u C O 3 isn't iso lable when I was student...and guess what, I was wrong. It can be made;) It's on you to find how
hereno.
EDIT: BTW I had an im p r e s i o n t h a t h e a v y m e t a l s a l t s a s A g , F e a n d o t h e r s c a n p r o m o t e d e c o m position of persulfate in

solution, so I wouldn't use Cu salt with am monium-persulfate anyway! Think about it and tell us if you find something
interesting, I never research subject to d e e p .
Mumble Novem ber 29th, 2004, 09:16 PM

Generally it exists as a com plex with copper hydroxide, also kno wn as basic copper carbonate. I've h e a r d s o m e t h i n g a b o u t
h e a t i n g C u O i n a C O 2 a t m o s p h e r e , b u t it reverts to the hydroxide com plex on contact with m oisture.
W hat I really don't understand is why use C o p p e r C a r b o n a t e ( I a s s u m e you have the basic com plex). Did you plan to boil the
m i x t u r e a n d h a v e t h e a m m o n ium carb o n a t e d e c o m p o s e a n d l e a v e t h e s y s t e m ? T h e p e r s u l f a t e w o u l d w i t h o u t a n y q u e s t i o n
decompose under these conditions. If you just were making a solution, the insolubility of the copper carbonate would severe ly
push the equilibrium to the left. Your best method would be to heat or reflux the sodium persulfate and an hydrous copper
sulfate under m ethanol, filter off the sodium sulfate and anything rem a i n i n g a n d b u b b l e d r y a m m o n i a i n t o t h e m e t h a n o l . T h e
crystals will p recipitate. This is the best way I know to prepare the tetraamine copper (II) complexes anhydrously. You don't
have to deal with them becom i n g w e t a n d a b o u t a s u s e f u l a s a n e x p l o s i v e a s t a b l e s a l t . T his would be the best of any chance
of preparing the com p o u n d y o u a r e h o ping to acheive.
hereno Novem ber 30th, 2004, 06:29 AM

Q u e s t i o n , I s t h e p r o b lem with aqueous solutions that the water form s a ligand with the com plex replacing NH3, or is it becau se
its a hydrated salt?
Acco rding to the link above, the formation of the com p l e x y o u w a n t c a n b e d o n e i n a q u e o u s s o l u t i o n s . W hy dont you just try
m ixing stoichiom etric proportions of NaS2O8/CuSO4.5H2O /NH4O H and try to precipitate it, no point getting complicated if it
isn't warranted!
The_Rsert Novem ber 30th, 2004, 02:55 PM

OK, i have ju s t t e s t e t m a k i n g T e t r a a m i n c o p p e r ( 2 ) p e r s u l p h a t e !
It works very well! Thanks!
Picture of yie ld of 5g copper sulphate:

http://m e m bers.fortu necity.de/potatoguns/TAC Persulfat.jpg
The crystalls were very wet an some ice was in the filter, too.
The "washing-water"(I don't know the right English word for this) was beautyful coloured :)
http://m e m bers.fortu necity.de/potatoguns/W aschwasse rTACPersulfat.jpg
metal dragon D e c e m ber 4th, 2004, 03:15 AM

Off topic but here is a m ovie of the tetra amine copper persulphate burning.
The soultion that the crystals are filtered from is a very nice purple.
http://www.in fernolabs.co.uk/filehost/teraaminecopperpersulphate.AVI
The_Rsert D e c e m ber 4th, 2004, 08:58 PM

Picture of yie ld of 5g copper sulphate:
http://m e m bers.fortu necity.de/potatoguns/TAC Persulfat.jpg
The crystalls were very wet an some ice was in the filter, too.
The "washing-water"(I don't know the right English word for this) was beautyful coloured :)
http://m e m bers.fortu necity.de/potatoguns/W aschwasse rTACPersulfat.jpg
The links are now deleted.

The new link is:
http://m e m bers.fortu necity.de/potatoguns/TAC Persulfat.htm l

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Synthesis of Amines
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Myrol December 5th, 2004, 12:45 PM

Hi Folks! I've searched some time around the forum, but I was unable to find useful data about the preparation of Amines, the sort doesn't play a role :)
Ok, my background to open this Thread is mainly Ethylene Diamine......PLX type Explosives are very promising for Guys like me wich have 5Liters pure Nitromethane handy :D
:D but no sensitizer! After seeing Axt 700ml PLX Blast I was so out of the House that I ordered 5Liters NM and want now an Amine!
NM could be sensitized with a lot stuff, Ammonia, Aniline, Ethylene Diamine, Methyl Amine, Propylene Diamine, Triethylamine, Propylene Triamine, Diethylamine and so
on......well but what would you say how can I make mainly Ethylene Diamine without applying pressure on Dichloroethane and Ammonia-mix? I have 1Liter 72%
Perchloric Acid in my stock, Ethylen Diamine dinitrate and the Diperchlorate are strong Explosives, thats also a reason to make EthDiAm! I can order it from Merck etc.
but thats inpertinent expensive (65 for 1,5Liters :o ). Aniline is easy without much effort preparable, but I'm lacking Benzene to make Mari Ban Oil (Nitrobenzene) and
then Aminobenzene!
Some Ideas are very recommed, because I'm planning a big Blast on Silvester with 1,5Liters PLX, Aerex, Ammex or whatever (Ammex is my Name for AMmonia-nitroMEthane-
eXplosive, just a little changed from Aerex).

I have a synthesis for ethyl, diethyl, and triethylamine. But it uses ethyl bromide and a concentrated ammonia and ethanol mixture under pressure. It sounded like you didn't
want to use this type of reaction. But I will upload the file anyways.
vurr December 5th, 2004, 04:05 PM

urea/carbamide is an amine.
also hexamethylenetetramine..
(if those can be used for NM)
what about ordering aniline?? should be cheaper

The amine needs to be a strong base. Maybe ethanolamine would work, its commonly used as a developer for home electronics boards.
FUTI December 7th, 2004, 08:28 AM

you can use hexamethylentetraamine for amine synthesis through alkylation with some alkyl-halogenide (you get ammonium salt) and after it decomposing the adduct to
obtain primary amine, formaldehyde and ammonia.
I like ethanolamine idea, it is good to try it.
Myrol December 7th, 2004, 01:53 PM

Hmm, Ethanolamine sounds good. Do I need Chloroethanole and Ammonia to prepare it or are there some other maybe faster ways? Perhaps I'll try first some Ammex as an
Explosive and later if it works good I invest some effort in REAL Amines. Thanks for replying, Has someone a book wich describes the posibillity of makinbg Ethylene Diamine
via basic hydrolysis of Ethylene Urea? Its a ringmolecule with nearly finished but hidden Ethylene Diamine in the molecule! I calculated a bit and it COULD work to hydrolize it,
but my first attempt was confusing.....Ethylene Diamine should smell very close to Ammonia....so I didn't know if I have made Ammonia water or the Diamine! I'll try to freeze
it, if it gets solid under 8,5C it should be the Diamine.....if not its waste (Ammonia water)
Mendeleev December 31st, 2004, 01:16 AM

Basically any primary, secondary, or tertiary alkylamine can be synthesized by reacting an alkyl halide with ammonia under anhydrous conditions, but this reaction is better for
secondary and tertiary amines because you would have to use a huge ratio of ammonia to alkyl halide to get a primary amine, something like 20 to 1. Methyl amine can easily
be made by by hydrolyzing hexamine. The reaction was pioneered by Organikum and goes something like 100 g hexamine dissolved in 100 mL water is added to about 325
mL 31% HCl and 130 mL ethanol, refluxed at 70-90 C for a 2-3 hours, then the ethyl formate distilled off, and the flask contents concentrated, preferably under vacuum, to
give a yellow sludge wihch is extracted with IPA, and the IPA boiled off to give methylamine hcl. People have claimed to get 120 g methylamine hcl from 100 g hexamine in
this reaction.
Marvin December 31st, 2004, 02:06 PM

The alkyl halide will always produce a mixture of primary, secondary, tertiary and quaternary, and since more highly substituted amines react faster the excess of ammonia
needs to be huge for a primary, and for secondary and tertiary attempts are just going to produce a mess.
General methods for pure primaries are available, like the gabriel synthesis.
"Methyl amine can easily be made by by hydrolyzing hexamine. The reaction was pioneered by Organikum "
Call me picky but this was pioneered by Eleusis on the internet in the mid 90's and widely known since then. Unless that is, I'm missing something apart from the chemists that
developed the reaction in the late 19th and early 20th centurys that is.
The_Duke January 1st, 2005, 10:31 PM

You can heat Ethylene Glycol (antifreeze) with H2SO4 (drain cleaner) and sodium chloride to produce ethylene dichloride, and then you must reflux this with strong household
ammonia cleaner to get Ethylenediamine. You can also use Ethylene glycol and HCl to make Ethylene chloride, and then make a Diamine from that. :cool:
Mendeleev January 2nd, 2005, 02:56 PM

Eleusis did pioneer the general reaction, but he was obscure about the benefits of adding alcohol to the mix, at least I found out from Organikum's posts that ethanol helps
even though I had read Eleusis's procedures. I don't know anyway...
Marvin January 2nd, 2005, 10:28 PM

The Duke,
I think making ethylene dichloride from the glycol has been discussed before without a convincing resolution. Making the chlorohydrin needs anydrous HCl and high temps or
yeilds are very low, and the second alcohol group does not replace under normal conditions.
Zeitgeist January 4th, 2005, 03:09 AM

Some 2-part epoxy adhesives have large concentrations of tertiary amines in the hardener, it has been used to sensitise NM before.
Jome skanish January 24th, 2005, 04:11 AM

Wonder how is ethylenediamine manufactured on the industrial level.
Only route I can think of is via ethylene dichloride and ammonia. But how could ethylene dichloride be made? Acetylene + HCl?
FUTI January 24th, 2005, 09:08 AM

But how could ethylene dichloride be made? Acetylene + HCl?
No! Addition of HCl on acetylene gives geminal dichloride. Better route would be ethene and chlorine (I guess dilution is needed?).
Jome skanish January 27th, 2005, 06:58 PM

Geminal? Never heard of that compound, what formula does it have?
Perhaps electrophilic substiution could be prevented by choosing the right solvent. But I dont know much about solvents. Or the other chloro-compound could be separated by
destillation.... but the procedure seems to be a bitch requiring a lot of advanced equipment.
Damn I cant find how industri does it either.
EDIT: Perhaps something like one of these could be used. http://ocean.otr.usm.edu/~leleuter/organic/amine1.html

I've heard that dibromoethane is prepared fairly simply by ethylene glycol, sulfuric, and Na/KBr. Perhaps this would be a better solution to the chloride problem. I know that the
bromide seems to attach better than the chloride ion, so perhaps going the bromide route would be easier than chloride. At least I have heard this. I've seen many people say
it is hard to make ethylene dichloride, but many posting success of ethylene dibromide. I know it shouldn't theoretically be this way though. Na/KBr may not be nearly as
cheap as NaCl, but it is not that over bearily expensive. It is available as a pool chemical. I think it was around $7-8
a pound.
As a side note, I don't think that the Ethylene dichloride + household ammonia method will work very well for EDA. All the water will kill the reaction. I've found a reference to
it's manufacture and it says that the less water the better. Liquid ammonia is best, but that is a bit hard to get and requires pressure apparatus. There was a mention of a much
more feasible solution. It said that strong reflux of ethylene dibromide and a methanol solution of ammonia would yield ethylene diamine. The methanol solution wouldn't be
too hard to prepare. I'll try and get the exact link tommorow when I am at school where the page is stored(I hope).

Jome,
Its an old school chemistry term indicating both substituants are on the same carbon, as opposed to adjacent ones (being vicinal). The abreviations more commonly seen are
vic and gem.
Markovnikov rules apply to the addition of HCl to chloroethene which is the theory behind FUTI's point.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Gammabutyrolactone
(GBL)
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nbk2000 January 29th, 2005, 08:36 PM

The reaction between tetrahydrofuran with trichloroisocyanuric acid at 0 C, w ith the addition of water, produces gamma-butyrolactone (GBL).
Benicasa, M.; Grandi, R.; Ghelfi, F.; Pagnoni, U. M. Synth. Commun. 1995, 25, 3463.
For those w ho don't know what GBL is, that's an immediate precursor for GHB, better known as 'The Date-Rape Drug'. :o
Has the advantages, when properly prepared, of being tasteless, quick acting (less than 15 minutes), water and alcohol soluble, quickly eliminated from the body, and leaves
the victim with amnesia of events having taken place immediately before and during the intoxication.
You can also use neat GBL for the same purpose, as this is the metabolic product of GHB breakdown, and the active ingredient, though it's a liquid and has a funky taste (so I've
heard)
Fuck 'em silly, rob 'em blind, or snatch 'em up...all are doable and have been done w ith this type of drug.
What could be better than than to make a powerful knock-out drug from pool chlorinator and PVC pipe solvent? :)
Now all that's needed is someone to look up the requisite reference and do a little home lab experiment. ;)
BTW, w hile looking for this, I found a google cached page from the Rhodium archive where he (Rhodium) mentioned doing the same thing using HTH instead of TCAA (perhaps
he confused the tw o?) and, naturally, some dumbass says "Why bother w hen you can buy GBL?".
Well, dumbass, you could buy GBL in '98 (date of the post), but you can't do that no mo'! So THAT'S why you learn how to make everything from anything, because the day
WILL come when you can't buy nothing for anything. :p
And w hile we're at it, how about converting starting-fluid ether to ethyl acetate?
Juenge, E. C.; Beal, D. A. Tetrahedron Lett-. 1968, 55, 5819.

Rhodium may not have been refering to the HTH shock product. HTH also makes a chlorination compound. And w hat ingredient does said chlorination compound contain you
ask? Why Trichloroisocyanuric Acid of course.
I've seen this proceedure before. You could easily buy both precursors at wal-mart, no questions asked. They are trained to look for bulk ephedrine purchases, and people with
gallons and gallons of acetone. They'll never see a container of PVC cement and a canister of organic pool chlorination as a w arning sign. I mean I have bought the two there
several times.
megalomania January 30th, 2005, 02:05 AM

I remember reading about a reaction to convert THF to GBL, but IIRC it w as rather complex and not likely to be OTC. I may have been reading a different procedure than this,
however. I just ordered supplies yesterday for the synthesis of 1,4-butanediol, the precursor of both THF and GBL.
Dave Angel January 30th, 2005, 10:54 AM

I have here a pdf of a paper on solvent free permanganate oxidations, which describes the use of combinations of KMnO4, CuSO4 and Alumina to oxidise among other things:
1,4-butanediol to gamma butyrolactone in a 95% yield over 14 hours.
Tetrahydrofuran to GBL in a 70% yield over 6 hours.
The components of the oxidant should be readily available to most; in the uk, alumina from ceramics supply and KMnO4/CuSO4 from the right garden centres - though I w ould
be concerned about the purity of the end product with garden centre chems...
OT: There also seems to be potential for the ever elusive simple oxidation of primary alcohols to aldehydes - they manage pentanol to pentanal with 80% yield, perhaps there
is hope for ethanol to acetaldehyde.
If the pdf attached is too big to be acceptable then the paper ref. is:
Tet. Lett. 42 (2001) 5833-5836
tom haggen February 1st, 2005, 03:49 PM

GHB is yet another chemical that has falling victim to the police state we are currently living in. I believe it is classified as a schedule 1 controlled substance, while I have read
that it has great potential for the treatment of alcoholism. Coincidentally there is a thread over at MSDB going on about a synthesis of GBL from GABA and sodium nitrite. While
the original post seemed quite shady, it would definitely be an easy route of obtaining GBL. While GHB is a date rape drug I believe the original date rape drug w as rohypnol. I
think its safe to say that GBL is a chemical that the government is going to have a hard time controlling.
megalomania February 1st, 2005, 11:33 PM

I have been interested in catalytic transfer hydrogenation as of late. There are some excellent articles in Rhodium's archive that describe using CTH with a microwave. I suppose
it is worth a shot putting a beaker of purified 2-butene-1,4-diol, alcohol, and U-Ni-A (or B, I have not decided yet) in the microwave and see if it w orks.
I will have to take a closer look at the catalytic synthesis of formaldehyde as well. That is really the only important ingrediant in this synthesis.
If I have not detailed the reaction as of yet it is formaldehyde + acetylene + CuO (cat) --> 2-butene-1,4-diol
2-butene-1,4-diol + H2 + U-Ni-A (or U-Ni-B) (cat) --> 1,4-butanediol
If I had not dissolved my bubbler this reaction may have worked better for me. Now I have much more CuO to w ork with, and using nbk's teflon bubbler idea I will not fail.
BTW, I know the potassium permanganate used for water softners is quite pure (> 99%) since it involves human consumption as the intended use.
Macgyver March 12th, 2005, 09:13 AM

What other interesting things can GBL be used for besides drug manufacture?
(Happen to have some that I got a few years ago, w hile it w as still available here in Europe).



I believe its main use is as a solvent for electronic components. According to Ullmann's Encyclopedia: "Butyrolactone is important as an intermediate in the manufacture of
pyrrolidone derivatives and as a solvent for polymers and agrochemicals."



I got my GBL for cleaning circuitboards from flux ressidue after assembly, but I happened to order more than I needed, thats why I want to know if there's any other interesting
uses if you're not into making drugs out of it.
(Probably have over 4 litres left). :D


trinitride3 March 13th, 2005, 08:28 AM

NBK I was wondering if you could post the exact synthesis for GBL using tetrahydrofuran and trichloroisocyanuric acid. I haven't had any luck finding it over at rhodium. much
appreciation

appreciation

appreciation
FU TI March 13th, 2005, 02:54 PM

corn cob...furfural...furan...THF....1,4-butandiol...GBL
loooong procedure but obtainable by almost everyone.


trinitride3 March 21st, 2005, 06:57 PM

NBK, could you please tell me the specifics regarding the reaction. Im looking to find the correct proportions of tetrahydrofuran and trichloroisocyanuric acid I need to use and
also time for the reaction to take place before the water is added. I've searched extensively for this information at Rhodium and all over the web but haven't had any luck
locating it. I would greatly appreciate any info you might be able to provide.


nbk2000 March 24th, 2005, 01:01 PM

If you're going to try it and report back the results, then I'll get you the specifics.
From memory, the THF and water are premixed, and .15 moles of TCCA per mole of THF are used, and stirred while cooled to about 3°C, and the TCCA added in small
amounts over the course of hours, stirring for 24 hours w hile allow ing to warm up to room temperature an hour after the last TCCA addition.
I'll find the specifics later.
nbk2000 March 24th, 2005, 01:01 PM

nbk2000 March 24th, 2005, 01:01 PM

nbk2000 April 19th, 2005, 01:19 PM

In order to moderate the reaction, the reaction flask was placed in an ice bath. To 60 ml (53.28 g, 0.74 mole) of tetrahydrofuran, containing 6 ml of water, was added 23.24 g
(0.10 mole) of trichloroisocyanuric acid at such a rate as to maintain a gentle reflux.
Upon addition of the first amount of trichloroisocyanuric acid, a yellow color appeared and quickly faded. A w hite precipitate formed immediately. After all of the
trichloroisocyanuric acid was added, the reaction mixture w as allowed to stir overnight. Cyanuric acid precipitated almost quantitatively and was removed by filtration.
The filtrate was combined with 60 ml of ether and extracted three times w ith 20-ml portions of 5% aqueous sodium bicarbonate. The ether layer w as distilled, and found to
contain only tetrahydrofuran.
The w ater layer w as acidified with aqueous hydrochloric acid, and the water and hydrochloric acid were removed by azeotropic distillation w ith benzene.
The benzene was removed by distillation, leaving 2.55 g (19%) of gamma-butyrolactone, bp 88-89C (10 mm).
nbk2000 April 19th, 2005, 01:19 PM

nbk2000 April 19th, 2005, 01:19 PM

MushroomMarkk September 2nd, 2006, 05:57 AM

I was unaware that THF could be picked up at walmart! Its a little off topic I believe, but could someone mention the brand name that THF is under. Unless I misunderstood
something :( that would be a dissapointment.
++ ++++ +++
This would be considered a spoonfeeding request and cause for banning. Don't repeat the mistake of asking for something that you can easily find out for yourself with a little
bit of UTFSE.
Hobbit Porn September 5th, 2006, 12:12 AM

On a completely unrelated forum, one of the posters put up this link
http://ww w.alloycleaner.com/
I Had a read around the site, and they are based out of the UK.
IIRC (please someone correct me if this is incorrect), 1,4-butanediol is metabolised in the body to GHB. If this is correct, it w ould probably be just as easy to focus on procuring
1,4-butanediol rather then GBL, since 1,4-butanediol is a very commonly used industrial solvent (at least in Australia).
nbk2000 September 5th, 2006, 02:59 AM

Here, the butanediol is regulated the same as the GBL, so if you can get either of the tw o, getting the straight GBL is to be preferred, as it's a much better product.
nbk2000 November 8th, 2007, 03:41 PM

Finally a toxic chinese toy that's useful. :)
Better hurry though, they're getting pulled off the shelves.
Australian scientists say a chemical coating on the beads, when ingested, metabolizes into the so-called date-rape drug gamma hydroxy butyrate. When eaten, the compound -
made from common and easily available ingredients - can induce unconsciousness, seizures, drowsiness, coma and death.
At least five children in the United States and Australia have been hospitalized after swallowing the toy beads, which are used in arts and crafts projects. They can be arranged
into designs and fused when sprayed with water.
...
The toys are called Bindeez in Australia, where they were named toy of the year at an industry function this year, and in the United States they go by the name Aqua Dots.
http://ww w.newnation.vg/forums/showthread.php?p=223002#post223002
bloodbob November 21st, 2007, 07:36 AM

I wonder if you could get reasonable yields substituting the alumina matrix with silica or at least a zeolite.
spetsnaz08 March 30th, 2008, 02:34 PM

http://ww w.mindandmuscle.net/forum/lofiversion/index.php/t8423.html
Dont break any law s, this is just for entertainment purposes:
GABA to GBL writeup

**this writup is only preliminary, and mainly is to facilitate perfection of this method **
--------------------------------------------------------------------------------
Introduction:
First of all, MANY MANY thanks to Chromic for helping to pioneer this method. This is simply w ithout a doubt one of the easiest methods to make GBL for the clandestine
chemist. Through some trial and much error, respectable yields finally have been obtained.
--------------------------------------------------------------------------------
Chemicals (in relation/ratio to the main precursor, GABA):
1 part Pow dered GABA ( *** Do *NOT* use @NC brand GABA. Although many nutritional stores claim there are no adulterants, there most definitely are. )
0.68 part Sodium Nitrite (*** NOT NITRATE)
0.5 part conc H2SO4 (H2SO4 is sulfuric acid)
(in other words, GABA:Sodium Nitrite:H2SO4 1:0.68:0.5)
ACS NaOH or Baking Soda ( ** if you cannot get ACS NaOH, USE BAKING SODA
DCM (possibly other solvent, let us know if any others work!) (dcm is dichloromethane, methylene chloride, CH2Cl2, non-polar solvent)
--------------------------------------------------------------------------------
Procedure:
1. Dissolve GABA and Sodium Nitrite in a flash with water in an ice bath.
2. Make a mixture of 1 part conc H2SO4 2 parts water.
3. Put this mixture in a bottle capable of dripping VERY slowly (swif uses those red and yellow plastic ketchup and mustard bottles).
4. With stirring/sw irling, let the H2SO4/water mixture drips very slowly into the GABA/NaNO2 mixture until all of it is used up. **IF YOU SEE BROWN GASSES, YOU ARE GOING
TOO FAST -- THESE GASSES ARE POISONOUS **
5. Put the flask outside or somehow vent it outside as some of the gasses emitted are also poisonous and let sit for at least a day, 2 is preferable. You should see little bubbles
of N2 being formed in the flask.
6. Now you need to convert all of the GHB/GBL into NaGHB so we can boil off all of the liquid. The GBL w ill steam distill, so that is why w e convert it to NaGHB. You can add
about 0.90 parts (compared to the original GABA) baking soda and reflux for 30 minutes to an hour. Alternatively, (swif's method of choice) you can use ACS NaOH (not lye)
until the pH is neutral (7-8, a little more basic than neutral is OK).
7. Boil off about half of the solvent and add 1 part H2SO4. This is to destroy any dangerous nitrosamines and to convert the NaGHB back to GBL.
8. Extract the GBL with DCM ( uncertain if any other solvents will work, eg toulene, xylene) two or three times and combine the extracts.
9. Now you must separate the DCM from the GBL. One easy way of doing this is to prepare a boiling water bath and place the flask in there. The DCM w ill boil away, but the
GBL w ill remain since its boiling point is much higher. *NOTE*
10. What you have left is GBL and some impurities. You can distill out the GBL at 200 deg. celcius. (Obviously, you cannot use the w ater bath ) *NOTE*
11. Congratulations! You have successfully made GBL. You can consume as-is, or convert to to Na/K GHB. An active dose is 1-2mL of GBL. GBL is a harsh mucous membrane
irritant; be sure to dilute it in something! Enjoy!
*NOTE* There is another hypothetical method of separation that has not been tested yet. If it w orks, let us know ! Titrate the DCM/GBL mixture with 50% NaOH and when the
water is pH 8 or so, separate the w ater, and add enough vinegar until it is pH7 again.
Again, many thanks to Chromic and the hive in general for all the help in helping to formulate this procedure!
You can find the w hole right up and some tweeks on the method at the hive . UTFSE and look under Success making GBL! . THere you should be able to put it all together and
from the looks of it you can "dream" of making TONZ of gbl for really cheap. Of couse this is only in your dreams if you live in the military state called usa

a n d I m provised C hemistry > Protecting a Double-Bond
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View Full Version : Protecting a Double-Bond
Tricosane March 23rd, 2005, 05:13 AM

I've been trying to figure out a way to theoretically synthesize Testostero ne (or if that fails, Androstenedione) from
Progesterone. I've run into a bit of a snag, though. I intend to turn a C-C single bond into a C=C bond, then break it via
ozonolysis. However, the molecule has a pre-existing C=C double bond elsewhere that would also be broken. Do yo u know of
any way to protect that double bond? Any sort of protecting groups out there?


FUTI June 29th, 2005, 06:43 PM

Try addition of brom ine over double bond, then ozonolysis, and after that rem ove the brom ine with zinc forming the double
bond again.
FUTI June 29th, 2005, 06:43 PM

Try addition of brom ine over double bond, then ozonolysis, and after that rem ove the brom ine with zinc forming the double
bond again.

and Improvised Chemistry > A review of chromium compound synthesis
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View Full Version : A review of chromium compound synthesis

While doing some digging for my website I have compiled this little primer for the improvised synthesis of many different
chromium compounds. Since they all seem to be interrelated synthesis wise (one is used to make another) I thought I would
combine them all on one page. Since the information is rather hard to come by, anyone that wishes to expand on what I have,
or add corrections if I made a mistake, please do so.
I know there are many different chromium containing compounds, but these are the common ones. I have also expounded on
where one can obtain OTC sources of chromium.
Synthesis of chromium compounds
The primary source of the element chromium is the naturally occurring ore chromite, or iron chromate, a mixture of ferrous
oxide and chromium oxide, FeO Cr2O3. The most abundant OTC sources are from ceramic and pottery suppliers that se ll
chromium compounds as pigments and glazes. Another major OTC source is suppliers of metalworking chemicals that sell
chromates as patinas (chemicals that make metal look aged).
Depending on what kind of chromium compound you get, and where you get it, the price is rather reasonable. Iron chromate
sells for as little as $0.80 per pound from ceramics suppliers, and chromium oxide goes for $6-$7 per pound. Potassium and
sodium dichromate goes for $5-$10 per pound from ceramic and patina suppliers.
Many other kinds of chromium compounds exist, but are not so easily found. Chromium compounds tend to be rather toxic,
so this limits their usefulness in consumer products. Dichromate salts may be more difficult to obtain because they are
watched chemicals by the DEA.
Chromium compounds are quite interchangeable. The inexpensive and readily obtainable chromium oxides are quite easily
converted into the more useful dichromate salts.
Potassium chromate: A finely powdered mixture of iron chromate, potassium carbonate and potassium nitrate are strongly
heated in a furnace with frequent stirring. The nitrate ignites the mixture and the chromium oxide is oxidized to chromium
trioxide, which then combines with the carbonate forming potassium chromate. Potassium chromate can also be formed by
adding a solution of potassium hydroxide to a solution of potassium dichromate.
Sodium chromate: Can be prepared exactly as potassium chromate except sodium compounds are used in place of
potassium.
Lead chromate: Lead chromate can be precipitated from a solution of either sodium or potassium chromate by adding a
soluble lead salt such as lead nitrate or acetate.
Potassium dichromate: Acetic acid (vinegar) added to crystals of potassium chromate will form a solution of potassium
dichromate that crystallizes as ruby red prisms. It may also be prepared by thoroughly mixing a finely powdered mixture of
iron chromate with potassium carbonate and calcium oxide. The mixture is heated to 150 C to dry it, and then to bright
redness with frequent stirring. The mass is allowed to cool, and then digested in a small quantity of boiling water. A small
amount of potassium carbonate is added to the solution to decompose and calcium chromate that may have formed, thus
precipitating calcium carbonate which is filtered off. The solution is then acidified with any aqueous acid to form potassium
dichromate. The solution is evaporated to dryness leaving behind crystals of potassium dichromate. The crystals can be
purified by recrystallizing from water.
Sodium dichromate: Can be prepared as potassium dichromate except sodium compounds are used in place of potassium.
Lead dichromate: Strongly heat potassium nitrate until it is liquefied. Slowly add lead chromate to the liquid salt and stir. Allow
the mixture to cool and add to water to dissolve the potassium dichromate and unreacted potassium nitrate. The insoluble red
powder of lead dichromate will remain. Lead dichromate can also be made by boiling 2 moles of lead chromate with 1 mole of
calcium hydroxide.
Chromium oxide Cr2O3: May be prepared by heating sodium or potassium dichromate, or chromium trioxide, to red heat and
washing the product with water. It may also be prepared by strongly heating chromium oxide heptahydrate to drive off the
water. Chromium oxide heptahydrate can be prepared by boiling a solution of potassium or sodium dichromate with
hydrochloric acid. Ethyl alcohol is added turning the solution green. Ammonium hydroxide is then added to precipitate crystals
of chromic hydroxide heptahydrate. Chromium oxide green, or chromium oxide dihydrate can be prepared by heating the
heptahydrate to 200-220 C in an inert oxygen free environment. It may also be prepared by heating a mixture of 10 g of
potassium dichromate and 18 g of boric acid to low redness. The cooled mass is digested with water forming the dihydrate.
These compounds may also be referred to as chromium hydroxides.
Chromium (IV) oxide CrO2: May be prepared by bubbling nitric oxide gas (NO) into a warm dilute solution of potassium
dichromate. Chromium (IV) oxide is slowly precipitated. The precipitate is washed with water, then with ethyl alcohol, and dried
at 250 C for several hours until a constant weight is obtained.
Chromic acid: Add 1 part of a saturated solution of potassium dichromate to 1.5 parts of concentrated sulfuric acid (about
95%). Chromic acid is also formed by adding chromium trioxide to water.
Chromium trioxide: Add 1 part of a saturated solution of potassium dichromate to 1.5 parts of concentrated sulfuric acid
(about 95%). Cool the solution in an ice bath to precipitate crystals of chromium trioxide. Decant off the acid solution and
place the crystals on filter paper to absorb the remaining acid and moisture. The drying should be done in a desiccator to
protect the crystals from moisture. Chromium trioxide can also be obtained by evaporating a solution of chromic acid to
dryness. For high purity chromium trioxide see the procedure for chromium fluoride below.
Chromic chloride: May be prepared by dissolving hydrated chromium oxide in hydrochloric acid and evaporating off the liquid.
It may also be prepared by adding, by weight, 1 part of either sodium or potassium dichromate to 6 parts of hydrochloric acid
and gently heating for a few seconds to initiate the reaction. Chlorine gas will be evolved, so do this reaction is a well
ventilated area.
Chromous chloride: May be prepared by passing dry hydrogen gas through a strongly heated tube containing chromic chloride.
Chromium oxychloride: Dissolve potassium dichromate and an excess of sodium chloride in a minimum of water. Evaporate
this solution to dryness obtain a co-crystallized mixture of the two salts. Place the crystals in a distillation apparatus and add a
small volume of concentrated sulfuric acid (95%). Gently heat the mixture to distill over the red-brown gas of chromium
oxychloride.
Chromium fluoride: May be prepared by distilling a mixture of lead chromate and fluorspar (calcium fluoride) in concentrated
sulfuric acid. The distillation receiver must be cooled to -100 C to condense the chromium fluoride and the entire apparatus
must be protected from moisture. Glass will decompose chromium fluoride, and is attacked by the subsequent hydrogen
fluoride gas, so some other material such as lead or stainless steel must be used in the distillation apparatus. Upon exposure
to moist air chromium fluoride decomposes to hydrofluoric acid and chromium trioxide. The chromium trioxide thus obtained is
of high purity. When the ultimate desired product is either chromium trioxide or hydrofluoric acid super cooling is not necessary
and the distillate can be passed directly into water.
Ammonium chromate: Add chromium oxychloride to ammonium hydroxide. A yellow colored liquid will form containing
ammonium chromate.
Ammonium dichromate: If acid (hydrochloric or sulfuric) is added to the ammonium chromate solution prepared above the
color will change to a red-yellow indicating the presence of ammonium dichromate.
Chromium nitrate: Strongly heat a crucible of chromium oxide with a Bunsen burner. Add the heated chromium oxide to a
beaker of boiling concentrated (>95%) nitric acid. Upon cooling the acid in an ice bath, brown crystals of chromium nitrate 15
hydrate precipitate. After decanting off the acid and washing the dried crystals become the gray colored 9 hydrate when left in
the open air.

potassium.
calcium hydroxide.
ventilated area.
oxychloride.
ammonium chromate.
the open air.

potassium.
calcium hydroxide.
ventilated area.
oxychloride.
ammonium chromate.
the open air.
Marvin March 27th, 2005, 11:31 AM

Its a fair overview, but its like watching a professional chemist from another building with binoculars. Almost all the details that
should be present in a synthesis are missing. For example,
"Potassium chromate: A finely powdered mixture of iron chromate, potassium carbonate and potassium nitrate are strongly
trioxide, which then combines with the carbonate forming potassium chromate. "
How is this actually supposed to be done by the reader? How much iron chromate, how much pot carbonate, how much pot
nitrate? If strongly heated, how strong? Until red hot? White hot? Until fumes stop? will this evolve nitric oxides? Do we need a
fume hood, a gas mask? After we've done this, how do we extract the product, leaching, recrystalisation? Which products can
be filtered, what will crystalise first?
Under dichromate, you have a different synthesis for the chromate starting material with no reason for the change using
calcium oxide and no oxidising agent. Why the difference? What's the oxidising agent, air? Again how much of anything do we
use? When we acidify, how much acetic acid will we need? What pH should the resulting solution be at and how is this best
measured? Can we use the yellow/orange colour change of the chromate/dichromate itself?
"Chromic acid: Add 1 part of a saturated solution of potassium dichromate to 1.5 parts of concentrated sulfuric acid (about
95%). Chromic acid is also formed ..."
Huh? Thats it? How is this even supposed to work? Am I supposed to take the still mostly sulphuric acid solution and just put it
in a bottled marked 'Chromic acid' or was this a very badly butchered chromic oxide method and adding that to water?
So far, nothing leads me to suspect these methods have actually been tried in this form. That bothers me because there are a
fair few reliable inorganic prep books and individual methods floating around that give detailed instructions for this sort of
thing. The only use I can see of a compiled file would be to offer tried and tested modifications to these in order to use other
starting materials or improvised equipment.


nbk2000 March 28th, 2005, 08:12 PM

How is this actually supposed to be done by the reader?
This is where the 'skilled in the arts' clause comes into play. :p
nbk2000 March 28th, 2005, 08:12 PM

nbk2000 March 28th, 2005, 08:12 PM


Well as for some details being missing, that is due to the rarity of information. If you say there is better out there I believe
you, but I have not seen any. Good details for the really old chemicals are rather hard to come by.



This is what Ive been able to scrape together in a few days. Ive been caught a little off guard by the use of 'chromic', its not
consistant as an oxidation state. Chromic oxide is Cr2O3, ie Cr (+3), chromic chloride is CrCl3 also Cr (+3) but chromic acid is
H2CrO4 (or perhaps more apropriatly CrO3.H2O with CrO3 being called chromic anhydride) ie, Cr (+6)
Details for chromite + alkali + lime. Amount of alkali carbonate should be stoichiometric for formation of chromate. Lime is
added for several reasons, one important one seems to be that it keeps the mass from fusing, which would vastly reduce the
surface area oxygen can get to. The lime process doubles yeilds according to one text and should be added to the extent of
80% of the weight of the ore if the Cr2O3 contents are 30 to 40% and 120-130% if in excess of 50% Cr2O3. Oxidation is
typically 95% complete at 1160C after 30mins and decomposition sets in around 1260C. At 700C oxidation is 'slow' but no
details are given.
According to Polverone in a sciencemadness thread, Cr2O3 can be fused with alkali nitrates to yeild dichromate directly (no
acidification step). This is unexpected but not impossible.
The better information I was thinking of turned out to be a permanganate method, not dichromate. Whoops, but a fair
amount of stuff is present. It should also be noted that Cr 3+ salts are much less toxic than Cr 6+ salts.
Chromic trichloride classic method is to heat chromic oxide (Cr2O3) in a stream of sulphur chloride or carbon tet vapour in a
tube furnace. Not very convenient. Dissolving Cr2O3 in concentrated hydrochloric acid and then evaporating to dryness
produces a hydrate, if this is heated strongly it loses virtually all of the water but some decomposition to C2O3 occurs
colouring the mass green. If the residue is heated to a high temperature, 700C seems in the right range, the chromic chloride
sublimes leaving the chromic oxide behind.
From Inorganic preperations by walton (scan by S.C. Wack). The extraction by precipitation of the strontium salt is a must to
avoid but the oxidation step is clearly sound.
Potassium Dichromate from Chromite.
Chromite, FeCr2O4, is the principal ore of chromium. Chromates and dichromates are obtained from it by fusion with sodium
or potassium carbonate with access of air; the iron is oxidized from the ferrous to the ferric condition and the chromium from
oxidation state +3 to +6. The melt is taken up with water, sulfuric acid is added, and the dichromate is separated by a rather
complicated frational crystallization process which is a good example of the use of phase diagrams (34).
The procedure which follows is adapted to the small scale of the laboratory. Potassium nitrate is added in the fusion to hasten
oxidation, and the chromate is separated from the solution of the melt by precipitation instead of by fractional crystallization.
In an iron dish place 20 grams of potassium carbonate, 20 grams of potassium hydroxide, and 10 grams of potassium
nitrate. Support the dish on a piece of asbestos board with a hole cut to fit it, and heat with a Meker burner until the mixture is
melted. Then add 20 grams of finely powdered chromite, a little at a time, stirring with a stiff iron wire or the end of an old file.
Heat as much as is necessary to keep the mass fluid. Effervescence occurs as the mineral is added. When all the chromite has
been added, heat as strongly as possible for 20 minutes, stirring occasionally, and then cool. While the dish and contents are
still hot but not so hot that undue spattering is caused, place the dish in a large evaporating dish containing enough water to
cover it, and boil until all the material in the dish has been loosened. After a few minutes boiling the solution should be bright
yellow. If it is still green after 10 minutes' boiling, add a little hydrogen peroxide. Then filter, washing the residue on the filter
paper with hot water. What is this residue?
Evaporate the combined filtrate and washings, which contain the chromate, to 100 to 150 ml. Add 1:1 hydrochloric acid or nitric
acid carefully, with stirring, to the hot solution to neutralize excess alkali and decompose carbonate. A precipitate of silica will
probably appear. After a point the mixture will start getting brownish. Stop adding acid, and filter. Add to the hot filtrate about
25 grams of strontium chloride hydrate and enough concentrated ammonia (about 4 ml) to cause the formation of a large
yellow precipitate of strontium chromate. Cool to room temperature and filter off this precipitate. It may be possible to recover
more strontium chromate from the filtrate by adding ammonia. Wash the precipitate with dilute ammonia water, dry it, and
weigh. To prepare potassium dichromate from this strontium chromate, add the calculated amount of potassium acid sulfate
dissolved in aboat 50 ml of water, and digest on the steam bath until the solid appears pure white. This process should take
about half an hour. Then filter and evaporate the filtrate until crystals start to form. Cool to near 0C, filter off the crystals, dry,
and weigh. Calculate the percentage yield, assuming that the chromite contained 30 per cent of chromium.
34, See H. A. Doerner, Chem. and Met. Eng., 47 (1940), 688.
From Rhodium's collection (still down last I checked), untested but supported by the walton procidure which uses hydrogen
peroxide to correct any unoxidised chromium.
Potassium Dichromate from Chromium Metal or Cr(III)

by Nitro
--------------------------------------------------------------------------------
Hey chemists out there! This is a new synthesis of POTASSIUM DICHROMATE, a potent oxidizer which can be used to make
GOOD things. I cannot give you refs cause I have discovered this myself. The idea came from a german chemistry lexikon,
Rmpp's, which said that Cr(OH)3 reacts with NaOH/H2O2 to form chromate.
WARNING
This file was written for informational purposes only. You should not attempt to make it and to use this controlled (in Europe it
is) stuff to make illegal drugs or to poison someone. :) :) Potassium dichromate is toxic. A dose of 4-10 g of it can and will
cause the death of a man if ingested.
Starting material can be:
Chromium metal
Chrome-nickel wire
Any Chromium(III) salt
Synthesis
Weigh out 104 g Chromium metal and dissolve it in 500 ml of fuming (37%) HCl (or equimolar amount of dilute H2SO4) in a
preferably large beaker. Add the metal to the acid in small portions and warm if the rxn goes too slowly. When it's all
dissolved, filter the solution to remove insoluble material the chrome was contained with. In another beaker, dissolve 245 g
pure NaOH in enough water and let the solution cool to 20-40C. Add this alkali solution slowly to the filtered chromium(III)-
chloride solution. A greenish or grayish precipitate of Cr(OH)3 will form. Filter this, squeeze it out and wash it 3 times with
distilled water. You don't need to dry it, just put it into a clean beaker and add: 1) a solution of 160 g NaOH in just sufficient
water and 2) approx. 350 ml of 30% hydrogen peroxide. Add the reagents carefully for that they don't splash. The green
Cr(OH)3 will dissolve and the soln will turn a very beautiful yellow of sodium chromate. If you boil the solution for some time
and then crystallizate it, you can get Na2CrO4, but we want to proceed to potassium dichromate now.
Add 164 ml of concentrated HCl. The color will immediately change to orange. This is the color of the Cr2O72- anion. Now boil
the solution down to approx. 50% its original volume. After cooling white crystals of NaCl can be removed and discarded.
Now weigh out 149 g of Potassium chloride (or equimolar amount of either K2CO3, KOH, or KNO3). Dissolve it in 80C hot
water to prepare a hot saturated solution. Pour this solution into the orange solution of sodium bichromate. Orange crystals of
the crude product will form. Filter them after cooling to 10C.
Recrystalizate the product twice from distilled water. Store in well-stoppered bottle.
If you started from chrome-nickle, then some insoluble nickle(II)-hydroxide will remain undissolved after adding NaOH/H2O2.
This can be filtered. If you had Cr(III)-salts, then just dissolve them in water and add NaOH soln.
The solubility of K2Cr2O7 is only 7 g/100 g water, but that of Na2Cr2O7 is more than 100 g/100 g. Therefore, if you add a
potassium salt solution to Na2Cr2O7 soln, K2Cr2O7 will crystallizate readily.
The yield of this synth is almost quantitative, around 280-290 g if you did it right (>95%). There is only loss of material which
remains on the filter etc.
Some more useful stuff from walton (same scan, S.C. Wack) for chromic anhydride,
Chromium Trioxide.
Chromic acid is a rather weak acid and is also unstable, losing water easily to form its anhydride, CrO3. This oxide is
extremely soluble in water, but the solubility is greatly reduced by adding sulfuric acid, as will be seen in the phase diagram in
Fig. 21. It is therefore an easy matter to precipitate chromium trioxide by adding an excess of sulfuric acid to a solution of a
chromate or dichromate. The difficulty comes in drying and handling the product, which is extremely hygroscopic and powerfully
oxidizing.
Dissolve 30 grams (0.10 mole) of sodium dichromate, Na2Cr2O7.2H2O, in 25 ml of water. Stir into the cold solution 40 grams
of concentrated sulfuric acid (22 ml), adding the acid slowly as soon as the precipitate begins to appear. Let the hot solution
cool to about 25C and filter the crystals on a glass or asbestos filter under suction. Use the apparatus shown in Fig. 22, which
is designed to permit dry air to be sucked over the crystals to remove excess solvent. The filter is a cylindrical tube A in the
bottom of which is fused a coarse sintered glass plate B, or, less desirably, a perforated porcelain or glass plate on which is
laid a circle of glass filter cloth or a mat of asbestos fiber or glass wool. The tube A should first be weighed dry, with the filter
in place and the upper end closed by a solid rubber stopper. During the filtration and drying, the tube is kept closed at the
upper end by a rubber stopper which carries a tube connected to a phosphorus pentoxide drying tube D and a calcium chloride
tower C, as shown in Fig. 22. First suck the crystals as free as possible from adhering mother liquor. Then turn off the suction,
pour over the crystals about 10 ml of concentrated nitric acid, and suck the acid through slowly. Repeat with two more 20-ml
portions of concentrated nitric acid and then suck dry air through the crystals for two hours or more until the crystals are
perfectly .dry and loose. Quickly replace the stopper at the top of A with the solid stopper, and weigh the tube and contents.
The difference in weight between this weighing and the weight of the empty tube gives the weight of the product.
A phase diagram is given, but its small and seems illustrative only, the text says,
"Fig. 21. The system CrO3 - H2O - SO3. The compositions are in moles. The curves for 25C and 40C are practically the same.
(Data of Gilbert, Buckley, and Masson, J. Chem. Soc., 1922, page 1934.)"
Fig 22 is what is described, two towers one to dessicate the air with P2O5 (!) and the other to run this air over the CrO3. Why it
isn't simply dried using a dessicator is not clear, an analysis method is also provided.

details are given.

by Nitro
--------------------------------------------------------------------------------
WARNING
Chromium metal
Chrome-nickel wire
Synthesis
Chromium Trioxide.
oxidizing.

details are given.

by Nitro
--------------------------------------------------------------------------------
WARNING
Chromium metal
Chrome-nickel wire
Synthesis
Chromium Trioxide.
oxidizing.

Mega, and others, thanks for the info. I've often found that intensive
searches of chemistry forums usually yield what I'm looking for.
Sometimes, a university professor will put a synthesis on the net so the
students have an easier access. As for starting materials, Mega, you
hit the nail on the head. I found both chromium oxide and iron chromate
at my local pottery supplier. BTW, chromium oxide mixed with magnesium
powder makes for a spectacular thermite ! :D :D :D


Jacks Complete April 19th, 2005, 07:13 PM

Just a note, but Chromium is a cancer-causing agent, as well as toxic. Don't eat the stuff or breathe it.


Marvin April 23rd, 2005, 05:09 PM

Chromium (+6) is carcinogenic, chromium (+3) is a human dietary requirement. Doesn't make it safe, but t its not worth going
overboard safety wise. To dispose of a chromium compound reduction to Cr 3+ and running down the drain with water should
be fine.
Now then, here is a very useful one, its not in any of my books as a synth, and I havnt been able to find it nosing through any
of the scanned iorganic prep books. Its in the Society of Amateur Scientists electronic newsletter in an article by Norm Stanley.
It is not a difficult matter to prepare small quantities of this reactive liquid in the home laboratory. The chromyl chloride (b.p.
117 C) is recovered by distillation from the reaction mixture. Since the vapor and liquid attack organic materials (including
rubber stoppers) it is preferable to work with all glass apparatus. If you're fortunate enough to own or have access to a good
selection of standard taper ground joint ware, or that venerable symbol of the chemist, a glass retort, then you'r e all set.
Otherwise, don't despair; I used the apparatus shown in Figure 2 with satisfactory results. Rubber stoppers were used; these
may have to be replaced after one or two uses in the corrosive environment. Applying a thin coating of silicone stopcock
grease may retard attack The air condenser was bent from a length of glass tubing. I recommend neon sign tubing, which is
easily worked in a gas flame. If you have some glass working expertise, you can blow a bulb in the riser to serve as a trap for
any liquid that may spurt over. The condensed CrO2Cl2 is collected in a U-tube cooled by immersion in a jar of cold water.
The distillation should be carried out in an efficient fume hood or in a well-ventilated area, preferably open air, as CrO2Cl2
vapor is toxic and extremely irritating(1).
Thoroughly mix 20 g potassium dichromate and 8 g sodium chloride (don' t use iodized table salt) and place in a 500 mL
Erlenmeyer flask. Add 100 mL conc. sulfuric acid and attach the condenser and receiver. Heat cautiously with a Bunsen flame,
taking care that the mixture doesn't froth and spurt over into the condenser. Continue distillation until no more material
distills over. Theoretically, the yield should be about 20 g (10 mL) of CrO2Cl2. Store in a glass-stoppered amber glass bottle.
The full article is currently here,

http://www.sas.org/E-Bulletin/2002-04-19/chem/body.html
The Etard reaction mentioned in the article is a high yeild general reaction for turning methyl groups on an aromatic ring into
aldehyde groups. For the simple case of benzaldehyde there are easier and safer methods of course.

be fine.


be fine.

Jome skanish April 23rd, 2005, 05:29 PM

I've had Cr2O3 sitting in a test tube with 30% hydrocloric acid for over 24 hours now, there seem to be nothing happening at
all, the acid is still without any sign of turning Cr+3 - green. Is something wrong with the procedure Marvin mentioned or does
it need high temperature or something? The difference between 30 and 37% cant be that great, can it?
It would be great to have access to chromates and dicromates from Cr2O3 without having to melt things in crucibles.


I can't personally vouch for any of these methods, I will say they look sound though.
I also can't see where anything Ive quoted talks about adding Cr2O3 to hydrochloric acid. Nitro's method talks about
chromium metal which I had previously thought not active enough to liberate hydrogen but I'm prepaired to suspend my
disbelief on that count.
Pottery grade Cr2O3 is much much less reactive than the freshly precipitated hydrated oxide. Again I can't vouch for this, the
closest experience Ive had is with lapidary ceric oxide in my somewhat successful attempts to produce ceric sulphate, another
potent oxidiser. I would be inclined to try sulphuric acid of different concentrations, starting with concentrated, and pounding
the oxide into a very very find powder first. Reducing to chromium with aluminium is one possibility or its back to a furnace
until you get enough in salt form to recycle.


Jome skanish May 25th, 2005, 05:46 AM

Guess I misunderstood what you wrote. The hydroxide behaves completely different than the oxide, simply by adding more
KOH I got it to dissolve very fast, and I'd think the same thing would happen if hydrochloric acid was added. The oxide does
not react at all, even for weeks it seems. The dehydration seems to be quite irreversible.
Cr-metal from Cr2O3/Al thermite dissolves fast in 30% HCl. I had to bring it outside because the heat made lots of HCl vapor
to fly around, but that might be due to a small ammount of Al and Al2O3 in the Chromium.


kurtz May 26th, 2005, 07:03 AM
Chromium
A Comprehensive Treatise on Inorganic and Theoretical Chemistry
Volume 11, Chapter 60
J.W. Mellor
1931
362 pp.
can be found at:

http://rapidshare.de/files/1988880/mellor_actitc_11_60_cr.rar.html

Chromium
J.W. Mellor
1931
362 pp.
can be found at:


Chromium
J.W. Mellor
1931
362 pp.
can be found at:

Moltar July 24th, 2006, 03:39 PM

I have a detail to the potassium dichromate and the chloric method. 1 mol of
finely powdered sodium dichromate and 3 mol of potassium chloride is heated and stirred in a beaker. The will form
potassium dichromate and sodium chloride.
Na2Cr2O7 + 2 KCl -> K2Cr2O7 + 2 NaCl
In what solution is the sodium dichromate soluble that it can removed and filtered from the remainder of the sodium chloride
?
The potassium dichromate is heated above 500 degree centigrade, it will decompose into potassium chromate,
chromium(III)oxide and oxygen.
2 K2Cr2O7 -> Cr2O3 + 2 K2CrO4 + 1,5 O2
Thermiteisfun September 22nd, 2007, 05:07 PM

I have a grout that contains iron oxide as well as chromium oxide, but for the life of me I can't find the proportions.
I'm wondering if I can possibly use this in a pyro comp or somehow separate the silica. The product is called "Polyblend
sanded grout" labeled "3 grout. The instructions state to mix 1 pint water with 7lbs powder.
Would it be possible to use this in any kind of comp with the silica in it?
Edit: I didn't want to make a new thread so I found one that had the chromium oxide because that is what I want, the mix
also has Fe2O3 which I also want.
http://www.skcinternational.com/nioshdbs/npg/npgd0521.htm
http://www.chemexper.com/chemicals/supplier/cas/2425-85-6.html
nbk2000 September 23rd, 2007, 02:40 AM

I don't suppose the thought of using a MAGNET ever occurred, did it?
The only thing in those lists that is magnetic is the iron. :p
As for the chromium...

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > The Road to
Furazans
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View Full Version : The Road to Furazans
Microtek March 24th, 2006, 04:36 PM

For the last few months, I have been undertaking a low-intensity study to establish a workable route to the very attractive nitro furazans. As a group they contain almost all
the desirable properties that energetic materials can have: Insensitivity, high density, high heat of formation, thermal stability, melt castability and ( not least ) some of the
highest VODs ever achieved.
Not all these properties are present in a single compound obviously, but the furazans remain a very interesting group of compounds.
The precursor to most furazan compounds is diaminofurazan ( DAF ), so my work has been concentrated on synthesizing this chemical.
The synthesis goes as follows:
nitromethane --> hydroxylamine --glyoxal--> glyoxime ---> diaminoglyoxime

--KOH--> diaminofurazan
Hydroxylamine:
20 ml nitromethane and 30 ml HCl, 30 % was placed in a flask with a screw lid. The cap was protected with teflon tape and was screwed firmly onto the flask.
The flask was then placed on a hotplate and heated to ca. 100 C. This temp was held thermostatically until homogenous, which required about 20 hrs.
Most of the liquid ( water, HCl and formic acid ) was distilled off and then the remains was allowed to cool very slowly. This caused large crystals to precipitate. When cooled to
0 C, the supernatant was decanted and reconcentrated. This process was repeated until only about 5 ml remained and this was discarded.
The crystals where washed with a small amount of isopropanol and dried over CaCl2 for two days. Yield was roughly 15 g, but this can undoubtedly be done better.
Glyoxime:
6.32 g hydroxylamineHCl was dissolved in 10 ml water along with 2.5 g NaOH at 0 C. 40 % glyoxal ( 5.1 ml, 44.6 mmol ) was added dropwise with stirring, maintaining temp
at 0 C.
Temp was kept at that level for 15-20 min and was then allowed to rise to room temp. It was left to stand overnight covered with a watchglass.
Precipitate quickly began to form ( perhaps 10 min after end of glyoxal addition ) and the next day the mix was a thick slurry.
The precipitate was suction filtered, washed with a little water on the filter and dried over CaCl2 for several days. Yield was 3.247 g or 82 % ( crude product ).
Diaminoglyoxime:
3,7 g NaOH was dissolved in water and diluted to 18.5 ml.

3.25 g glyoxime was added in one portion and quickly dissolved.
Then solid hydroxylamineHCl ( 5.13 g ) was added in one portion and immediately produced a tan precipitate similar in appearance to solid glyoxime.
A reflux condenser was attached to the flask which was then heated to slow reflux. This caused the precipitate to dissolve almost completely.
The reflux was maintained for 6 hrs and then the mix was allowed to cool down very slowly. This caused yellow-orange needle-like crystals to precipitate. These were filtered
off and washed with 5 ml cold water and were then dried over CaCl2, giving 1.4996 g or 34 %.
That's as far as I have gotten until now. The next step calls for aqueous KOH at 175 C which means an autoclave... I'm a bit worried at the thought of a homemade autoclave/
pipebomb exploding in my kitchen.
nbk2000 March 29th, 2006, 02:17 AM

A potential 'autoclave' that should be very safe to use would be the CO2 tanks for paintball guns.
They're designed to contain 3000PSI of pressure, and are made of steel, so should be more than adequate for your purpose.
If you buy the disposable CO2 cartridges for paintball guns (look like giant version of the pellet gun type), than a simple cap fitting would be all you'd need to make to use it as
such. Only cost about $7 for two.
Microtek April 16th, 2006, 09:36 AM

I was thinking about using a piece of pipe used for plumbing it's made of galvanized mild steel, 3 mm wall thickness with threaded caps at both ends and has a 25 mm internal
diameter. It has the advantage that I could place an open test tube inside to hold the reactants, thus avoiding corrosion and contamination. A steel tube would probably
passivate in the alkaline environment, but may cause contamination.
Unfortunately, I haven't been able to find pressure ratings for this exact type of pipe, so I'm going to have to do a test in a safe location...
nbk2000 April 17th, 2006, 01:44 AM

If it's schedule 40 galvanized, either continuous weld or seamless, than it's rated for 700 PSI.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Kurt Saxons
Method....
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View Full Version : Kurt Saxons Method....
Red Beret March 29th, 2006, 10:04 PM

Has anyone personally tried Kurts method for making knockout drops? I am planning on trying this, I will be using denatured ethanol, so hopefully the additives wont cause any
side reactions, they make up about one percent of the mix I think.
The reason I'm asking is that occasionally, Kurt dosent write the most accurate procedures. Do the drops work as well as he states? Information I have from the net is
questionable. Thats why I'm asking someone with first hand experience. Is is worth the use of valuable H2S04? I have someone in mind to try this substance on (not
myself):rolleyes: . Also, is the reccomended dosage (a couple of drops) correct?
Interestingly, there is a chemical supplier that sells chloral hydrate in crystaline form, they sell to the public. They do ask questions but never get too inquisitive. Its listed as
being a toxic substance. If anyone is interested in this supplier PM me. Only long time members please. Too many suppliers have tightened up because too many people knew
of them.
Thanks for any help anyone can offer.
Alexires April 6th, 2006, 01:24 PM

Haven't read about Kurts method but... (goes and fetches organic chem book)
From "Organic Chemistry for Medical, Intermediate Science and Pharmaceutical Students" by A. Killen Macbeth (1946), pg. 103 we get
Chloral. Trichloroaldehyde CCl3.CHO - This important substitution product of acetaldehyde cannot be prepared by the direct action of chlorine on the parent substance. It is
manufactured on a large scale by the action of chlorine on alcohol (assuming Ethanol - Alexires), first at ordinary temperatures and later at its boiling point. Chloral alcoholate is
the product, but by distillation with concentrated sulphuric acid chloral is produced. (Ill try and give the picture - Alexires)
. . OC2H5
. . ./
CCl3C-H --------------> CCl3.CHO + C2H5OH
. . .\ . . . . . . . . . . . . . .(Chloral) . . (Alcohol)
. . . OH
(Chloral Alcoholate)
The action leading to the production of chloral alcohloate is not yet clear. It is suggested that the alcohol is first oxidised to aldehyde, which is converted into acetal, and this in
turn gives trichloroacetal, going then to chloro alcoholate.
Chloral is an oily liquid boiling at 97 C. On treatement with water, it forms a white, crystalline substance known as Chloral Hydrate, CCl3.CH(OH)2. This and the parent
substance are both converted into chloroform on boiling with lime of caustic alkali.
Hope that helps a bit. Useful little book this is. So far I've got info for chloroform, carbon tetrachloride and mustard gas. A few other things too, but cant remember.
This was straight from the book, I haven't tried it. So be careful.
(edit - the picture of the chloral alcoholate is ment to have the OC2H5 and the OH attached to the last carbon. Stupid formatting. Stupid me not knowing how to. Excuse all
underscores)
akinrog April 6th, 2006, 09:09 PM

Chloral. Trichloroaldehyde CCl3.CHO - This important substitution product of acetaldehyde cannot be prepared by the direct action of chlorine on the parent substance.
I doubt this statement. From my high school organic chemistry knowledge, I remember that in order to make chloroform first one reacts ethyl alcohol with chlorine (which
produces Chloral) and when you treat this with alkali (NaOH or KOH) it gives chloroform.
I believe the author of the book is mistaken or what!... Regards
Alexires April 9th, 2006, 09:21 AM

Akinrog - I don't profess that this book is in any way correct. I stated in my post I haven't tried it. I remember it saying earlier that Chloral was the exception to the rule in
regards to direct chlorination.
This book was found in the University library, so I figured it couldnt be too wrong. Then again, it was written by the Professor of Chem (or something like that) for the Adelaide
University, so it might not be that right *wink*.
akinrog April 9th, 2006, 11:52 AM

This important substitution product of acetaldehyde cannot be prepared by the direct action of chlorine on the parent substance.
Now I understand it better: The keyword here is parent substance. When I saw it, I thought parent substance is ethyl alcohol. But on the second thought, I understand it's
acetaldehyde, which makes that statement true. Sorry for the mess up. :( Regards.

That's fine. I'd be happy to be pointed wrong on any of my posts, as long as there is evidence that I am actually wrong. Those old books seem to be rather obscure at times,
for instance insisting on calling Ethanol Alcohol all the time. It can be confusing.
Unfortunately, they are the only manuals that have the good stuff, the new University manuals don't even hint at these synthesis.
nbk2000 April 10th, 2006, 05:59 PM

If you asked someone to pick you up some alcohol from the store, would you be pissed at 'em if they picked up everclear? 'Alcohol', by default, means ethyl alcohol, unless
otherwise stated.
Want confusion? Try the REALLY old journals, like from the time when 'ether' was the stuff the universe was made of. :p

Ahhh, the good old days.
I remember reading about ether. They might not have actually been to far off the truth (physicists, that is).
*laugh* Maybe I'm just too conditioned. Whenever I think of "alcohol" I think of a hydrocarbon chain with an OH attached, not ethanol, hence why it took a minute to work out
they were talking about ethanol, not the broad class of alcohols.
Red Beret April 14th, 2006, 05:06 AM

Thanks guys, the input has been helpful.
I have the oportunity to buy crystaline chloral hydrate, what is everyone opinion on how it works?
Is it a simple as; a few drops in a drink and they are out for the night, regardless of previous alcohol consumption?
I could always make chlorobutanol, but unless I want to buy chloroform, I will have to make it, and in turn but a fractional distilation setup.
Easier to buy the chloral hydrate, not as much fun as making it though.;)
nbk2000 April 15th, 2006, 10:04 PM

Alchohol is an enhancement to the sedative effects of chloral hydrate.
Also, chlorbutanol is supposed to have a nasty taste, so why use it?
Red Beret April 16th, 2006, 02:29 AM

The only reason I'm considering using it is that its rather easy for me to get hold of. Chlorobutanol manufacture seems fairly straight forward, but I would have to buy the
chloroform. Unless of course I made it, which requires fractional distilation. So I guess I am just weighing up the pros and cons.
Apparently the taste is well hidden by orange juice etc. I'm just getting into this area of chemistry (sedatives I mean), and I'm just a bit impatient, can't wait to test it;) . I'll
read up as much as I can before I make my choice.
nbk2000 April 16th, 2006, 08:56 AM

I'm just a bit impatient, can't wait to test it. ;)
Just be sure to wear a condom! ;) :p
Alexires April 17th, 2006, 12:15 PM

*chuckle* practical advice once again NBK, but I have a feeling that if he falls asleep while sleeping with his girl, not wearing a condom will be the least of his problems.
Be eager, but don't be TOO eager. Play it safe, and contemplate the risks of such experimentation. Buy a hamster or something first, so you can work out the average
dosages, and to see if you screwed up and its actually poisonous.
nbk2000 April 17th, 2006, 09:25 PM

I don't think he'd be the one getting knocked out, nor would it be 'his' girl. ;)
Hence, the condom. :D
Thank God for chemistry! Otherwise, what would fella's do to get a date after the rohypnol supply dries up?
FUTI April 18th, 2006, 12:38 AM

I thought that only GBL or 1,4-butandiol has that potential abuse properties...so this one is new for me.
Beware for whatever use you try to use it, that in some people those compounds cause death as dosage and metabolic clearance isn't same in every man/woman. NBK give
you a hint...search the Google and find more to learn.
You can make chloroform using almost the same way as for chloral hydrate.
Chloral hydrate were once in the old time known among the barmens as "Mickey Finns" AFAIR. They use it for putting nasty customers in the dreamland through mixing with
alcohol. That can be used also, but as robbery tool...and that is something I don't approve. I heard of some cases where people were knocked down by drinking coffee with
"nice polite people that kindly bring them the drink from the counter" but in modern times anyone can buy some kind of sedative for that purpose, so although I'm against
spreading the recepies for potential dangerous substance - I don't think this thread will make a change. People with criminal intention will probably buy something OTC then
make it themself.
nbk2000 April 18th, 2006, 01:46 AM

I'm against spreading the recepies for potential dangerous substance
Then you've come to the wrong place! :)
Chloral hydrate feel out of common use as more potent sedatives, like barbituates, came into being. But, there's always something to be said for a classic. ;)
bipolar April 18th, 2006, 03:56 AM

I never realized how easy it was to make GHB. All you need is GBL and sodium hydroxide(I think). They used to sell GHB kits in the US with the two ingredients in two
premeasured containers.
You just mix together and bam you have GHB. You just have to use litmus tests to make sure all the acid got used up in the reaction or something.
Now GBL is heavily regulated in the US. You can still easily order pharmaceutical grade GBL over the internet from europe as an Alloy-Cleaner(or other things). They charge a
high price because they know what they are selling it for. Apparently people do it all the time. The directions are on the internet.
A lot of people take GBL recreationally. They say people crave sex on it more. It causes the same effect in lower doses as alchohol. It is dangerous to use enough to knock
someone out.
I hope you all aren't serious about the above. If you are, I recomend the Double Your Dating ebooks by David Deangelo instead. TMP has them on his FTP, or just get them
from a torrent site.
FUTI April 18th, 2006, 07:38 AM

Talking about barbiturate...I heard a story describing how they got their name. Chemist that made them name it after his mistress...what to say...she made him relax and
calm...not like his wife;). I couldn't resist to share this info even if it turns to be hoax.:D
inthekitchen May 15th, 2007, 07:29 AM

So did the knockout drops work using the denatured ethanol? In some states the concentrations of alcohol cannot exceed 75 percent. If one wanted to make chloral hydrate
they'd have to buy 95% denatured ethanol or distill the 75% stuff. Distilling is a pain in the ass so it'd be great if you could use denatured/regular alcohol interchangeably. I'm
just curious if that's possible with the production of chloral hydrate.
Gammaray1981 May 15th, 2007, 12:10 PM

"Must not exceed"? Do you mean "be below?" It appears that a higher concentration of ethanol is desirable, not a lower.
zeppelin69 May 15th, 2007, 02:10 PM

"Must not exceed"? Do you mean "be below?" It appears that a higher concentration of ethanol is desirable, not a lower.
I'm pretty sure that Inthekitchen is saying that some states require "denatured" alcohol to not be over 75% ethanol
Enkidu May 15th, 2007, 02:59 PM

@kitchen: I wouldn't use denatured alcohol. Denatured alcohol is a mix of ethanol and methanol. The methanol constituent is at least 5% of the mix and sometimes a lot
more.
@Gammaray (and NBK): From Synthetic Organic Chemistry by Wagnor and Zook,
Direct halogenation of aldehydes is more complicated. Substitution on the aldehyde carbon as well as the a-carbon may take place. Thus, acetaldehyde in aqueous solution
yields chloral, whereas, in the absence of water, acetyl chloride is formed.
As a side note, chlorine dissolved in water is in equilibrium with hydrochloric acid and hypochlorous acid, or H2O + Cl2 <--> HCl + HOCl. I have a gut feeling that those acids
(especially HOCl) are important in the mechanism for chloral.
The chlorination/oxidation of ethanol produces no water. Contrary to NBK's post in kitchen's recent DDT thread, you should not use absolute ethanol.
Of course, the reaction of chloral and water produces chloral hydrate. Therefore, I think that you need enough water in your reaction for use first in the formation mechanism of
chloral and then to continue the reaction to chloral hydrate. In other words, if you have very little water in your reaction, I think that you might use it up early on and then
spend the rest of your time forming acetyl chloride (which is highly useful, but DO NOT drink it.)
Once you get chloral hydrate, you can convert it back to chloral by dissolving it in conc. sulfuric acid and distilling off the chloral.
I haven't spent much time looking into this; feel free to disagree, because it's very possible that I could have overlooked something. Of course, don't take my word as gospel,
especially if you're going to be ingesting anything.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > sodium azide
synthesis
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Moltar July 22nd, 2006, 03:11 PM

Anyone made some sodium azide from sodium nitrate and sodium amide?
1 mol of powdered sodium nitrate and 3 mol of sodium amide is mixed in beaker and this is molten at 175 degree centigrade. The mix is heated until no ammonia is bubble off
and the cooled mass will give a mix of sodium azide and sodium hydroxide.
NaNO3 + 3 NaNH2 -> NaN3 + 3 NaOH + NH3
How can you remove the sodium hydroxide from the cooled mass ?
By the way, a much better method to obtain sodium azide is when dinitrogen monoxide is passed over heated sodium amide at 180 degree centigrade.
NaNH2 + N2O -> NaN3 + H2O
Dinitrogen monoxide is formed when ammonium nitrate is slight heated above the melt point. A Distilling Column will help.
NH4NO3 -> NH3 + HNO3 -> N2O + 2 H2O
Any reply is more than helpful.
sprocket July 23rd, 2006, 08:27 AM

This is a very dangerous procedure, which I'm about to make even more dangerous. Good temperature control and protection is essential.
To separate sodium azide from sodium hydroxide you can convert the azide to hydrazoic acid (highly unstable) by acidification. The hydrogen azide is then distilled off (bp
30C). The heat of neutralization should be more than enough to evaporate the hydrogen azide, so add the acid slowly. It's probably a good idea to have some water in the
receiving flask to dilute the distilled hydrogen azide as it's fairly stable in low concentrations.
Pure sodium azide is then obtained upon neutralization of the hydrazoic acid.
Obtaining pure nitrous oxide from ammonium nitrate can be tricky. A temperature of 180-200C must be maintained and the stream of gas thoroughly dried. At temperatures
above 230C other nitrogen oxides form.
Keep in mind that sodium amide reacts with water to form sodium hydroxide and ammonia. If you do not dry the nitrous oxide you will end up using even more sodium amide
than with the sodium nitrate reaction.
With drying of the nitrous oxide the reaction would be:

2 NaNH2 + N2O --> NaN3 + NaOH + NH3
sprocket July 30th, 2006, 10:19 AM

Found a couple of nice procedures in Handbook of Preparative Inorganic Chemistry, Volume 1 Second Edition by Georg Brauer.
A solution of NaN3 is mixed with a small amount of litmus and sulfuric acid ( 2 : 1 diluted with H2O) is slowly added. When an excess of acid is present, the mixture is
slowly distilled. By repeated fractionation one obtains 91% acid, which can be made anhydrous by distillation over CaCl2. However, extraordinarily violent explosions
sometimes occur with this procedure. According to Gunther and Meyer, HN3 can be prepared in a relatively safe fashion by replacing the sulfuric acid with stearic acid.
Pure NaN3 is mixed in a round-bottom flask with stearic acid; a trap cooled to 40C is f used directly to this flask. The reaction flask is evacuated and heated. The HN3
is then purified by distillation at 50 to 80C.
SOLUTIONS OF HYDRAZOIC ACID

Because of the very high danger of explosion with pure HN3, it is expedient to work only with its relatively harmless solutions.
I. Aqueous solution: A solution of NaN3 (15 g.) and NaOH (5 g.) is prepared in 150 ml. of water in a 250-ml. distillation flask equipped with an addition funnel and a high-
efficiency condenser. The end of the condenser is connected by means of an adapter to a 500-ml. suction flask, which contains 100 ml. of water. The suction outlet of the flask
is connected to a tube leading directly to the hood. The contents of the flask are heated to boiling (very important!), and 90 ml. of 40% H2SO4 is added dropwise. The
distillation is continued until about 50 ml. of the solution remains in the flask. In this manner one obtains a solution containing about 3% HN3 (0.6-0.7N). The initial addition of
NaOH is a precautionary measure which definitely precludes too high a concentration of HN3 in the cold solution.
II. Anhydrous Ether Solution: Since the distribution of HN3 between water and ether is approximately 1:7, one can extract an aqueous solution of HN3 with ether. However,
even in this case it is preferable to use a distillation method: NaN3 (30 g.) is dissolved in 100 ml. of water, 150 ml. of ether is added, and the mixture is placed in a 500-ml.,
round-bottom flask. The latter is equipped with an adapter fitted to a condenser, followed by a suitable icecooled receiver flask containing 100 ml. of ether. The roundbottom
flask is also equipped with an addition funnel, the tip of which is immersed in the liquid and through which 30 ml. of concentrated H2SO4 is slowly added. The bulk of the ether
and HN3 distill off during the addition of the H2SO4. The remainder is driven off by heating on a steam bath. The ether distillate is dried over CaCl2 and then distilled from this
desiccant.
lacrimachemist August 27th, 2006, 06:05 PM

If this method using hydrazoic acid is used, be EXTREMELY careful. Not only is it highly explosive, but it is extremely poisonous. Hopefully you know this, but just in case...
meyer25 September 5th, 2006, 10:22 PM

Prepare a solution of 40g (1,0mol) NaOH in 50-60mL distilled water. Cool down and adjust the volume to 100mL (10M conc.). Add 62g (1,0mol) 80% hydrazine hydrate and
cool down to 0-5C. Under temperature control of 0-5C (ice bath) and stirring, add dropwise 90g isopropyl nitrite over an hour. After adding all isopropyl nitrite, stirr by 0-5C
for additional 15minutes, then stop stirring and let the mixture warm up to room temperature. After this is done, evaporate almost all volatile parts under vacuum. You may
evaporate the reaction mixture by heating it gently, but avoid open flame or similar because of the isopropanol and traces of isopropyl nitrite boiling off the mixture. Avoid also
exposure to iPrONO, as it is toxic. After evaporating all liquids, the solid rest is fairly pure sodium azide. Do not dry the solid substance by heat! Just put it in an desiccator and
let it dry by normal teperature. Keep in mind that it is a violent poison.

a n d I m provised C hemistry > Synthetic Cocaine
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Nitrophuric Aci August 17th, 2006, 03:47 PM

I h a v e a g o o d deal of respect for roguesci. But there are many out there who are kewls and call them selves chem ists in light of
the fact that they have probably read alot of explosive articles an experim ented a few times and n ow call them selves pro's. To
those true chemists (if any still around ) perhap s you can form ulate a substance very similar to cocaine using simple over the
counter items or proceedures. Since co caine m anufacture is nearly im possible in the states and requires a great deal of effort
(i believe cultivation of crops is at least 6 m onths) a true chemist could idealy come up with a synthetic product that num b s t h e
m o u t h a n d s p e e d s y o u u p . A n y o n e u p f o r t h e c h a l l e n g e ? Or is this sim ply just explosives "experts" posing as chemists

W o u l d t h e r e b e a n y d o m e s t i c o r g a n i z a tions with large am ounts of cash a nd a vested interest in producing synthetic cocaine?
Any gang banger with even half a brain that would rather invest in legitim ate business opportunitie s rather than blin g bling
Are there are organizations outside of the US that would hunt yo u down and kill you if you interrupted their countries major
export, and their personal source of vast wealth? Ahh, there is som e g u y n a m e s C a r l o s a t t h e d o o r f o r y o u , l o o k s C o l u m b i a n ,
m ean disposition
As this is not a drug forum , th is is not the crowd for that. The laboratory synthesis of cocaine is absolutely possible, like m a n y
other naturally occurring pharmaceuticals, but that does not m ean it is easy. There m a y y e t b e m a ny viable synthetic
alternatives m a k i n g c o c a i n e s y n t h e s i s a n e c o n o m ically viable procedure, but dont expect the procedure to appear in the
journal Synthesis anytime soon.
Nor would I expect and drug d ealers who have figured it out to spread their procedure onto the streets. Business is business.
As I am not familiar with the synthesis of cocaine, I would direct you to the library first and foremost. Hit the journal stacks, the
p a t e n t d a t a b a s e , a n d a f e w p h a r m a c e u t i c a l d a t a b a s e s t o s e e i f a n y o n e h a s p u b l i s h e d a g l i m mer of info. It is more likely you
would have to do a retrosynthetical analysis with current synthetic techniq u e s . T h e p i e c e s o f t h e c h e m ical puzzle may be there,
b u t n o o n e m ay be willing to put them together for coca ine.
A true chem ist would not bother wasting his tim e doing your hom ework for you so that you can get high, or get rich trying. :) I
would say try www.syn thetikal.com but they always appear to be having troubles. Oh I m iss The Hive.
Cobalt.45 August 17th, 2006, 10:10 PM

Although the phenylisopropylamine substructure is an integral part of m ost known stim ulants, the well known and m u c h a b u s e d
stim ulant, co caine, does not share this structural feature. The cocaine m o l e c u l e i n s t e a d c o m p a r e s m ore closely to the structure
of atropine. The synthesis of cocaine has recen tly been revisited b y C a s a l e a n d m any of the procedural techniques are
explained in sufficient detail so that any com petent organic chemist can now mak e t h e C - 3 e q u a t o rial cocaines (Casale 1987);
however, it is still a tedious and dem anding synthesis, and in my opinion will only be enco untered on rare occasions in
clandestine laboratories. The particular pharma cological behavior of cocaine is unquestionably due in major part to the
stereochemistry of the molecule as determ ined by the fused bicyclic tropane ring system (Clarke et al. 1973). Given the
present difficulties associated with the synthesis of the tropanes and the ready availability of the natural product, it is unlikely
that a synthetic CsA of this com pound will appe ar in the near future. However, it is the case that ce rtain modifications of natural
coca ine can result in products having substantially greater potencies than cocaine. The compounds 2-carbom ethoxy-3-(4-
fluorophenyl)tropane and 2-carbom e t h o x y - 3 - p h e n y l n o r t r o p a n e a r e b o t h s o m e 60 tim e s m ore potent than cocaine (C larke et
a l . 1 9 7 3 ) . T h e s e c o m pounds could well be of interest to s o m e c l a n d e s t i n e c h e m i s t s a s t a k i n g o n e k i l o g r a m or cocaine and
converting it into a product som e sixty times m ore potent would obviously be quite cost effective.
Kind a like gold from seawater. C an be done, sure. But profit margin? Unless you were able to synth the aforem e n t i o n e d
"Superdope", there's no m oney in it.
As the manufacturers' cost of organic dope is pennies per pound, they could beat you down in a price war. But m ost likely, they
would either kill you or drop a dim e o n you. Either way has a shitty outcom e.
Instead, why don't yo u perfect a sim ple "holy g rail" organic peroxide synth or the like?
chemdude1999 August 17th, 2006, 11:30 PM

Try this out. Good Luck.
http://leda.lycaeum.org/?ID=12948
http://en.wik ipedia.org/wiki/Richard_W illst%C3%A4tter
Of course it has been done before.
I agree with Cobalt.45. Let us stick to explosives and the like. There are plenty of drug sites.
Chris The Great August 18th, 2006, 02:15 AM

Better to look at fentanyls IMO. They're starting to pop up with greater frequency, and are nearly 1000 tim es strong er than
herion, so you can make 10g and have the equivalent of 10kg smack.
Best to not g et involved in a big city, far to risky, lots of gangs. I doubt you'd get "noticed " by crim e lords by selling o n a
"small" scale , I m e a n y o u d o n ' t s e e c o k e d e a l e r s s h o o t i n g m eth dealers for taking their m arket. Nor would your 10kg herion
s u b s t i t u t e m a k e a b l i p o n a m arket that brings in m etric tons of it every year.
Meawoppl August 27th, 2006, 04:16 PM

You want to get in on an unutilized m arket . . . m odafinil check that out.
"wakefullnes prom oting, m e m ory enhancing, m ood brightening psycostim ulant" T he perfect school drug. . . I would love living
a 40 hour awake 8 asleep schedual, they did it for fighter pilots. Also you have to worry less about crackdown on it, its not
physically addictive, and people on it behave fairly norm ally. Shit i could hold a full tim e j o b s y n t h e s i z e m y s e l f m o r e m odafinil
and go to school in 40 hours of uptim e. Also you dont have to worry so m uch abo ut cutting into other drug rings. Th ey m ight
sell less m eth, but at the sam e tim e, m eth is rarely associated with large cartels etc.
e - m a i l / p m m e if you are interested in figuring that out, this foru m is not for drug related stuff anyway.
nbk2000 August 27th, 2006, 05:52 PM

Private comm unications regarding the synthesis of controlled substances = Criminal Conspiracy.
Public discussion regarding the synthesis of controlled substances = Constitutionally protected Freedom of Speech.
Your choice.
Also, you're not going to be able to go on two days up, 8 hours down, for long before inevitably we aring down. The m ind
evolved to the wake/sleep cycle its at for a reason.
FUTI August 28th, 2006, 04:38 AM

NBK has it right Meawoppl. Always try to stick to normal living/working condition/status. Russians have practice to ex pose their
pilots to higher G forces regularly...that reduce their effective work span (due to d amage to physical fittness) for 30% down
IIR C.
I'm aware that U S DoD experim ent with mind altering substances to increase com bat readiness etc. But I wait that project to
fail to laugh about it.
Synthetic cocaine? W hy on earth would anyone try som ething stupid as that...natural supllies are a lready MO R E t h a n a b u n d a n t .
By yourself a ticket to Columb ia instea d.
nbk2000 August 28th, 2006, 05:33 AM

Natural coke can be interdicated along a long supply chain.
Synthetic coke m a d e i n d i g e n o usly wouldn't nee d to be transported, but then becomes subject to precursor restrictions.
Only if a truely OTC process was developed for one of the fluorocaine analogs, would it then be worth the effort. Until then...fly
to Colombia. :)

M o d a f i n i l o n l y e n a b l e s 4 0 h o u rs of wakefulness twice, with 6 hou rs of sleep in between, before requiring you to mak e up the
bala n c e o f t h e l o s t s l e e p . M o d a f i n i l i s b e s t u s e d t o s u s t a i n w a k e f u l n e s s d u r i n g t h o s e t i m e s w h e n y o u m a y b e f a t i g u e d . T h i s
m ay include m ath lectures, study times, long driving trips, and all nighters. The d rug is intended to help yo u m aintain
alertness while still getting a full nights rest. If you do not sleep, your im m u n e s y s t e m will not function. Many people are
u n a b l e t o m aintain alertness even after a full nights sle ep, or have sleeping difficulties that m ay m a k e t h e m tired at critical
m oments. Modafinil is not a stim ulant, and the re are conflicting studies that it actually enhances m e m ory or mood in healthy
adult men.

a n d I m provised C hemistry > C o n d o n e P r o v i d o n e ?
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View Full Version : Condone Providone?
sd1904 August 20th, 2006, 11:42 PM

It is the only iodine seen around these parts. (San Diego) So the question is .... Is providone able to produce iodine crystals.
Or is it possible to condence down to a % that it will be?

I b e l i e v e t h e r e u s e d t o b e a p rocedure floating around on the Hive about doing this, but since their demise I can't direct you
there.
The product is called povidone by the way, or m ore precisely povidone-iodine. Povidone is actually an organic polym er used to
disperse other chem icals. The iodine is bound to the po vione, which is in turn dissolved in alcohol or other compoun ds
d e p e n d i n g o n t h e m anufacturer.
I would suggest you research various reactions of iodine to see what kinds of reactions you might be able to do with the
compound. You should try bro mine and chlorine too since they have very sim ilar reactivity in many ways.
Just off the top of m y head I would say the povidone-io dine may react with some compound to form a salt you can isolate a n d
further process for elem ental iodine.

I believe it m ay be possible to collect the iodine by sublim ation. Maybe by heating, and collecting the iodine on som ething
cold.
c.Tech August 28th, 2006, 07:51 AM

C o n d e n s e i t i n a m etal pipe surrounde d by a water jacket constantly pum ping water. W hen the pipe fills up the crystals could
be pushed or washed out, then purified.
Purification h ere (http://www.frogfot.com /synthesis/iodine.htm l).

Yes, yes, that's how you collect and pu rify pure iodine, but the iodine in povidone-iodine is chem ically boun d in som e way. It
needs to be reacted to free th e iodine; that's what we are after here.

So, I'm gue s s ing t hat m eans that it's not really Iodine, but an Iodine containing m olecule .
If th at is the case, then maybe find out what else is in the solution, and m a y b e g o from there.

a n d I m provised C hemistry > W ould this work to m ake Sulfuric Acid?
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View Full Version : Would this work to make Sulfuric Acid?
Declan August 28th, 2006, 05:55 AM

Since sulfuric acid is getting harder to get around where I live, yet phosphoric acid (H3PO4 ) is still 7 bucks a gallon at Hom e
Depot, I thought of this (MgSO4 is Epsom Salts, at the supermarket):
H 3 P O 4+MgSO4-->H2SO 4 + M g 3 ( P O 4 ) 2
Of course not balanced. SO4 -2 is solu ble with Mg 2+, so it would dissolve. PO 4 2- is insoluble with Mg, so it could b e filtered
out m a y b e ?
Also, H3PO4, already not a ve ry strong acid, basically never reaches the conjugate base PO 4 3-. Therefore, I think it would be
m ore like:
H 3 P O 4+MgSO4-->H2SO 4 + M g 3 ( P O 4 ) 2 + M g H P O 4 + M g ( H 2 P O 4)2
I'm probably m i s s i n g s o m e t h i n g h u m ongous here that'll make it all not work, but if it does, I found a good source for Sulfuric,
at least for m e, and possibly for more people when it becomes controlled in urban areas in the far future.
c.Tech August 28th, 2006, 08:13 AM

I'm still learning chemistry and am not the best yet but here are som e other m ethods which can be used.
Their fairly simple and have been around for a long time.
SO2 + H2O2 --> H2SO 4
SO2 + NO2 --> SO3 + NO

2NO + O2 --> NO2
SO3 + H2O --> H2SO 4
Skean Dhu August 28th, 2006, 10:53 AM

Car batteries, and acid refills for them will work if you ta ke the tim e to boil off the water(they're ~3 5 % H 2 S O 4 )
W h i l e n o t t h e m o s t e c o n o m ical path to sulfuric acid, the y do work and for m a n y p e o p l e h e re that is their chosen rou te
Declan August 28th, 2006, 02:15 PM

I'm still learning chemistry and am not the best yet but here are som e other m ethods which can be used.
Their fairly simple and have been around for a long time.
SO2 + H2O2 --> H2SO 4
SO2 + NO2 --> SO3 + NO

2NO + O2 --> NO2
SO3 + H2O --> H2SO 4
Guys, I know that you can get in in batteries, and a number of other ways, but I was asking if this works.
By the way, it's generally:
S+O 2-->SO2 burned in the presence o f O 2

2 S O 2 + O 2 - - > 2 S O 3 o x idized with a vanadium ca talyst
SO3+H2O-->H2SO4 usually actually form ing H2S2O7, because straight to sulfuric is too exotherm ic.

W ell, Declan, why don't you te ll us? I'll not do any hom ework I d on't really have to, so here is a hint: Using the Arrh e n i u s
equation calculate the activation energ y needed for the reaction. W hat you will ne ed to find, and why I don't want to do this for
you, is the rate constant for the reaction. I suggest you look for the far more com mon reactions between sulfuric acid and
p h o s p h a t e s a n d u s e t h a t r a t e c o n s t a n t a s a g u i d e . T h e n a l l y o u n e e d t o d o i s f i g u r e a t w h at tem perature the reaction proceeds
with any useful speed.
DONMAN D e c e m ber 4th, 2006, 02:11 AM

MgSO + H2O 2 +MgO2 + H2SO 4
Try that.
Universal D e c e m ber 9th, 2006, 11:59 PM

W ell now isn't that a strange reaction, no apparent prod ucts of it at all. That must be a ne w m a g n e s i u m sulfate, I've never
seen it before.
D i d y o u m e a n M g S O 4 + H2O2 --> MgO + H2SO 4.
I still don't think it is going to work. H2O2 maybe trying to get fid of som e O 2 but not really the H2, the phosphoric acid way.
If some reaction did occur it would m ore likely be.
H 3 P O 4 + MgSO 4 --> Mg(HSO4)2 + Mg(H2PO 4)2

W hether hea t effects this or not I don't know. But unlikely.
c.Tech D e c e m ber 10th, 2006, 12:37 AM

D i d y o u m e a n M g S O 4 + H2O2 --> MgO + H2SO 4.
Y o u s h o u l d k n o w t h e b a s i c a c i d / b a s e c h e m istry before you start giving advice on reactions to try.
Acids react with metal oxides to form water and a salt, MgO + H2SO4 -> MgSO4 + H2O an d acids also react with carbonates,
m etals, hydrogen carbonates, sulfides and sulfites.
BTW , where did one atom o f o x y g e n g o f r o m the first half of your reactio n? On th e first half you have 6 oxygen atom s but o n
t h e s e c o n d h alf you have just 5.

a n d I m provised C hemistry > Tetrahydrofuran via dehydration of 1,4-butanediol
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immortal02 S e p t e m b e r 7 th, 2006, 02:59 PM

i have been working on project related to Tetrahydrofuran,
i came across various m anufacturing routes through encyclopedias, patents and books.........as in i found most simple process
for manufacturing THF by dehydration of 1,4-butanediol though BDO is difficult to obtain.........
i got an idea through one of the recent patents that dehydration of BDo and subsequent cyclization in presence of Alum inium
Oxide as a catalyst gives THF with high percentage yield and alm ost 100% conversion along with high selectivity.
T h e r m o d y n a m ic conditions are around 150 deg ree C an d pressu re approx 1 bar.
i have quite a few doubts regarding its reaction m echanism.......and catalysts activity and deactivation.........
c a n a n y o n e p l e a s e g i v e m e s o m e guidance for above issues and certain other similar issues.........
Cobalt.45 S e p t e m b e r 8 th, 2006, 02:51 AM

c a n a n y o n e p l e a s e g i v e m e s o m e guidance for above issues and certain other similar issues.........
I s u s p e c t y o u r g o n n a g e t s o m e guidance, alright. I'll go now, I don't want to get any on m e.
c.Tech S e p t e m b e r 8 th, 2006, 03:01 AM

INGSOC NEW SPEAK DICTIONARY;
*Definition*
S P O O NFEEDING
A d e m a n d ( s o m e t i m es phrased as a request) for highly detailed procedures and current sources of m aterials, for a task or
process that could otherwise b e found if the user could be bothered to UTFSE, rather than asking long-time m e m b e r s t o
s p o o n f e e d t h e i n f o r m ation to the zero-post n00b like a coddled infant.
It's a bannable offence here
nbk2000 S e p t e m b e r 8 th, 2006, 09:27 AM

First of all, m a n k i n d h a s b e e n chasing after the illusionary goal of imm ortality sin ce the beginning of time, and has yet to
achieve it.
So im mortal is dead. :)
Then there's the decided lack of gram m ar skills, indicating a lazy and disorganized m i n d , i n c a p a b l e o f u n d e r s t a n d i n g a n y
knowledge that m ay be im parted to it by the generousity of the existing mem bership.
So the question is m oot.
And as for m a k i n g T H F b y b r e a k i n g d o wn 1,4-Butanediol...:rolleyes:
Talk s about doing things bass-ackwards!
THF is very com mon in PVC glues, in large quantities. 1,4-B, on the otherhand, is very difficult to find (in the US) because of
it's use in GHB m anufacture or substitution.
T h e r e a r e p e ople who've figured out how to ma ke 1,4-B from THF, but why the fuck would you want to destroy it to m a k e a
comm on solvent? :confused:
Anyways, banned for i/I, Spoo n f e e d i n g , a n d g e neral stupidity. :p
megalomania S e p t e m b e r 8 th, 2006, 09:54 PM

Talk about doing that the hard way... Dosn't anyone read m y stuff?
http://www.roguesci.org/theforum/chemistry-related/3258-theory-otc-tetrahydrofuran-thf-synthesis.htm l?
high light=tetrahydrofuran

a n d I m provised C hemistry > N-m ethylpyridine synthesis
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Abigail S e p t e m b e r 7 th, 2006, 03:53 PM

I k n o w s o m e of m e g a s r e c i p e s o f e x p l o s i v e s u s e s p y r i d i n e . I h a v e c h o s e n a detail of a side reaction of a reported method wich
u s e s a l u m i n i u m chloride as a substituent to yield N-m ethylpyridine.
Place 2 m ol of m etha n o l i n a 1 0 0 0 m l b e a k e r a n d 1 . 4 m o l o f a n hydrous alum iniu m chloride is stirred to the methanol. Prepare
a s e cond solution of 2 mol pyridine and 4 mol of m ethylene chloride in a 5 0 0 m l b e a k e r .
The pyridine/methylene chloride solution is stirred to the methanol/aluminium chloride m ixture and the flask is sealed with
glass wool.
The flask is stirred for one day at 50 C, cooled and 400 ml of 1 0 % hydrochloric acid is stirred to the solution and the crystals
of N-m ethylp yridine should be precipate from the solution.
D o e s a n y o n e k n o w s o m e a b o u t N - m ethylpyridine ?
nbk2000 S e p t e m b e r 8 th, 2006, 10:13 AM

This wouldn't be, by any chance, intended for conversion into a fentanyl or other synthetic opiate n ow, would it?
meyer25 S e p t e m b e r 8 th, 2006, 07:17 PM

W hat are you writing about wh en you mention N-methylpyridine? AFAIK, there are only N-methylpyridinium salts. Did you me a n
N-methylpiperidine?
n b k : I ' m n o t a v a r e o f a n y r e a g e n t , a b l e t o o x i d i z e N - s u bstitued piperidine into N-R-piperidine-4-one. I rather doubt there are

s o m e such.
A g o o d m ate rial to start with would be 4-hydroxypyridine.
Chris The Great S e p t e m b e r 8 th, 2006, 07:34 PM

It's pyridine, not pipe r i d i n e / o n e n e e d e d for fen tanyl. Pyridine is an aromatic system and is very different than the p iperidine s
needed for fentanyls. I could be possible to reduce to p iperidine with catalytic hydrogenation but why bother when piperidine is
readily available from chem ical suppliers? Pyrid i n e i s n ' t a n y e a s i e r t o g e t a n d h a s a t o n o f h a z m at etc on top of everything.
meyer25 S e p t e m b e r 8 th, 2006, 08:07 PM

It's pyridine, not pipe r i d i n e / o n e n e e d e d for fen tanyl. Pyridine is an aromatic system and is very different than the p iperidine s
needed for fentanyls. I could be possible to reduce to p iperidine with catalytic hydrogenation but why bother when piperidine is
readily available from chem ical suppliers? Pyrid i n e i s n ' t a n y e a s i e r t o g e t a n d h a s a t o n o f h a z m at etc on top of everything.
Yes, but you need your piperidine to be 4-substitued to be a reasonable precursor for fentanyl syn thesis. And you don't get
anything like that (N-R -piperidine-4-one, N-R-4-hydroxypiperidine, let alone N-R -4-anilido piperidin e) readily from chem ical
supplier, because the y are all listed as precursors for narcotics (for obvious reasons).
4-Hydroxypyridine instead, could be purchased. O r prep ared e.g. by sulfonation or nitratio n of pyridine-N-oxide, subsequent
alcalic hydrolysis (pyridine-N-oxide-4-sulfonic acid) and reduction, or reduction (4-nitropyridine-N-oxide to highly toxic 4-
a m inopyridin e), diazotation and hydrolysis.
Next, quarterize the 4-hydroxypyridine with 2-phenylethylchloride, reduce with metalic sodium in anhydrous ethanol, oxidate
with Jones re agent to N--Phenylethylpiperidine-4-one. Further steps are well-kno wn, I assume.
This is why to bother with pyridine if yo u wants to m ake fentanyl, unless you have access to scheduled precursors.
nbk2000 S e p t e m b e r 8 th, 2006, 10:11 PM

http://opioids.com/fe ntanyl/synthesis.htm l
W ell, while it's not directly use d for ma king fentanyl, I'm fairly certain it's not being used for explosives or poisons, which
greatly lim its what it'd be used for, considering the natu re of The Forum , eh? ;)
It just has th at drug 'feel' abo ut it.
Abigail S e p t e m b e r 9 th, 2006, 03:59 PM

Yes it is not usual for known explosives, but not to get. I would guess N-m ethylpyridine is a liquid and it dissociates in the
solution.
C5H5N-CH3(+) Cl(-) ---> C5H5N-CH3
W hat N-methylpyridin ium salt do you m ean ? You can get pyridin e-N-oxid e from p yridine b y oxidation possibly in a m ixture of
trichloroacetic acid/H2O2 but i`m not shure it is right to reduce from 4-methylpyridine-1-oxide.
Chris The Great S e p t e m b e r 1 0th, 2006, 01:04 AM

\And you don't get anything like that (N-R-pipe ridine-4-one, N-R -4-hydroxypiperidine, let alone N-R-4-anilidopiperidine) readily
from chem ical supplier, because they are all listed as precursors for narcotics (for obvious reasons).
Suspicious, yes. Im possible, no. As of yet it is not illegal.
http://www.chemicalregister.co m/N-Methyl-4-Piperidone/Suppliers/pid9584.htm
FUTI S e p t e m b e r 1 0th, 2006, 03:00 PM
Pyridine-N-oxide could be of some use for E&W comunity, it can be easie r nitrated then pyridine itself, as for N-methyl-pyridine
salt I wouldn't be so sure.
As for 4-hydroxy-pyridine there is some procedure I have with m ixed 2- and 4- substitutio n of pyridine-N-oxide with acetate
IIR C. I have thought to give it to the students but now I have to change that decision due to bloody nannies who don't know a
shit and call law enforcm ent forces when see a far-distant-cousin-of-a-precursor-of-m i s s u s e d - p h a r m aceutical.
meyer25 S e p t e m b e r 1 0th, 2006, 06:28 PM

Yes it is not usual for known explosives, but not to get. I would guess N-m ethylpyridine is a liquid and it dissociates in the
solution.
C5H5N-CH3(+) Cl(-) ---> C5H5N-CH3
I'm sorry to say that, but you have to learn some theory of orga nic chem istry. N-m ethylpyridine ex ists only in form of its salts/
catione, sim ply because of the configuration of the nitrogen atom e in pyridine heterocycle. There is e.g. N-m ethyl-1,2-
dihydropyridine, but that's not straight pyridine methylated on the N1 atom. Its em pirical form ula would be C5H6N-Me.
W hat N-methylpyridin ium salt do you m e a n ?
W hatever you wish. The m ost com m o n a r e h a l o g e n i d e s o r m ethylsulfate (mesylate).
You can get pyridine-N-oxide from pyridine by oxidation possibly in a m ixture of trichloroa cetic acid/H2O2 but i`m not shure it
is right to reduce from 4-m ethylpyridine-1-oxide.
You can get pyridine-N-oxide by oxidiation of p yridine with peracetic acid, which is used as a disinfectant. Virtually by any
percarboxylic acid, in my opinion.
W hat I don't understand is ho w you got the 4-methylpyridine-1-oxide though. No one was m entioning it in previous posts.
Anyway.
Suspicious, yes. Im possible, no. As of yet it is not illegal.
http://www.chemicalregister.co m/N-Me...rs/pid9584.htm
T h e s i m ple fact, that you find a supplier for a chem ical doesn't mean that it's not scheduled/controlled. I won't mess up with
precursors. Especially not in a country like USA, where 'Analogue Act' or som ething like that is in power.
For instance, you m ig ht find even N-benzyl-4-piperidone (the original Janssen precursor for fentanyl) suppliers:
http://www.buyersguidechem.de/AliefAus.php?pname=1 -Benzyl-4-piperid i n o n e & p n u = 1 6 0 5 7 5 7 2 0 3 5 5&cass=
But you may be sure that you can't purchase it unless you own a com pany authorised by state for m aking controlled
substances, and any identified attempt to obtain this and similar substances would draw a ttention of law enforcement organs
upon you.
cutefix S e p t e m b e r 1 0th, 2006, 11:56 PM

C h e m ically speaking never he ard from heterocyclic chemistry that N-methyl pyridine exist as a stable derivative from pyridine.
T h e r e i s 2 a n d 4 m ethyl pyridine( picoline)
Now I am not sure wh at particular pyridine products was used in m egas explosive files.... and is their a need to really
synthesize this N m ethyl derivative and be useful?
Abig ail could you point out what particular inform ation is a pyridine derivative used in explosive synthesis?
Chris The Great S e p t e m b e r 1 1th, 2006, 04:58 PM

W ell, I never said it wasn't suspicious. In Canada it isn't even on a list, for the US I am unsure if it is listed as a precursor. But
it isn't illegal, I know that for sure, and if you a re willing to risk a bit of piggy attention it is possible to order it and have it
shipped over here. If you happen to have a fake mailbox, then there isn't any danger at all, except it might be seized by
custom s.
Abigail S e p t e m b e r 1 2th, 2006, 03:03 PM

You are right, a stable N-methylpyridin e should e x i s t a s
N-methylpyridine hydrochloride and I think that is correct.
C5H5N(+)-CH3 Cl(-) It should be useful than pyridine hydrochloride as substituent, prepared from a cooled m ixture of pyridine
and HCl.
I g u e s s t h e s y n t h e s i s i s u s e f u l to get N-methylpiperidine from m ethyl glycol/alum inium ch loride and piperidine in m ethylene
chloride. You can get ethylene glycol and N-methylpiperidine in one step by distillation of their boiling points.
I think it looks interested ! I don`t want post crap but the theory of `bring up a useful explosive from browsing a index` is n ot
help ful.
I l i k e m e g a s r e c i p e s , a c o u p l e o f g o o d stuff to inspire a n y o n e t o b r i n g u s e f u l i d e a s t h e f o r u m .
I will thinking a while about pyridine and som e g o o d e x p l o s i v e s .

cutefix: What do you mean ?
Now I am not sure wh at particular pyridine products was used in m e g a s e x p l o s i v e f i l e s . . . .
I have listet som e e x plosive compounds within pyridine which yo u can m a k e f r o m m egas recipes, i would think it is correct.
4,4,6,6-tetranitro-2 ,2bipyridine
C10H4N6O 8
3 3 6 , 1 7 5 g / m ol
2,3,4,6-tetranitropyridine
C5HN5O 8
2 5 9 , 0 9 g / m ol
4-amino-2,6-dinitropyridine
C5H4N3O 4
1 7 0 , 1 0 g / m ol
2,3,4,5,6-pentanitrop yridine
C5N6O 1 0
3 0 4 , 0 8 g / m ol
3,3'-diam ino-2,2',4,4',6,6'- hexanitrob ipyridine

C10H8N8O 8
3 6 8 , 2 2 g / m ol
cutefix S e p t e m b e r 1 4th, 2006, 04:55 PM

Yes. casually looking ..pyridine is one of the co mponent but are you sure its exactly N-Methyl pyridine as the precursor?
nbk2000 S e p t e m b e r 1 4th, 2006, 06:15 PM

Y o u c a n m a k e e x p l o s i v e s f r o m m i l k s u g a r s , b u t that do esn't m ake it worth doing.
Are the pyridine based explosives worth the effort and risk of ob taining a m eth precursor?
meyer25 S e p t e m b e r 1 4th, 2006, 08:32 PM

Are the pyridine based explosives worth the effort and risk of ob taining a m eth precursor?
As for trinitro pyridine (TNPy) a nd trinitropyridine-N-oxide (TNPyOX), they are "potent explosives" (Meyer, Khler, Hom burg:
Explosives, ISBN 3-527-30267-0) with det. velo cities of 7.470 m/s at 1,66g/cm for TNPy and 7.770 m/s at 1,72 g/cm for
T N P y O X , b u t t h e y a r e t o o e x p e n s i v e a n d c o m plicated to synthetise (direct nitration to trinitroderivatives is not possible by any
r e a s o n a b l e r e a g e n t s ) , i f y o u c a n m uch m ore easily synthetise PETN, RDX or just picric acid , there's no reason to deal with these
pyridines.
Maybe it wou ld be of interest to see how powerful TNPy-perchlorate is, bu t that's still nothing for wide use.

direct nitration to trinitroderivatives is not possible by any reasonable reagents
W hy not possible ? I know you have m any com p o u n d s t o m a k e a n e x p l o s i v e . I f t h e y e x p e n s i v e a n d c o m plicated to synthetise

or not, The question is, a useful explosive or not and what will you do with it.
T h i s s e e m s i n t e r e s t e d , 3 , 5 - d i a m ino-2,4,6-trinitropyridin e, DATNPy, C5H4N4O 6
Tell me, why deal with pyridines ?

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > quick, how can I get
a hold of some cesium :D
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Sausagemit September 19th, 2006, 06:20 AM

I did not realize that Cs and Rb are this reactive with water!!
http://www.youtube.com/watch?v=G9bTYM_W_-g&mode=related&search=
c.Tech September 19th, 2006, 06:49 AM

K, Na, Cs and Rb are reactive with water because they occur under the same group in the periodic table, therefore they have similar properties e.g. low melting points, oxide
easily, reactive with water.
Gives me an idea for an improvised grenade. Using a large amount of Rb and water, have a piercing instrument to break a water balloon and bang.
At the same time mixing H2O2 and MnO2 with an outside ignition source would have interesting effects.
Specially designed glass vial which can dissolve in water with an argon atmosphere? Never heard of that.
They said that they wouldn t let them have francium.
But web elements states "Francium is found in uranium minerals, and can be made artificially by bombarding thorium with protons. It is the most unstable of the first 101
elements. The longest lived isotope, 223Fr, a daughter of 227Ac, has a half-life of 22 minutes."
So even if it could be made, by the time it was transported to the site it probably would have changed into a different element.
Jacks Complete September 19th, 2006, 06:31 PM

From memory (I've not done chemicals buying in years) Lithium in cold water and Calcium in hot water are about the same reactivity. Lots of bubbles, no flames.
Sodium is reactive with even air moisture in the cold. Get it molten first for big bangs, by adding a tiny drop of water. The heat liberated will get rid of the protective oil, and
cause it to melt! It also floats on water due to the gases generating thrust/uplift. Sink it (fast) with your air rifle for fireworks, or wrap it carefully in something heavy like wire,
then throw it in the lake. I found twigs to be cheap and strong enough to push into the sodium blocks, rather than messing around.
Lithium is (was) ten times more expensive than Sodium, and 5 more than Calcium. Potassium is (was) ten times more than Sodium, and Rubidium was the same price for 1/
10th of the amount (yes, 100 times more by mass, even less by volume.) I never could source any Caesium, but I guess another factor of ten would get you there. Francium
is one of the most expensive elements in the world to produce. It would also be insanely reactive. And with a halflife of at most 22 minutes, you'd better only need a tiny
amount.
Up-to-date prices:
10g Li : 30
100g Na : 19 (high grade under oil)
1Kg Na : 12 (lower grade foil wrapped)
10g K : 10
1g Rb : 13
1g Cs : 52
It has been estimated that there might be from 340 to 550 grams of francium in the earth's crust at any one time, making it the second rarest element in the crust, next to
astatine. If you get a few grams, throw them swiftly into the nearest deep water and *film it*!
borax September 19th, 2006, 10:16 PM

I was under the impression that francium had a really really short half-life, the amount in the crust is probably constantly being refreshed.
Sausagemit September 20th, 2006, 12:20 PM

Gives me an idea for an improvised grenade. Using a large amount of Rb and water, have a piercing instrument to break a water balloon and bang.
I've often thought of ways to make an improvised and somewhat dangerous explosive out of Na, water, and kerosene. The idea behind it would be to fill a jug part of the way
with water and part of the way with kerosene. Seeing as how kerosene is lighter than water it will float. Then you suspend the sodium in the kerosene either by a stick or
string (a string being stuck in the threads of the cap would be preferable making it much harder to disarm). Tip it on it's side and BOOM!!
I don't know if the sodium will produce enough flaming debris to ignite the kerosene but that would be sweet if it did. If it did than a little bit of water with a lot of kerosene
would be preferable.
Hirudinea September 20th, 2006, 09:24 PM

I've always thought that sodium would be a good anti-tamper device for a bomb, simply wrap a plastic bag of sodium around the bomb (small bomb of course) and when they
use a water disrupture on it, well it would be an interesting suprise.
lucas September 20th, 2006, 10:53 PM

Glass is made from silica and soda is added to lower the melting point, but makes it soluble in water, so lime is used to make it insoluble. So soluble glass is made from silica
and soda.
nbk2000 September 21st, 2006, 08:17 AM

You wouldn't be referring to 'Water Glass', now would you? That's also known as Sodium Silicate.
And how the fuck does this relate to Cesium or such?
lucas September 21st, 2006, 08:36 PM

It's what those samples of cesium and rubidium in the video were contained in.
c.Tech said "Specially designed glass vial which can dissolve in water with an argon atmosphere? Never heard of that."
So I replied about the glass.
nbk2000 September 22nd, 2006, 03:24 AM

Why not encase it in PolyVinyl Alcohol? PVA is inert to most non-polar chemicals, can be formed under heat and pressure into very robust forms, and would dissolve in water. :)
a_bab September 22nd, 2006, 03:54 AM

That film and the Brainiac show in general is "spiced up". All, but all the explosions are fake; they add loads of gasoline to make the hollywood-like fireballs.
As about this small clip, there is no such thing like "our special designed glass that disolves in water". Cs and Rb are packed in glass vials, and they can't explode like an
"underwater mine" or whatever they stated; not in less then a gram quantities they used anyway.
Have a look at the bath tubs: they have wires so that means charges etc.
I'm wondering if they don't do that to intoxicate the people, like nbk2000 saw once in a book about bombs making, where they asked to "dump a mix of potassium chlorate,
sulphur and steel balls into a pipebomb, screw the cap and shake it to mix the contents"
Think before you believe. You may know enough to understand what's crap.
c.Tech September 22nd, 2006, 07:28 AM

Have a look at the bath tubs: they have wires so that means charges etc.
Thanks for pointing that out, I wouldnt have picked that up in a million years.
I thought they would have been smart enough to not show the wires by filming from a different angle.
Three more things.

1. If it was so dangerous that one guy had to run into the caravan wearing the face shield looking through a hole in the window, why was the other guy wearing no safety
equipment from nearly the same distance away.
2. If it was so dangerous that one guy had to run into the caravan wearing the face shield looking through a hole in the window, If anything did happen the window might have
killed him. Think of shattered glass falling around your neck.
3. Even if it could explode like that there was no flames present. The reaction of the elements with water causes them to form a hydroxide and hydrogen gas, the hydrogen
gas would then ignite to cause a explosion, an example (http://www.theodoregray.com/PeriodicTable/Stories/011.2/index.html) from the thread sodium party started by
a_bab, thanks :).
E.g. with potassium. 2K + 2H2O -> 2KOH + H2
And when were there any flames present from the burning of hydrogen?
lucas September 22nd, 2006, 08:19 AM

I have actually seen sodium, which normally fizzes on water with flame, explode after being dropped into water. Live, not on film. It was definately sodium causing an
explosion.
c.Tech September 22nd, 2006, 08:23 AM

I have also seen sodium and potassium live on film, worth to watch. Probably be even more fun to be chucking chunks in water.
It was definately sodium causing an explosion.

What was? the link I provided from another thread of the Cs and Rb?
Lewis September 24th, 2006, 06:19 PM

I think it's best not to think too hard about shows like Myth Busters and Brainiac. They're anything but scientific, and really just lame showbiz types making fireballs on TV.

The wires might not have been to explosive charges, but a mechanical device to break the vial open.
I may be giving them too much benefit of the doubt here...
Sausagemit September 26th, 2006, 12:06 AM

I wouldn't exactly call this (http://www.youtube.com/watch?v=Dy1b4k4nbMQ) lame if I were you. ;)
They used many many bags of ANFO for that explosion.

Read my post above. Sodium metal can easily be made to explode, with nothing more than water.
Sausagemit September 27th, 2006, 10:09 PM

Here is a real Cs water reaction. Keep in mind that this is 5 times as much Cs as what was supposedly dropped into the tub on the brainiac clip.
http://www.theodoregray.com/PeriodicTable/AlkaliBangs/055_Cs_underwater.html
I'm gonna go ahead and call shenanigans on myself for posting such a grosely misinterpeted video. :D
Lewis September 27th, 2006, 10:46 PM

I wouldn't exactly call this (http://www.youtube.com/watch?v=Dy1b4k4nbMQ) lame if I were you. ;)
They used many many bags of ANFO for that explosion.
That's exactly my point. If I wanted to see significant quantities of HE detonated in a field, I'd just watch videoes of F-18s bombing the middle east. Myth busters is supposed
to give real, useable information, but all they've really proven in that episode was that explosives will destroy a truck.
shannon dove September 29th, 2006, 02:51 PM

If the water/sodium reaction is not violent enuogh for you, then try dropping a peice of sodium metal in hydrochloric acid but not concentrated acid as it may need some water
(I'm not sure about that).
The reaction to form sodium chloride should release a lot more heat than the reaction to form sodium hydroxide ,to enhance it even more use hot hydrochloric acid/water.
Also do not use any more acid water than neccesary because extra water/acid just pulls in a lot of heat and cools the reaction down.
Do not use five gallons of acid/water for a peice of sodium the size of a penny.

If you want a full on explosion from your 1cm cube of sodium, I'll repeat myself, just this once.
Add a small drop of water to your sodium block. It will melt. Stand well back and throw a bucket of water onto it. Bang!
a_bab September 30th, 2006, 04:40 PM

nbk, with all due respect but having wires for a "crushing system" and stating the use of a "a special designed glass that dissolves in water" and then running like hell after
dropping the vial and the unbelievable explosion that follows just doesn't fit. I didn't buy that from the moment I saw the movie; and I must confess I did play alot with Na and
K.
Here is the real story: http://www.theodoregray.com/PeriodicTable/AlkaliBangs/

I was trying to give them the benefit of the doubt, but it was obviously misgiven.
Thank god for TV, huh?
sanguine raptor October 1st, 2006, 03:44 AM

Crew members confirm that the experiments failed:
Absolutely bloody nothing. The density of caesium ensured it hit the bottom of the bath like a lead weight. The volume of water then drowned out the thermal shock. They
could not go home empty-handed. So they rigged a bomb in the bottom of the bath.
http://www.badscience.net/?p=270
shannon dove October 2nd, 2006, 07:14 PM

While we are on the subject of alkali metals I should mention in the book "the chemistry of powder and explosives" by Teny Davis, he talks about explosions from an alloy of
pottasium and sodium contacting a halogenated hydrocarbon such as tetrachloroethylene or something like that.
USE
He says it explodes with flash that is visible in direct sunlight. What about grinding the sodium into a course powder?
PARAGRAPHS!
And I know that grinding up sodium is not easy, it would have to be protected from air as a powder would spoil very quickly from humidity and carbon dioxide and oxygen in
the air, but if someone did have sodium powder, how much better would that work?
NBK
ShadowMyGeekSpace November 7th, 2006, 04:08 AM

http://www.badscience.net/?p=270
shannon dove November 8th, 2006, 07:28 PM

What about using sodium metal powder in these mixtures:
sodium mixed with iron chloride

sodium mixed with copper chloride
sodium mixed with lead chloride
The sodium should reduce these metal chlorides just like aluminum will reduce iron oxide in thermite.These mixtures should generate a lot of heat like thermite does.
The advantage of using sodium instead of aluminum is that the sodium has a much lower melting point and lower boiling point, so this should make the sodium react much
faster, the same way a hydrocarbon with a low flash point will react with air much faster than a hydrocarbon with a high flash point.
These sodium mixtures should burn extremely fast in the open, and they should explode with a sharp report when confined, much like good flash powder.
These mixtures probably do not generate as much heat as aluminum/pottasium chlorate flash powder, but they should still explode very good.
Does anybody think these mixtures would work?
Yes, I know these mixtures are probably dangerous, much like pottasium chlorate/sulfur mixtures.
FUTI November 10th, 2006, 03:52 PM

You could also try sodium and CCl4. Every couple years by government regulations they send "new" guys from firedepartment to "teach" US (?!) a fire protection etc. We
always piss ourself when they say the famous sentence "for fire you need three things combustible material, energy source and oxygen" - when we aren't bored to death we
enjoy to kick their ass with silly billy questions :D. But we should continue the science molestation rant against Braniac continue.
shannon dove November 13th, 2006, 07:04 PM

I did some calculating about the heat given off by iron chloride/sodium mixtures, and I am very dissapointed that the calories per gram is less than that of iron oxide/aluminum
thermite, and it is way less than pottasium chlorate/aluminum flash powder.
Here are some measurments of heat given off by different mixtures:
iron oxide/aluminum 0.95 kilocalories per gram.

copper oxide/aluminum 0.98 kcal. per gram.
iron chloride/sodium 0.86 kcal. per gram.
potassium chlorate/aluminum 2.33 kcal. per gram (extremily high!!)
These calculations are assuming that the reaction goes as planned,for example, in the flash powder , all the KClO3 is converted to KCl and all the Al is converted to Al2O3.
good1 January 26th, 2007, 07:46 PM

Talking of Cesium (Used in atomic clocks) and other radioisotopes, read the book of this posts title, it's a fantastic book and worth the time.
It has some simple ideas for obtaining radioactive elements from everyday items.
drunkenpanda March 8th, 2007, 12:38 AM

While it appears to have been staged, it was quite entertaining to see a bath tub blown in half. Besides, don't they claim the show to be "science abuse?" These shows are
meant primarily for entertainment, and need to be viewed as such. As nbk said: Thank God for good TV.
xenon24 March 18th, 2007, 11:29 PM

If you really want a large explosion, try using a large block of sodium. You can cut it into smaller cubes and release it as one large charge, or simply use the intact block.
Because sodium hangs around for just the right amount of time before it generates enough heat to ignite the hydrogen gas that it produces when it reacts with water, it makes
the best explosions. Potassium is a bit faster and tends to make explosions that violently pop, whereas sodium makes one large bang. I haven't tried caesium (too expensive)
but rubidium is actually pathetic compared to sodium...it just reacts too fast.
Besides...sodium is relatively cheap to purchase/make.
Meawoppl March 21st, 2007, 06:33 PM

There are LOTS of water soluble glass compositions:
http://en.wikipedia.org/wiki/Sodium_silicate
http://en.wikipedia.org/wiki/Potassium_silicate
http://www.springerlink.com/content/j88577037888771x/
All are high temp melt processed. (aka not practical for most of us)
Much better is sodium tetraborate:

http://en.wikipedia.org/wiki/Sodium_silicate
You can process that as low (snickers) as 800-900 C. A bit beyond the typical home capability.
You would have a hard time encasing a low m.p. solid metal in something that hot. Also notably "soluble" is a rather relative term. It takes days to soak off of Pt crucibles we
use in a glass coloring lab.
Lastly, it would be far more practicable to use water soluble polymers or something like wax paper with a small hole:
Small leak -> some heat ->melts wax ->more heat
In terms of chemical potential for destruction, it is probably on the order of dry ice bombs. Nothing impressive.
sirthomasthegreat May 10th, 2007, 10:17 PM

Here is a real Cs water reaction. Keep in mind that this is 5 times as much Cs as what was supposedly dropped into the tub on the brainiac clip.
http://www.theodoregray.com/PeriodicTable/AlkaliBangs/055_Cs_underwater.html
I'm gonna go ahead and call shenanigans on myself for posting such a grosely misinterpeted video. :D
You realize that was sodium not Cs right? The title says sodium, and second of all I have done a 0.5g Cs explosion and it shattered the earlenmyer flask. It has to be in a glass
vial to start because it oxidizes so fast, it looks really cool when it oxidizes too because it looks like it is melting really fast.
Cindor May 29th, 2007, 01:18 PM

Has anyone tried Sodium and Hydrogen Peroxide ?
It will release Oxygen when the H2O2 decompose, generating more gases per mol, and Oxygen will make Hydrogen burn faster (no need to use O2 from air)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Condensation of
nitromethane
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sprocket September 22nd, 2006, 09:13 PM

This one has been nagging me for a while. It seems well-known that nitromethane forms nitroacetaldoxime (methazonic acid) in basic aqueous solution, but never have I seen
a mechanism for it. In various papers they mention a certain mechanism being similiar to that of methazonic acid, but no references are given (Ex: http://www.iupac.org/
publications/pac/1989/pdf/6107x1217.pdf).
There is also a short article about nitroacetaldoxime in PATR 2700 on page A16 with references. However I have been unable to get hold of those papers. It also seems our
dear Federoff either made a typo or forgot to enter one of the references in the table, because there are four references in the text and only three in the table.
Refs: 1) Beil 1,627 2)O. Schultze, Ber 29, 2289(1896) 3) W. R. Dunstan & E. Goulding, Ber 42, 2030-1(1909)
It is clear that nitromethane reacts with hydroxides to form the enolate (nitronate) H2C=NO2-. This must be the first step in the reaction, followed by a condensation of some
sort (this is what bugs me) and finally an E1cB elimination. The product here should be the conjugate base of methazonic acid, which must then be acidified to obtain the actual
nitroacetaldoxime.
Now to the weird part. I prepared a small batch of nitroacetaldoxime sodium salt by treating nitromethane with aqueous sodium hydroxide following this procedure:
To a 250 ml Erlenmeyer flask 25 ml nitromethane (technical grade) and 25 ml 5M NaOH solution was added. The reaction progressed slowly at first; the liquids were in
separate phases. After about 30 seconds of swirling the flask the liquids had turned red and completely mixed with significant evolution of heat. The flask was then swirled in a
stream of 20C water to control the temperature. After about 2 minutes the solution instantly solidified into a brown moist mass. Swirling then stopped and the reaction vessel
was allowed to cool to RT. The brown precipitate was transferred to a filter paper and washed with 50 ml cold distilled water. After 12 hours of drying a small amount of the
sample was dissolved in D2O and the 1H-NMR chemical shifts were determined in a Bruker 500 MHz NMR.
Results: 1H NMR (500 MHz, D2O) ppm 6.74 (d, J = 8.93 Hz), 7.13 (d, J = 8.84 Hz), 7.62 (d, J = 8.84 Hz), 8.10 (d, J = 8.93 Hz)
Clearly this is not nitroacetaldoxime, seeing as it has four doublets. If this was nitroacetaldoxime there would be two singlet peaks and one doublet. I realize now that I forgot
to acidify the solution, but I should still have one single and one doublet peak if it was the nitroacetaldoxime sodium salt I obtained. What happened?
If the nitroacetaldoxime could form an enolate that would have two doublet peaks, but is this possible?
Attached is the NMR-spectrum.
hereno September 23rd, 2006, 02:40 AM

Grab the attachments in this thread:
http://www.sciencemadness.org/talk/viewthread.php?tid=5309#pid60474
Attachment 3rd post down contains a number of old articles detailing the synthesis and extraction of NM condensation products.
Depending on conditions you'll get methazonic acid, a condensation product of methazonic acid (the red colored stuff) or nitroacetic acid.
What do you intend to do with methazonic acid?
nbk2000 September 23rd, 2006, 06:22 AM

Depending on conditions you'll get methazonic acid, a condensation product of methazonic acid (the red colored stuff) or nitroacetic acid.
In this thread (http://www.roguesci.org/theforum/other-explosives/5700-tris-nitromethyl-amin-way-nta.html), Nitrilotriacetic Acid is used in a process to make Tris-Nitromethyl

Amine (whatever that is used for).
Would Nitroacetic Acid be useful for making the Nitrilotriacetic Acid used in the linked thread?
sprocket September 23rd, 2006, 07:07 PM

Thanks for the replies.
I searched SM using the keywords 'methazonic' and 'nitroacetaldoxime', but unfortunately they didn't appear in the thread hereno linked to. The articles in that archive were
exactly what I was looking for!
I believe my product was the disodium salt of methazonic acid with the structure Na.O-N=CH-CH=NO2.Na (another nitronate!). Taking E/Z-isomery into account, this would
explain all peaks in the NMR-spectrum. Interesting to note is how pure the product is despite the crude procedure and few purification steps.
I'm synthesizing these substances to still my curiosity, mainly regarding their explosive properties. While evaporating some solvent from a solution containing disodium
methazonate I got a sneak preview; a small amount splashed onto a hot plate, producing a sharp bang. Later I will test if the substance can be initiated by means of a small
detonator, or maybe even used as a primary explosive if somewhat confined. Perhaps it can be used to sensitize secondary high explosives as well.
My only concern so far is its storage stability, though some tests of friction and shock stability might be useful.

a n d I m provised C hemistry > Alpha-Hydrogen Chlorination
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I`ve converted som ething from Megas sites, chlorination of the alpha hydrogen in precence of red phosphorus. I would guess
it can work with a alkohol instead a carboxylic acid. I belive you can get the upper m e n t i o n e d c o m p o u n d s b y this m e t h o d .
4-Chloro-1-Butanol:
C 4 H 1 0 O , 108,56 g/m ol, bp ~50C
183 ml 1-butanol is mixed with 10 g red phosphorus in a 500 ml glass flask, connect the flask to a claisen and a re f l u x
condenser. C onnect a therm o m e t e r t o t h e a d a p t e r a n d a g l a s s t u b e t o t h e b o t t o m o f t h e m ixture. Put the apparatus to a
sunny place that the flask can receive as much sunlight as possible. After that, a regular current of dryed chlorine is
bubbled through the flask for 12 hours. You can use a chlorine generator and two drying tubes with concentrated H2 SO4 to dry
the chlorine. To increase the yield the flask is short hea ted to 45 C at the end of the reaction. Than the crude 4-chloro-1-
butanol is rem oved from mixture by distillation above 5 0 C. The distilate contains som ewhat wate r and rem ainders of di- and
trichloro-1-butanol. Maybe it will work when a few gramm o f a a n hydrous substance is added to the distilate bevor it purifyed by
distillation.
1,4-Dichlorobutane:
C 4 H 8 C l2, 127,01 g/m ol, bp: ~155 C
1,4-dichlorobutane can be pre pared exactly as 4-chloro-1-butanol by 209 m l 1-ch l o r o b u t a n e a n d 1 0 g r e d p h o s p h o r u s .
I don`t know i tinking correct, you can get a alkohol when a solu tion of potassium or sodium hydroxide
is stirred to the chlorinated substance, the m ixture is heated for a while and the crude stuff is than distilled.
1-Butanol:
C 4 H 1 0 O , 74,12 g/mo l, bp ~116-117 C
May be it can prepared from 1-chlorobutane an d 1 mol dilute po tassium hydroxid e solutio n.
1,4-Butanediol:
C 4 H 1 0 O 2, 90,12 g/m ol, bp: ~230 C
1 mol of 4-chloro-1-b utanol and 2 m o l p o t a s s i u m hydroxide solution.
D o e s a n y o n e h a v e i n f o s t o t h e c o n d i t i o n s t o t h e p r o c e s s ? W hen this is correct, you can get easy 1 ,4-Butan ediol from 1 m ol of
d i c h l o r o b u t a n e a n d 2 m o l o f p o t a s s i u m hydroxide solution.

Now there is a topic near and dear to my heart, but first I m ust ask: how can you be certain you will get 4-chlorobutanol? You
have adapted the procedure for chloroacetic acid. In theory I can see where you are going with this, but you are not replacing
the alpha hydrogen with this reaction. The alpha hydrog en is on the C2, that is to say the carbon right next to the carbon
attached to the hydro xyl. W hat you are reacting is the gamm a h ydrogen when using butanol. The m e c h a n i s m for th is reaction
would also be quite different owing to the fact you do not have a carbonyl and its inherent stability.
I would conjecture all you will end up with is butyl chloride. Unless you are deriving this procedure from som e sort of published
literature source, in which case I will defer to the published procedure. Th at source would be?

Yes that`s right, the m echanism is quite different to the chloroacetic acid and yield a sligh t a m o u n t o f s o m e d e r i v a t e s b u t t h e
phosphorus will help that only one hydrogen is chlorinated. I would guess the procedure will work correct.
I h a v e f o u n d a process on a kind of chem supplier page many years ago, benzyl chloride in KOH/H2O will yield benzylalkohol.
M a y i s a s k a q u e s t i o n , d o y o u can found a refe rence to the men tioned procedure ?

a n d I m provised C hemistry > Phloroglucinol Synthesis
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Marck October 14th , 2 0 0 6 , 0 4 : 1 1 P M

I searched around for a while to find a proper method to obtain phloroglucinol (1,3,5-trihydroxiben zene) but i can't found
s o m ewhat to a useful synthesis. The stuff is se lls for around $20 per pound from chemical suppliers. I was thinking about this
f o r s o m e t i m e a n d i h a v e c o m piled this short synthesis which contains two steps. If you have 1,3,5 -trichlorobenzene, you can
prepare 1,3,5-triam in o b e n z e n e and then 1,3,5-trihydroxybenzene from that. You need a littel am m o n i a e q u i p m ent.
++++++++++
Step 1: Preparation o f 1,3,5-triam i n o b e n z e n e , C 6 H 3 ( N H 3 ) 3

P r e p a r e a s o l u t i o n o f 1 4 6 m l anhydrou s ethyl a l k o h o l a n d 1 0 g o f p o w d e r e d
1,3,5-trichlorobenzene in a 1000 m L round-bottom e d f l a s k . C o o l the flask
to 10 C and slowly bubble anhydrous am m onia into the solution for 8-10
m inutes. After that, the solution is gently heated to 78 degree C and careful reflu x e d f o r 3 0 m i n u t e s . T h e n t h e e t h y l a l k o h o l i s
e v a p o r a t e d a n d t h e o b t a i n e d m ass is washed with 3 - 5% hydrochloric acid. The mixture is stirred for a while and the solid
m ass is colle cted by evaporating the liquid. The collecte d pieces are grinded with a m otar to a fine powder to use the crystals in
the next step. To purify the crystals, dissolve them in enough carbon tetrachloride, the solution is filtered, the liqiud is
evaporated and the purifyed product is then collected.
Y i e l d i s a b o u t 6,7 g.
Step 2: Preparation o f 1,3,5-trihydroxybenzene, C6H3(OH)3

Place 28,1 m L of 96-100% sulfuric acid to a 500 mL rou nd-botto med flask and careful dilute the acid with 232 m L of water.
P r e p a r e a s e c o n d s o l u t i o n o f 1 3 , 1 g o f s o d i u m nitrite in 62 m L water in a 100 mL beaker and the obtained product prepared
above is stirred to the dilute sulfuric acid. Slowly the second m ixture is combined to the first and the flask is gently heated to
5 0 d e g r e e C f o r 6 0 m inutes. The solution is then concetrated m uch as possible to evaporate the water. Add enough sodium
chloride until it becom es saturated, extract the solution several tim es with ethyl ether, com bine the extracts and filter the
s o l u t i o n . A d d a s m a l l a m o u n t o f s o d i u m sulfate to the solution and let it stand fo r a few h ours. Filter the solution again and
the ethyl ether is then evaporated. The pieces are collected and dissolved in enough anhydrous ethyl alkohol, the solution is
filtered and the ethyl alkohol is evaporated to collect the pices o f anhydrous phloroglucino l.
Y i e l d i s a b o u t 2 g.
Anyone that have something useful to this, please comm ent on this. I have a
variety of nice suggestions to similar com p o u n d s a n d i h o p e i c a me up with it
it the next few days.
nbk2000 October 14th , 2 0 0 6 , 0 7 : 2 7 P M

Phlo roglucinol.
This phloroglucinol ca n serve as the starting m aterial for synthesis of 1,3 ,5-trinitro-2,4,6-triam inob enzene (TATB), which is a n
im portant thermally stable energetic m aterial u sed by the U.S. military. TATB possesses a higher density and deton ation
velocity relative to TNT. TATB is characterized by reduced shock sensitivity and increased thermal stability relative to the high
explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).
The Draths route to p hloroglucinol stands in stark contrast to the current manufacture of p hloroglucinol from 2,4,6-
trinitrotoluene (TNT) by a route involving an oxidation u tilizing Na2C r2O7 . B e y o n d t h e e x p losion hazard, environmentally
p r o b l e m atic and carcinogenic chrom ates are generated along with other salts as waste streams during synthesis of
phlo roglucinol from TNT.
Beyond synthesis of TATB, phloroglucinol can be exploited for th e synthe sis of resorcinol. Draths has developed a high-yielding
route to reso rcinol involving catalytic hydrogenation of p hloroglucinol. Resorcinol is widely used in novalac resins, which are
u s e d i n a d h e s i v e a p p lications ranging from plywood to tires. There may also be com mercial opportunities for replacing
reso rcinol with phloroglucinol in novolac resins. Phloroglucinol-ba sed novolac resins would likely have a m ore highly cross-
linked structure and have been predicted to cure almost instantaneously at room tem pera ture.
W hen posting a synthesis, you need to state what the chem ical is useful for (and it'd better be E&W related), and whether or
not the synthesis is som ething you m ade up, or if it's som ething you got out of a journal. If you got it out of a journal, we
need to know which one, with year, volum e , a n d p a g e .
There was someone banned from here just a short while ago for doing this very sam e thing...posting a synth with no uses and
no clarification on whether it was his own synthesis or from a journal.
I've highlighted som e of your gram m a tical erro rs. Please correct them.
Also, considering how inexpen sive the chem ical is ($20/pound), it's rather silly to bother with m aking it. Though, of course, be
prepared to m ake everything yourself, since yo u never know when it'll be com e a n 'evil' chem i c a l a n d b e b a n n e d .
megalomania October 14th , 2 0 0 6 , 0 8 : 4 4 P M

Phlo roglucinol is one of the new precursor com p o u n d s o n m y website, alas the synth has been rele gated to a lower priority. I
have it listed in the synth of trinitrophloroglucin ol: http://www.roguesci.org/m e g a l o m ania/explo/trinitrophloroglucinol.html
Marck October 26th , 2 0 0 6 , 0 3 : 2 1 P M

T h i s s y n t h e s i s w a s d e v e l o p e d b y m e . S e e m s possible that it can b e p r e p a r e d f r o m 1 , 3 , 5 - t r i m e t h y l b e n z e n e . I h a v e n o s o u r c e s
which provides a sim ilar
procedure lik e that. Might such a process can be used specific to obtain
1 , 3 , 5 - t r i a m i n o b e n z e n e a n d t h is have a little im portance.
1,3,5-Triam i n o b e n z e n e :
C6H3(NH2)3
Molmass: ~123,16 g/mol
I have starte d a search over the web a nd in sig ma-aldrich to find more about
the com pound. This stuff is not to get. I don`t know the calculated quantity
of EtOH in the process is sufficient to dissolve the trichlorobenzene. May be it is p ossible to use THF, p-dioxane or acetonitrile.
Excuse m e for som e spelling errors in the topic, I will co rrect them .
megalomania October 29th , 2 0 0 6 , 1 1 : 2 0 P M

P o s s i b l e , m a ybe, but all the theory in the world is useless (and is in fact technically hypothesis) without experimentation. There
are other websites for theory
nbk2000 October 30th , 2 0 0 6 , 0 8 : 4 5 P M

I t s e e m s a b o u t e v e r y w e e k o r s o t h a t I h a v e t o b a n s o m e o n e w h o k e e p s p o s t i n g 1 + 1 c h e m istry synthesis 'procedures', after
failing to provide citations or sources. :rolleyes:
Silly rabbits, don't they ever learn?

a n d I m provised C hemistry > C ivil W a r C h e m istry
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megalomania Novem ber 14th, 2006, 06:05 PM

I was asked to start this threa d because the poster is obligated to a higher autho rity not to do so. If anyon e can assist,
plea s e d o s o
The History Channel had a recent two hour special: Civil W ar Terror. It was an insightful little piece. My wife and I co uld not
take our eyes off the televisio n. It was the type of histo ry that doesn't get taught in high school, but should be taught because
it is so gripping.
In a few history courses over tim e, I heard one instructor or another say that the Am erican C ivil W ar (1861-1865) was the first
"modern" war. They cited the m ass transportation of the railroad, the ind ustrialized state, war of economy, modernized
c o m m unications in the telegraph (the updated form of which we use today), etc. Only infrequently did any one mention
sabotage, or to an organized resistance within the Federal north, and only was there an occasional reference to the
Confederate Secret Service, or what that secret service might have been or done.
M o s t p e o p l e f o c u s o n t h e l a r g e s c a l e o f conventional op erations, with some hum an interest stories relevant to the conventional
war.
T h e t w o h o u r H i s t o r y C h a n n e l s p e c i a l l o o k e d a t s o m e o f t h e s a b o t a g e , u s e o f m o dernizing chem istry, and intrique fom e n t e d

b y t h e C o n f e derate Secret Service. It showed that hum an beings have generalized patterns -- in this case, with the advent o f
the industrialized state, the program showed the very sam e patterns we would see in the secret wa r run by the SOE in Europe
during the Second W orld War. The patterns of hum an behavior in secret warfare were the sam e. Only, in 1940, the technology
was better.
So, I dialed up my good friend, Mr. Internet. But, Mr. Internet lives in a very cluttered hou se. It is sorely difficult to sort
through millions of hits because it is related to the Ame rican Civil War. My tim e could have spent than trying to sort through
t h o s e m illion s of hits.
T h e p r o g r a m , for exa m p l e m e n t i o n e d a C o n f e d e r a t e c h emist, Richard Sears McColluh, who defected to the South from the
North in 1863. McColluh made improved "greek fire" which spontaneously com b u s t e d , s o t h a t a g e n t s c o u l d s p r e a d m a y h e m in
Northern centers of in dustrial or political gravity, such as New York City. He also apparently developed poison gases. After the
war, he settled in the South to teach chem istry at a regional college.
If, a c r o s s t h e b r o a d m e m bership of the forum , you have knowledge of Civil W ar chemistry, or of the C .S.S. and its operations,
m ight you fill us in?
M y k n o w l e d g e o f c h e m ical theory is m eager. NBK2000 m ay jum p all over that, saying this is not a teaching forum. However,
goin g through the historical developm ent of chem ical progress is not the 1+1 chem istry th a t p r o v o k e s p e o p l e . I t i s
understanding how chemistry developed, where it was in a time of historical im portance, and how it influenced that time. In this
case, it m igh t be really very interesting to look at chemistry in the C ivil W ar, if anyone has insight into that time period by way
of focused study.
If you have a chance, please see Civil War Terror on the History Channel.
In closing, here is a related link to sabotage and terror operations carried out by the Confederate Secret Service in Federal
controlled territory:
http://www.civilwarstlo uis.com /boatburners/inde x . h t m

For m y part I can say I have spent mu ch time perusing the stacks of old chemistry books and journals. A couple of years ag o I
m ade a rather startling revelation that mid 19th century chemistry was fa r more a dvanced than they ever let on in schools.
Sure they talk about the m odern discoveries of atomic theory and all of that physics crap, but I m ean the REAL chem istry: the
getting your hands dirty, actually m a k i n g c h e m i c a l s k i n d o f c h e m istry.
T h e a n c i e n t s k n e w H O W to m a k e a l m ost everything we have today, they just didnt know W HY thin gs worked the wa y they did.
The distinction is vast, but are we any better off knowing the why of things? Sure there are advantages in being able to predict
chemical behavior, the physical properties of compounds, and whether some reaction is likely to happen, but for 99% of
people, and a good many of them scientists as well, it is the results that really matter. Give m e a product that does X.
Knowing the why from the how is one of the distinguishing characteristics of a scie ntist versus a chef, say, o r a laborer that
m ixes chem icals. Still, I often lam ent that scho ols dont teach anything of practical value in chemistry. I can talk about entropy
u n t i l y o u f a l l a s l e e p f r o m b o r e d o m , b u t does it help you build a faster ca r, life saving drug, bigger TV, or cost efficient home ?
Nope.
Cindor Novem ber 21st, 2006 , 06:46 PM

I always love d what alchemists use to do... the really ch ange the world, they seed the bases for the actual chem istry... they
don't know what were they doing... but they were getting som e t h i n g .
Like ancient egypt's: calcinate d ashes + fat => soap !!! Magic ! :P hehe
Charlie Workman Novem ber 24th, 2006, 02:58 AM

That show was great. My ancestors served under Lee in the 92nd Virginia Infantry. From what I've been able to find out, greek
fire was a catch all term during the period for pretty m uch any incendiary agent. T he CSS was alledged to have used white
phosphorous dissolved in carbon disulphide as the weapon in the attacks in NY. It ignited after the C D e v a p o r a t e d . I
r e m e m ber in an old version of the movie "Incident at O wl Creek Bridge", the saboteur had a can o f com m ercial product
labe lled greek fire. It didn't ig nite when he ope ned the can, and he had a match ready to light it. I'll have to check som e o f
m y old Kurt Saxon stuff to see if his old form ularies have anything.
PS- This should not b e confused with "geek fire", which is lighting your own farts.
__________________
"To paraphrase Aristotle, life is a gas!"

-Gidget
Hirudinea January 16th , 2 0 0 7 , 0 9 : 2 1 P M

For m y part I can say I have spent mu ch time perusing the stacks of old chemistry books and journals. A couple of years ag o I
m ade a rather startling revelation that mid 19th century chemistry was fa r more a dvanced than they ever let on in schools.
Although I know this thread has been dorment for quite a while I was loo k i n g o n g o o g l e b o o k s f o r c h e m istry related books and
found several full books on chemistry (from basic, teaching, to advanced ) from the 19th century, but they were pretty old,
1829, 1853, etc... so the question I have is are these b ooks worth downloading?
nbk2000 January 16th , 2 0 0 7 , 1 0 : 5 6 P M

If th ey have any procedures for preparing reagents, I'd say yes, as the chem ist o f the tim e s m a d e c h e m icals from the m ost
basic of (now O TC) in gredients back then, since Aldrich and FedEx didn't exist, so no ordering the stuff. :p
c.Tech January 19th , 2007, 08:14 AM

so the question I have is are these books worth downloading?
I would say indeed. O lder boo ks are less likely to have all the good stuff taken out, now the chemistry that is taught is shit,
n o t h i n g a b o u t m aking chem icals or useful reactions.
If its not too much trouble could u provide the nam e s o f t h e s e b o o k s w i t h a l i n k ? T h a n k s .
Hirudinea January 19th , 2 0 0 7 , 1 0 : 0 5 P M

If its not too much trouble could u provide the nam e s o f t h e s e b o o k s w i t h a l i n k ? T h a n k s .
I j u s t s e a r c h e d g o o g l e b o o k s u s i n g t h e t e r m " c h e m istry" and the "full book" option, I haven't downloaded them yet due to
their age, he n c e m y q u e s t i o n , b u t l o o k t h e m up and see if their worth it.
tiac03 January 20th , 2007, 02:23 AM

I rem e m b e r r e a d i n g a b o u t h o w P e o p l e kept finding glass vials a long bodies of water that dated from the civil war. T hey were
determ ined to have contained Sulfuric acid and they were wondering why and what they we re for.
Ended up that they were part of a Civil war Mine. They would take a powd e r k e g a n d m odify it to have soft tin/lead bowl shaped
c o m p a r t m e n t s a l l a r o u n d t h e k e g . T h e Keg was filled with Black Powder a nd in each of the "bowls" was a Vial of acid and a
sugar+chlora te mix. W hen a boat would hit the floating mine it would deform the tin/lead bowls, crack the vial, and... well you
know the rest.
I'm still amazed by the ingenuity of people in tim es of war.
Another good show on the history channel was Som ething along the lines of "Inventions of war" Sh owed how lots of things we
use on a daily basis were all made/invented because of war.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > VP racing fuel
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DMSOnMyVeins November 18th, 2006, 02:37 AM

I was reorganizing my garage and found 5 x 15 gallon drums of VP racing fuel. It says it contains MTBE and tetraethyl lead on the labels. These were here when I purchased
the place and have no idea what to do with this stuff besides take it down to hazardous waste disposal, hate to waste chems.:(
With the price of gas being so high it would be great if I could use this in place of gas.
I just found an MSDS for this (U 4 racing fuel) it contains:

Benzene 10%
Toluene 10%
Ethylbenzene 10%
Styrene 10%
1,3-Butadiene 5%
Isoprene 10%
n-Hexane 2%
Pentane/Pentadiene 10%
Cyclopentadiene 10%
Lead 10%
That leaves the MTBE concentration being 3%
nbk2000 November 18th, 2006, 06:28 AM

Distill off all the hydrocarbons and use the concentrated TEL solution to make organo-lead sternutators, similiar to Adamsite.
Match November 20th, 2006, 10:53 AM

With the price of gas being so high it would be great if I could use this in place of gas.
Leaded oxygenated fuel such this won't work in late model vehicles which are equipped with an oxygen sensor and a catalytic converter. This type of fuel also isn't
recommended to be left in the vehicles fuel system for an extended period of time.
All that aside, Most forms of gasoline tend to have a limited shelf life, and as a complicated fuel such as it is, I can't imagine it being any good anymore if its been at your place
awhile.
If the fuel is in fact still good... You might be wise to sell it; 75 gallons would fetch quite the penny at your local motor park.
Cobalt.45 November 20th, 2006, 04:31 PM

If the fuel is in fact still good... You might be wise to sell it; 75 gallons would fetch quite the penny at your local motor park.
This really would be the way to go. If the cans are "factory" sealed, you'd get ~$2-3/gallon, easily.
Thing is, it's only 92 octane. Too bad it's not the 114 octane type.
Or, you've got lawn mower gas for life...
c.Tech November 20th, 2006, 05:46 PM

Oxygenated fuel you say? Thats giving me the impression it would rust the pistons screwing whatever you use it in.
nbk2000 November 20th, 2006, 07:50 PM

Fractionally distill it for all the hydrocarbons and the TEL content.
You've any idea how expensive gallons of TEL are, if they'll even sell it to you?
Cobalt.45 November 21st, 2006, 01:42 PM

Curious as to what the lead could be used for?
nbk2000 November 21st, 2006, 11:11 PM

Refer to my previous post about organo-lead based sternutators (vomiting/sneezing) agents, similiar to Adamsite.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Sufuric Acid turned
black!
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BigArt47 November 24th, 2006, 09:07 PM

My stock of H2SO4 has turned black!
What causes this and how do I fix it?
What is the best way to concentrate this to "fuming"?
I assume that the acid has taken in some kind of contaminate but I have been very careful not to allow any contamination so it must be either water or gas from the air or
something in the bottle or lid:mad: !
Cobalt.45 November 24th, 2006, 09:29 PM

Check the cap, under the seal.
FUTI November 25th, 2006, 04:16 PM

Did you foolishly tried rubber/wooden cork to seal the flask/bottle where you keep your stock? Manufacturers are obliged to sell the products in proper package so I assumed
you have to resort to DIY technique for some reason. Describe how do you hold your acid.
Universal November 26th, 2006, 03:51 PM

I imagine that it is carbon, sulfuric acid is a powerful dehydrating agent that will react and extract the water out of carbohydrates and rubbers.
C6H12O6 ---H2SO4---> H2O + C
Not balanced but that is probably what is happening, filter it to get the C out, if you can find a suitable filter that is.
a_bab November 27th, 2006, 11:16 AM

Due to the dust, impurities of all kind, not a proper cap (rubber for instance) the SA has the tendancy to turn black. It's a prof you've got good acid there.
A suitable, resistant filter can be a wad of clean glasswool. It'll take long to filter due to the viscosity, so a vacuum filtering system would help.
On the other hand, depending on what you need it for, it'll still work and the carbon that contaminates it wouldn't produce side reactions (in a nitration for instance).
PeterB2 December 13th, 2006, 05:57 PM

I had a sulfuric acid disaster! I was trying to condense my battery acid to a higher concentration of sulfuric acid (hopefully >90%). I used small, single tip acohol burner with
250mL florence flask on top of the burning stand with 250mL of battery acid.
I checked it periodically about every half hour. After about 1 1/2 hours, I went out to check on it (it had been moderately boiling) sulfuric acid was all over the place in about a
2 ft. radius. The acid was eating through my burner and stand leaving both severely corroded.
I was left with about 200mL of acid in the flask--the other 50mL must have partly evaporated from the boiling and partly dissipated from the explosion (dare I call it an
explosion?). The flask seems to still be intact with no cracks or holes...and it holds water without any leaks.
Both the burner and the florence flask were brand new...what could have happened?!? I had done the same proceedure just yesterday on a smaller scale with about 100mL of
battery acid leaving me with about 20mL of reasonably concentrated H2SO4 after about 4 hours using the same equipment. I am partly mad and partly flabbergasted ...
Cobalt.45 December 13th, 2006, 07:28 PM

Sounds like a case of "bump".
Often. adding inert chips of ceramic material will prevent this occurrence.
c.Tech December 13th, 2006, 11:18 PM

Something probably fell into the concentrated acid causing it to boil over, like when you add water to acid.
And peter, please use paragraph breaks.

Ceramic material? With the sulfuric acid inside the flask? I'll have to make sure to do that next time.
c. Tech, I poured the acid that remained in the flask into a beaker for inspection and there didn't seem to be an contaminates. Why would not having ceramic pieces in the
flask make it boil over the way it did?
Sorry about the paragraphs...I'll edit it. >_<
c.Tech December 14th, 2006, 04:31 AM

Maybe what fell in was boiled over or dissolved into the acid. Its only a possibility, birdshit would be the most likely to drop into my flasks because they are always
open outside.

Liquids often boil in an uneven fashion, or bump. They tend to bump when there aren't any scratches on the walls of the container where bubbles can form. Bumping is easily
prevented by adding a few boiling chips to the liquid, which provide a rough surface upon which bubbles can form. When boiling chips are used, essentially all of the bubbles
that rise through the solution form on the surface of these chips.
+++++++++++
You can't just post a quote, with no reply, as the software requires at least 20 characters of text to prevent +1 replies.
Also, make sure your posts are properly formatted before posting them, such as making sure quote tags are properly used. ;)
NBK
DONMAN December 17th, 2006, 03:34 PM

Does any one know the percent sulfuric acid that drain ro go drain cleaner is? Its sold in a jug in a bag. This cleaner also has some black dye added in. I was wondering does
any one have an estaminet what percent this is?
c.Tech December 17th, 2006, 10:23 PM
>90% from what I heard, doesnt it tell you on the jug?
stupid939 December 17th, 2006, 11:09 PM

You usually have to look at the msds, but the stuff I get (Liquid Fire Drain Line Opener) is 88%. Most of them are in the range of 88-95%. Another is called something like
Professional Drain Opener and IIRC it is 93%.

I got some Rooto drain opener. It says it contains concentrated sulfuric acid, but I checked the manufacturer's website and they do not have any MSDS's for their products--I'm
sueing :rolleyes:
stupid939 December 18th, 2006, 06:51 PM

Peter, I searched google for "rooto drain opener msds" and the second page I found had a msds that said 93.2% Sulfuric acid. Try a little harder next time because
spoonfeeding can get you banned around here, as you probably know. If you would like it, the link to the pdf is:
http://www2.itap.purdue.edu/MSDS/docs/12070.pdf
Oh, and I forgot that most of the dyes in the drain cleaner sulfuric acid can be oxidized. I forgot where I read it, but you heat up H2SO4 on a hotplate or stove to about 100C
or so, and slowly add H2O2. I used baquacil (27%) and it worked well. I forgot how much was added, but I did it until it was kind of clear.
I started with Liquid Fire (dark brown color) and when I heated it and added the H2O2, it turned fairly clear for awhile and then turned dark again, but after it cooled down, it
turned pretty clear again. The hydrogen peroxide breaks down into O2 (oxidizing dyes) and H2O, so it adds a little bit of water to your H2SO4, but it is better then doing some
reactions with a dark liquid.
PeterB2 December 19th, 2006, 11:14 AM

Opps, sorry >_<. Thanks for the link.
Is the H2O2 totally inert to the sulfuric acid? Still, great idea...and since its already hot anyway, it shouldn't be too hard to boil off the last little bit of water. As I found out the
hard way, just be sure to put some sort of media in there (porcelin bits or boiling stones) so that the boiling liquid doesn't erupt. :o
Cindor December 19th, 2006, 12:38 PM

H2O2 + H2SO4 --- H2SO5 + H2O
Maybe the Peroxysulfuric Acid oxidize with the dye and the Sulfuric Acid come back.

This warrants some investigation. This source: http://chemistry.about.com/cs/toxicchemicals/a/aa603003a.htm (acessed on December 27, 2006) says not to mix sulfuric acid
with hydrogen peroxide as it may spontaneously detonate.
nbk2000 December 27th, 2006, 05:14 PM

UTFSE for "piranha fluid". ;)
SafetyLast December 28th, 2006, 07:42 PM

The "Rooto" brand Sulfuric that I usually buy is very dark, almost black.
I'm not sure what kind of contaminants it has in it, but I do know that it is 93% concentration and works for most nitrations except will sometimes make a product with slightly
different color.
I'm reminded of that stupid book "Two component explosive mixtures" which was mostly a list of what chemicals will react violently with each other. I could have read that in
almost any chemistry book!
PeterB2 December 29th, 2006, 02:30 AM

Hmm...I didn't know piranha fluid was potentially explosive though. Corrosive and dangerous, definitely, but explosive? Also, from what I read, the concentrated sulfuric acid
must be mixed with >50% conc. H2O2 in order to produce efficient amounts of Caro's acid. Would 3-10% H2O2 make a mixture that would "spontaneously detonate" (if the
Caro's acid is indeed explosive in the first place)?

No amount of acid is going to turn 3% peroxide into piranha fluid.
Sworn December 29th, 2006, 10:15 AM

In my opinion, you had bought a cheap product or the industrial acid.
I didn't know what you want to use polluted sulfuric acid in sensible
liquids ? It turns black always when concentrated to fuming sulfuric acid.
The boiling point of sulfuric acid 100% is nearly 330 degrees C. Why don`t you
try to distill the acid in a high-quality distillation column. Concentrate
the acid much as possiple by boiling it and than distill gently that it not
decompose too much into sulfur dioxide.
I belive chilled piranha fluid will not spontaneously detonate, may it is usable
with sulfuric acid 95-99% and H2O2 >10%. You need a lot of sulfuric acid and the yield is very low.
PeterB2 January 15th, 2007, 06:16 PM

I'm going to by doing a titration soon to find out the concentrations of my various samples of sulfuric acid.
However, I'm wondering what the best base is to use for such a project. I was thinking about sodium hydroxide, but I'm not sure which products the reaction
thermodynamically favors : sodium bisulfate (NaHSO4) or sodium sulfate (NaSO4).
The balanced equation for each would be the following:
H2SO4 + 2NaOH --> Na2SO4 + 2H20
2H2SO4 + 2NaOH --> 2NaHSO4 + 2H2O
Another possibility would be that a significant amount of both sodium bisulfate and sodium sulfate is formed. If anyone knows, (or knows a good resource for thermodynamics
tables) this would help immensely in my stoichiometric calculations. Also, any suggestions for an alternative base are welcome. (I suppose, this could be why my previous
titrations with my battery acid didn't make sense.)
c.Tech January 16th, 2007, 02:39 AM
Although not as accurate you could always use a hydrometer to find the concentration. Should give you a close enough measure for its use in most explosives if thats
what you need it for.
SafetyLast February 28th, 2007, 04:53 PM

I didn't want to start a new thread about this since this one was already here.
I recently used a drain opener called "Liquid Lightning" which is labeled "virgin sulfuric acid". Now I've been using Rooto for a while which is dark color and works fine for most
things but this "virgin sulfuric" seems to be a bit weaker.
I read on an msds somewhere that the concentration was 93%, but now I can't find that msds anywhere. So here's my question: what sets virgin sulfuric acid apart from the
other concentrated drain opener variety? By the way this stuff is very dense and dark black like coffee.
chemdude1999 February 28th, 2007, 05:58 PM

SafetyLast, "virgin sulfuric acid" simply means the acid is "first use" as opposed to regenerated acid. Users often sell "spent" acid to facilities that regenerate it, ridding it of
contaminates. Virgin acid is supposedly higher quality. Honestly, it's just a selling point for the drain opener.
SA is naturally very dense and viscous. I would assume the dye is an indicator. For example, say you pour some in a tub and it is working its way into the clogged drain. Clear
SA would not catch the attention of a person that might subsequently use the tub, thus harming them. Also, I think it might be used as a branding method. Not positive,
though.
Shalashaska March 4th, 2007, 10:54 AM

I've actually been searching for an answer to this question for some time now, because Liquid Lightning is the brand available at Wal-Mart. The links when I search google are
mainly all leading to this
The Section 261.4(a)(7) exclusion applies only to spent sulfuric acid used as a feedstock in an
industrial furnace for the production of virgin sulfuric acid and does not extend to spent sulfuric
acid recycled in any other manner. Spent sulfuric acid is frequently burned in industrial furnaces
to derive sulfur. As part of the same process, this sulfur is then purified, chemically converted,
and absorbed into existing sulfuric acid. EPA has concluded that spent sulfuric acid that
undergoes this process is neither regenerated nor recovered, but rather used as an ingredient in a
production process (48 FR 14487; April 4, 1983). On the other hand, spent sulfuric acid
recycled by another method, such as filtration, is not excluded under Section 261.4(a)(7).
Alexires March 5th, 2007, 05:20 AM

Shalashaska - What was the point of that little piece of legislation? Where did it come from? What does it relate to?
An answer without a question.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Best w ays to
synthesize Copper Sulfate
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View Full Version : Best ways to synthesize Copper Sulfate

Since I didn't see an existing thread on copper sulfate, post you're ideas and techniques for synthesizing CuSO4 here...and yes, I know you can buy the stuff, but I want to gain
some more practical and simple lab experience.
Tw o methods that have worked for me so far:
1. Using copper electrodes for the electrolysis of a saturated Magnesium Sulfate in water. A blue precipitate that seems to be copper sulfate accumulates on the cathode.
Periodically wipe the precipitate onto a paper towel and allow it to dry. You can synthesize a small amount this way in a couple hours (depending on the voltage, size of the
cathode, etc.)
2. Mixing Sulfuric acid (I tried using battery acid of ~35% concentration and a low er concentration in an aquarium pH low ering solution) with a copper pot scrubber in a beaker
along with about 8 g of KNO3 (I think most nitrate salt should work for this experiment). This experiment produces a lot of fumes, so do it outside or cover it with plastic w rap
or something. Filter the reaction w hen it seems to have reached equilibrium and allow it to sit for a few hours and the CuSO4 precipitate should precipitate out of the filterate.
Any other ideas?
Does anyone know of any test I could use to test if these are indeed CuSO4, and, if so, how pure they are?
Universal December 11th, 2006, 01:08 AM

For no. 2 no KNO3 is needed, heat it up a bit. H2SO4 oxidizes Cu to CuSO4 in the reaction.
H2SO4 + Cu --> CuSO4 + SO2 + H2O.
It should react quite violently. To test for impurities, maybe bubble H2S through and see the different coloured sulfides, it should be black only if it is copper, if there are others
then find out what they are.
sprocket December 11th, 2006, 07:40 AM

Universal: Sulfuric acid alone is not sufficient to oxidize copper and your reaction formula is unbalanced.
However, the following two methods could be used w ith success:
1. Oxidize copper to copper oxides by heating in air. These basic oxides will dissolve in sulfuric acid forming Cu2+ -ions.
2. Oxidize copper in sulfuric acid using hydrogen peroxide. This is probably the easiest way to make pure copper(II) sulfate. Using hydrogen peroxide instead of nitrates has
several advantages; most notably a purer product and easier separation.
One fairly easy way to test the purity of your product is a gravimetric method. First w eigh an amount of fully hydrated copper sulfate, then proceed to dehydrate it (by heating
to above 150C). The anhydrous copper sulfate is then w eighed and the loss of mass should correspond to the loss of 5 moles of water from copper sulfate.

Sprocket, I tried the latter method with H2O2. This one could be dangerous--I saw some unknow n, rather thick brown fumes coming off the reaction w hich were pungent. It
seemed to yeild a homogenous solution of sulfuric acid and aqueous CuSO4. I'm not quite sure the best w ay to separate them. Maybe boil it?
To me, that's the most obvious advantage of using a nitrate like KNO3--the solid CuSO4 precipitates out of the solution after a few hours (it did for me anyway...I'm not sure
how atm pressure would affect it)
Universal, pardon my ignorance, but how do you bubble H2S through the solution? Do you need any special equipment to bubble gases through liquids?
I can take some pictures of the products and try to upload them if you like.

I have from time to time needed some copper oxide, but I find it to be very pricy when copper abounds around us. Being the cheap bastard I am, why not let the banks bear
the cost of my experiments? If you have the time and patience you can form your ow n copper compounds from pennies.
The reaction between copper metal and ammonia forms a hexaaquacopper(II) ion [Cu(H2O)6]2+ . I place all of my pennies in a gallon jug of household ammonia and let them
set. I have been doing this for a couple of years now. Over time the copper reacts and you get copper hydroxide precipitates once the ammonia concentration drops low
enough.
You can also add some sodium bicarbonate to form copper carbonate precipitates, and react that with sulfuric acid to get copper sulfate.
My way is slow, but it just sits there over time. The pennies can be cleaned up, rolled, and deposited at the bank. Give the bank a few bucks and they will give you many rolls of brand
new pennies to exploit , er us e.
Copper sulfate is sold at hardware stores in rather pure form as root killer for storm drains in quantities up to 5 pounds that I have seen. I believe it is also sold as a colorant for
fireplaces (makes flames different colors for parties, get togethers, and such), but it is far more expensive that w ay.
http://ww w.roguesci.org/images/copper_bottle1.jpg
http://ww w.roguesci.org/images/copper_bottle2.jpg

You might want to sort those pennies first. 1981- back are ~95% Cu, new er are copper plated zinc.

Yes, new pennies are a great source for zinc--just use a dremmel or a grinder to shave off the thin layer of copper and you have the precious (not "valueable" per se) metal
within. I havn't tried to make zinc dust yet, but I'm sure it would be quite easy.
Mega, would using a copper mesh pot scrubber (they're cheap--less than $1) increase the surface area of the reaction thereby speeding the process up? Also, I checked your
"Controversial Chem Lab" site for your opinion on how to synthesize copper sulfate but it wasn't there yet. Do you plan on doing any more on that site? There's some great stuff
there and I would like to see how you do some other sytheses. Keep up the great w ork on that site!
The only test I currently have to test for sulfates it to add H2O2 and a base (baking soda works great) to the sulfate in question. In the case of copper sulfate, the mixture turns
tar black and bubbles. I'm not sure exactly what's going on chemically there, buts its very interesting and seems to be a more or less accurate test for copper sulfate. Perhaps
the copper is being oxidized to Cu+2? With all other sulfates (that I've tried so far), the mixture bubbles but does not produce any color change.
sprocket December 11th, 2006, 09:39 PM

Sprocket, I tried the latter method with H2O2. This one could be dangerous--I saw some unknow n, rather thick brown fumes coming off the reaction w hich were pungent. It
seemed to yeild a homogenous solution of sulfuric acid and aqueous CuSO4. I'm not quite sure the best w ay to separate them. Maybe boil it?These brow n fumes are something
of a mystery to me. Are you sure you haven't confused the hydrogen peroxide experiment with the potassium nitrate one? Because the oxidation w ith nitrate w ould indeed
produce brown fumes, unlike oxidation w ith hydrogen peroxide.
Although the hydrogen peroxide method seemed good at first I'm starting change my mind. It works great for making copper(II) chloride w ith hydrochloric acid, but that's
mainly because the copper-chloride complexes help dissolve the copper. This is not the case with sulfuric acid; copper does not form complexes (at least not to a large extent)
with the sulfate ion. Thus the rate of reaction is much lower in the sulfuric acid solution.
Separating the copper(II) sulfate from the solution can be done by crystalization followed by filtration. Washing the crystals w ith an organic solvent is probably a good idea as
well.

Would it be possible to react a copper compound w ith some sulfate salt?
Alexires December 16th, 2006, 03:23 AM

It says on the net (here (http://www .copper.org/applications/compounds/copper_sulfate01.html)) that copper sulphate can be produced through heating copper w ith sulphur to
make copper sulphide which is then oxidized to copper sulphate. Otherwise there is Copper Oxide + H2SO4.

I remember making copper sulphate by boiling cut up copper wiring in dilute sulfuric acid (~33%) with a spoonful of sodium nitrate added in to kick it off.
It made the most beautiful blue crystals. :)
Sworn December 19th, 2006, 01:18 PM

Yes, this seems a nice procedure. Here is the formula to the process.
2 Cu + 2 H2SO4 + O2 -----> 2 CuSO4 + 2 H2O
I belive there is more than one w ay to make the product. I have modifyed a simple reaction betw een calcium sulfate and copper(II)chloride. There are the orginal formulas. The
process w ill not w ork w ith magnesium(II)sulfate, the magnesium chloride is difficult to remove. The hexahydrate dissolves w ith around 1670 g per litre in w ater.
2 KCl + 2 MgSO4 + 6 H2O -> K2SO4 * MgSO4 * 6 H2O + MgCl2

K2SO4 * MgSO4 * 6 H2O + 2 KCl -> 2 K2SO4 + MgCl2
Calcium sulfate dihydrate seems useful with around 2 g per litre.
2 CuCl2 + 3 CaSO4*2 H2O + 5 H2O -> 2 CuSO4*5 H2O + CaSO4*2H2O + 2 CaCl2

2 CuSO4*5 H2O + CaSO4*2H2O + CuCl2 + 5 H2O -> 3 CuSO4*5 H2O + CaCl2 + 2 H2O
A mixture of 2 mol copper(II)chloride powder, 3 mol calcium sulfate dihydrate powder and 90,5 mL of water is heated in a large beaker below the thermal decomposition of the
copper(II) sulfat. (around 88 degree C) The beaker should be sealed and mixture is stirred sometimes. After some hours, a mixture of copper(II)sulfate and calcium sulfate
should have formed, open the beaker, the mass is dryed and grindet with a motar, placed to a new beaker and a second portion of 1 mol of copper(II)chloride pow der and 90,5
mL of water is stirrd to this. The procedure is continued exactly as the previous step and the obtained mass is added to around 2400 mL of w ater, filtered and the blue solid of
copper(II)sulfat pentahydrate is then collected by vaporizing the water.
In my opinion, as a possible issue to obtain the copper(II)sulfate is the process to generate sufur dioxide and oxygen (ratio 2:1) and the gas is bubbled into a mixture of 2 mol
of copper(II)chloride and 126,5 mL water. It happens the dryed product is polluted with some hydrochloride but it should useful.
2 CuCl2 + 2 SO2+ O2+ 7 H2O -> 2 CuSO4*5H2O + 4 HCl (hydrogen chloride) + 2 H2O
A reaction betw een copper(II)nitrite and copper(I)iodide in concentrated sulfuric acid seems useful, if it exist. 2 mol of grindet copper(I)iodide is stirred to 4 mol of sufuric acid
>99%, 1 mol of copper(II)nitrite pow der is added in small portions and the mixture is stirred is continued until no fumes of nitrogen oxides w ill bubble off. Cool the mixture if
necessary and hold the temperature below 88 degree C. The mass is added to 3200 mL of w ater, filtered and the copper(II)sulfat pentahydrate is collected by vaporizing the
water.
2 Cu(NO2)2 + 2 CuI + 4 H2SO4 -> I2 + 4 CuSO4*H2O + 4 NO
This procedures are something costly and precisely worked but seems useful.
If there is more to a copper(II)nitrite procedure, please post your suggestions.
Any thought to my issues ?
DONMAN December 20th, 2006, 02:10 AM

I have from time to time needed some copper oxide... If you have the time and patience you can form your ow n copper compounds from pennies.
I have started this process, about how long will it take for the precipitate to form? Weeks? Months? I am using copper wire ..... that should speed up the reaction. My solution is
very blue now, but still no precipitate. It's been about 5 days now .

I'm thinking months, although I just let mine sit, so I don't know when it precipitated. I think I have had my penny jug for about 2 years now.
The more copper ions in solution, the sooner the ammonia won't be able to dissolve them, and then you get a precipitate. The precipitate pulls copper ions out of solution (as a
hydroxide) allowing for more copper ions to enter the solution (from copper metal). Lather, rinse, and repeat...
I recommend agitating the copper from time to time. It seems to form a scale that reduces surface area after awhile.
Universal December 26th, 2006, 10:10 PM

This seems like an awful amount of trouble to go to to make CuO. I made it by mixing CuSO4 w ith Al, and collecting the Cu powder. I wash it until it is nice and clean. Then I let
it dry. This makes a fine powder. I then heat this up w ith sulfur in the roght amounts, it turns to CuS, I then heat the CuS and high temperature until SO2 stops being made and
CuO is left.

But your w ay is more expensive.... The old saying is,"you have time or you have money.":rolleyes:

If you're using aluminum foil or cut-up soda cans, plus scrap copper, it shouldn't be expensive at all.
Universal, how fine is the copper pow der you get? Flour fine?
Pure copper powder has many uses, not the least of w hich is as a filler for flexible LSC liners. :)

The copper is not flour fine, unfortunately, but much finer than say salt or sugar. If you mill it, or mortar and pestle it like me, it is almost as fine as flour. And yes, it isn't very
expensive, just the SO2 is a bit annoying ;)

I bought some copper oxide about 2 years ago and it struck me as being very expensive for what little I got. Since I have enough CuO on hand to last me awhile, and I have
the idle time for the pennies to soak, I figured why not. Except for the ammonia, this process is almost free if you cash in the pennies after exploit..., err, utilizing them.
Every person has different motives and goals when it comes to obtaining and using chemicals. Those that can get chemicals easily and cheaply, god speed, but for the have
nots, or the have littles, any w ay you can get your fix is a good w ay.

Perhaps if the solution was rapidly stirred (mechanically) during the precipitation process it w ould be much finer.
Something for you to try, as extremely fine CuO mixed with Aluminum powder in an explosive binder forms very powerful explosives. :)
inventorgp January 5th, 2007, 07:36 AM

Here's a site/vid NBK,
Site: http://geocities.com/roguemovies9/index.html
Vid: http://geocities.com/roguemovies9/copper-oxide-aluminium-target.mpg
That was shot at.
Thats one of them but, Geo seems to be down some times. And I can't get a FTP working.
nbk2000 January 6th, 2007, 06:46 AM

Dude...that site is so old. :p
It w as originally put up by Axt before he got banned for his stupidity here.
TimedReport January 31st, 2007, 09:51 AM

I am mostly interested in firew orks, but have become increasingly interested in making high ex and sythesizing my own chems. This was mainly brought on because of the
CPSC and their move to ban all chemicals in an effort to create their communist, bliss-ninny utopia.
Anyway, this is my first post here, so hopefully it can be helpful to someone. After the CPSC started in with their stupid nonsense, I started focusing on ways to buy chemicals
through sources other than chemical supply companies. It becomes clear that many of our chemicals are used in other industries and merely telling a lie to the proprietor as to
who you are and what you want it for will yield fantastic results. Of course, in some cases you don't have to lie, but I digress.
Copper compounds are no exception (although you don't have to give them a story). Here are two sites that sold the absolute cheapest copper compounds that I could find. I
actually bought from them and they sent the forty and fifty lb buckets to me through the mail. I bought Calcium Carbonate, Copper Carbonate, Copper Oxide, and Barium
Carbonate. The prices, per lb, were $0.24, $3.95, $3.38, and $1.18, respectively. Of course, you have to buy a lot (10 lbs ranging to 50 lbs at a time).
I haven't tested anything for purity, but the chemicals work fine in color and glitter stars. They are at least technical grade, I would assume.
Good Luck,
Joel
http://ww w.seattlepotterysupply.com/Merchant2/merchant.mvc?
http://leslieceramics.com/artman/publish/article_143.shtml
chembio March 19th, 2007, 08:34 AM

You could try using copper (II) nitrate and sulfuric acid. I believe the equation would be like this:
Cu(NO3)2 + H2SO4 -----> CuSO4 + 2HNO3
This reaction w ould give you copper sulfate AND nitric acid. From most of the posts I've read, HNO3 is a hot item among fellow forum members.
Or if you want to use copper oxide, I would try this method:
________________________O
l
l_____P_________A________O
H1 H2
This diagram represents an experiment setup (in a boiling tube). The symbols:
A - Copper
P - Potassium permanganate
O - Glass Wool (plugging the mouth of the boiling tube)
H1/H2 - Heat.
Heat the copper until it melts. Then, heat the KMnO4 to release oxygen. The reaction should end with the oxidation of the copper.
Hope this helps! :)
Vigo March 20th, 2007, 01:08 PM

A little aside:
when you have obtained copper sulphate by w hatever method, take care not to inhale the dust as around here in Sw itzerland it is classed 3 on the poison scale (from 1 to 5).

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Quick way of making
Copper (II) Oxide
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I was fooling around and I discovered quite an expedient way of creating copper (II) Oxide. I stripped some copper wires and then I submerged them in house hold bleach
~3% (NaClO). Then I slowly added 3% H2O2 till the solution stopped bubbling off the H2 (I assume).
3CU(s) + NaClO(aq) + H2O2(aq) --> H2(g) + 3CuO(s) + NaCl(aq)
Is that right?
Do you have any other ways of making Copper (II) Oxide?
I hope to do this on a larger scale and make some really nice Thermite with some Mg. :D
c.Tech December 16th, 2006, 04:24 AM

(ag)? Dont you mean (aq) or aqueous?
And copper II oxide has the chemical formula CuO so your equation must be wrong.
Another way of making CuO is by electrolysis of copper in water, but why make it when you can buy it pure from pottery stores?

Yes, did mean (aq) that was a type-O. There now my equation works. This process works extremely well, and fast in comparison to electrolysis. I have a very strong source of
dc current and it took forever with copper electrodes. This is much faster and I am sure its cheaper(considering the electricity and time consumed for the electrolysis process). If
you cant find copper wire use pennies, although this may be slower. Bleach is cheap and so is hydrogen peroxide. I could buy this from a pottery store pre-made... but where
is the fun in that. It's like making a really good cake from scratch, you just feel more accomplished than if you would have just mixed some pre-made crap. Also I don't know
where the nearest pottery store is. :D

Good work...now I can try another method for copper sulfate! I'll have to try this method sometime. Hopefully, I'll have a chance to get some good 30% H2O2 from the local
pool store--or can you just use the 3% crap with some success?

I am using the 3%~ crap. The thing is if you use 30% your going to have to use 10 time the amount of bleach that you would normally to make your 30% fully react!
Now if you got some pure NaClO and some 30% percent H2O2 then you could seriously lower the volume required for the reaction. Does any one know where/how to get pure
or concentrated NaClO? I know you can't just boil bleach down, its got too much NaOH and other thickener crap in it.

Use Ca(ClO)2, from the pool store remove the insoluable mixer and dissolve as much as possible in water. NaClO pure is a dangerous chemical and is very hard to get (where I
come from), it is a liquid I think.
Cobalt.45 December 17th, 2006, 02:47 AM

Thanks for that, Donman. Just saved me a trip to who knows where, to buy some.
I'll have a blue comp yet, hopefully.

I cant find copper sulfate, so I will attempt to make this and add sulfuric acid.

I work at a retirement community (in the dining room), which is a very new facility, and I had to go to the laundry room to get some linens and I noticed a little container
above one of the pieces of machinery that said, "When flashing, add pure bleach."
Being curious (and stupid) I went over to open the lid and take a look at the substance. The smell (VERY strong bleach smell) filled the room almost suffocated me making
breathing very difficult. However, I was able to catch a glance at the substance inside: a white fine powder of assumedly pure NaClO.
Now I still have no idea where the average person would go to get the stuff, but professional launders (especially at newer facilities) might have some of it.

I doubt that would be pure NaClO, first of all it is unstable, it is a liquid, and pure bleach, or bleach powder is a 70% strength mixture of calcium hypochlorite. Calcium
hypochlorite smells very strong of chlorine, I know ;).
oregon-machinist December 19th, 2006, 03:36 AM

SNIPPED....If you cant find copper wire use pennies, although this may be slower. SNIPPED
If you attempt to use pennies, be very sure they are all Pre-1982, as a matter of fact, I would even go pre-81 to be sure!!!
Post 1982 pennies are 99 % Zinc, with a Copper Flash ([plated).
Also, prior years for pennies (pre-82) are now worth approximately three cents each BY WEIGHT, though it is illegal now, to melt them and sell it as scrap....
Hope that Helps someone...
Microtek December 27th, 2006, 11:55 AM

I use NaOH to precipitate Cu-salts as Cu(OH)2, then boil the suspension to decompose that to CuO and water.
Aqua_Fortis_100% June 23rd, 2007, 09:34 PM

3CU(s) + NaClO(aq) + H2O2(aq) --> H2(g) + 3CuO(s) + NaCl(aq)
Is that right?
don't work
i've tried by putting some fresh Cu wires inside of a plastic cup and added bleach just o cover. after, adding some 3% H2O2 slowly and the stuff fizzed a lot and a slight smell
of chlorine was sprayed in my backyard. actually the right reaction, after search more, is the H2O2 reacting with bleach and forming Oxygen (but i'm not sure of what the rxn
lead to chlorine..maybe a side reaction).. if you let the copper reacting with bleach ALONE, this will form a black layer on material, but i'm still not sure if this is copper oxide or
oxychloride..
the fastest way to do is as Microtek said: use NaOH(aq) and CuSO4*5H2O(aq)(or whatever copper II soluble salt you have on hand), react them, decant/wash/decant/wash...
reapeat several times to ensure the Cu(OH)2 obtained being really FREE NaOH (which can be dangerous , specially if you is planning to use in CuO/Al thermite), and finally ,
drive out the water by simple bolling them and heating more strongly the black residue(be watchful, the crappy black thing can spread in violent manner and fall in your skin/
eye..) .
another old and theoretically simple stuff to make CuO is apply red heat to copper things (coins, wires, etc) and scrape all black part (seems to be very messy, though)
a better and promissing method is put whatever thing made of copper into a strong ammoniacal solution, add a ammonium salt (eg (NH4)2SO4 ) and then bubble air thorough
this solution for several hours (eg use an innexpensive aquarium pump to do). your solution will goes to be very nice blue and depending of your reagents and conditions most
of the copper will be dissolved.. the atmospheric oxygen does the trick. this mean which you can use oxidizers to do: 3% H2O2 ,etc..but make the things more expensive and
can be dangerous (i've tested with 3% H2O2 and this developed lots of heat of the almost simultaneous eat of the copper coin i've put on the cup and leaving the blue
solution)..
after do this, you can decant/filter to remove unreacted copper, and heat (OUTSIDE!!!) the solution which will lose ammonia and the complex made before being destroyed to
release more ammonia and ppt at same time your nice and usefull CuO.

My pennies in household ammonia have recently gone from the light blue of hexaaqua copper to the dark purple of copper tetraammonium compound. I boiled the liquid in the
microwave and what appears to be copper oxide formed (a black precipitate). I also obtained this black precipitate by conventional heating (to rule out a microwave effect with
copper).
I should test to see if copper sulfate would better be reacted with ammonia. Ammonia is easier to get and cheaper than sodium hydroxide now that Red Devil Lye is off the
market. If a copper and ammonia compound does form, microwaving should produce a precipitate.
The reaction that you experimented with, aqua, sounds like it may be possible, but is one of those technical theoretical reactions that happens to a small degree, not a main
reaction that goes to completion.
There are many complex chemical reactions that CAN happen, but we are interested in a reaction that goes to completion, i.e. giving a substantial quantity of product. Aqua's
experiment demonstrated this. This is why practical experimentation always beats theory, or rather why theory always needs experimentation.
krick June 25th, 2007, 04:13 PM

An as fast as simple way to produce small amounts of copper oxide can be done like this:
Melt some ammonium nitrate, add copper to the liquid and keep heating it. The copper will soon be solved and the solution will turn blue immediately.
Then keep heating until all left over AN has decomposed and finally the formed copper nitrate will decompose quickly producing a cloud of NOX!! and copper oxide.
For your own safety:

Be careful, NOX!! will be formed in quit big amounts; probably it shouldn't be used more than 10g at once because of the risk of a detonation, but I'm not sure at all.
Glassware should better be left out, stainless steel will do its task.
DONMAN June 26th, 2007, 01:33 AM

The chlorine smell is simply the gas given off by the reaction splattering the solution causing the bleach to disperse into the air giving off the chlorine smell.
Atra June 26th, 2007, 03:58 AM

I don't know if this is correct, but I've been making copper chloride for years through the reaction of H2O2+Cu=CuO+H2O CuO+2HCl=CuCl2+H2O. Furthermore if not enough
acid is used a black layer of silt develops on the bottom that turns green and is instantly dissolved with the addition of more acid. Wouldn't this mean that H2O2 by itself
oxidises copper?
Cindor June 29th, 2007, 09:10 AM

Wouldn't this mean that H2O2 by itself oxidises copper?
H2O2+Cu=CuO+H2O Don't you think you've answered yourself ?
You don't even need to UTFSE, just read what you previously wrote !
And yes H2O2, is, in fact believe it or not, an oxidizer.
PeterB2 November 29th, 2007, 11:26 PM

I don't know what it is with me and copper salts, but now I'm trying to make Cu(NO3)2.
I made some the old fashioned way with nitric acid. But who wants to waste nitric acid?
Would it be possible to use a metathesis reaction with a copper salt (like copper sulfate or oxide) and a common nitrate?
Another interesting thing I read is that in the laboratory, copper nitrate is used to generate nitric acid by decomposing it and bubbling the gases into a cold solution of water.
Has anyone heard of this?

Peter, I am curious to know this as well, so I just looked it up... Turns out you can make copper nitrate (cupric nitrate technically) by boiling a nitrate salt with copper, copper
hydroxide, or copper carbonate. Copper carbonate in particular should work best. You can make copper carbonate by adding a solution of sodium carbonate (washing soda,
also by boiling baking soda, sodium bicarbonate) to a hot copper sulfate solution. Copper carbonate precipitates from solution.
tranquillity December 1st, 2007, 05:57 AM

Wouldn't the simplest way to make relatively pure copper nitrate be to simply mix (in water) commonly available copper sulfate and calcium nitrate? Calcium sulfate would
precipitate. For higher purity choose a metal nitrate with a more insoluble sulfate like barium or lead.
PeterB2 December 1st, 2007, 02:23 PM

Actually, Mega, copper nitrate is even easier than that: copper sulfate (I just used the root killer stuff from the hardware store) reacts directly with baking soda in a solution at
room temperature (tried it as referenced in "The Joy of Chemistry"). Just make sure both solutions are saturated, and presto! about 5 seconds later you have a nice insoluble
mass of copper carbonate. Through the reaction with any mineral acid, you should be able to make just about any corresponding copper salt.
Though with this method, you'd still have to waste/use nitric acid for copper nitrate.
I'm going to try your method for making copper nitrate as soon as I get back to my lab...looks promising. If that's relatively expedient, that might be a viable way of producing
nitric acid cheaply without a distillation rig.
Thermiteisfun December 3rd, 2007, 02:02 PM

So I've been trying to synth Copper nitrate with electrolysis of KNO3, I had a conversation about it with my friend who is in orgo 2 now and she concurred with me on the
theory.
Here is what I did:

I took 20 grams of KNO3 finely powdered and dissolved it into the smallest possible amount of near boiling, distilled water (25 ml).
After that I ran 12v at 1.25 amp with copper electrodes, the reaction resulted in a white gelatinous precipitate with a blue solution and what I assume to be hydrogen which I
confirmed with a flame test . NOx was evolved as well, it is my assumption that more NOx will evolve with higher current.
After a few minutes the solution turned black with what I believe to be copper hydroxide floating on top and copper(II) oxide suspended in the solution... The electrolysis
caused an awful amount of heat which lead to the decomposition of the Copper Nitrate. I'm going to try with a water bath to regulate the temperature.
I told her this and she said "oh god it's crazy! it's like got a bunch of H2O and OH attached to it with a billion numbers (the precipitate). I think dropping the wire in and heating
the solution works to if I remember right, I did that reaction in chem2" (at which point she spilled hot soup on her crotch ending the conversation).
If anybody knows the solubility and formula of the precipitate, please tell me. This could be an extremely easy way to make copper nitrate.
Edit 2: now that the solution has settled, it appears to be a VERY dark blue and cleans my silver very well :D , there is a hint of green though.
Edit 3: After the solution had fully settled, I decanted and put a paper clip in....Nothing! Galvanized nail.... NOTHING! No plating occured at all, it appears that this is not Copper
nitrate!
Links I found:
http://www.scienceforums.net/forum/showthread.php?t=15987
http://mooni.fccj.org/~ethall/2046/ch18/electrol.htm
http://www.scienceforums.net/forum/showthread.php?t=16006
Pyroman December 27th, 2007, 09:42 PM

(ag)? Dont you mean (aq) or aqueous?
And copper II oxide has the chemical formula CuO so your equation must be wrong.
Another way of making CuO is by electrolysis of copper in water, but why make it when you can buy it pure from pottery stores?
Last year i prepared some copper II oxide by elctrochemical method with water with common table salt dissolved in it.
After the process it must be water washed several times in order to remove NaCl traces.
The salt incerases drastically the condutivity of water reducing the loss of energy by warming the solution. It reduces the amount of voltage requied to get good amperage.
Note there is de amperage that makes the "conversion" not the voltage.
Happy new year.:)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Unforseen Happening
With nitration of cellulose
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DONMAN February 5th, 2007, 02:17 AM

I was just finishing my nitration of cellulose, and I was squeezing the acid out of the nitrocellulose with my thick rubber gloves, when all of the sudden I feel this heat from the
glove and it partially combusted burning the glove. I was using the NH4NO3 method of nitration, if that helps....
Now I have a few theories as to what caused this:
I squeezed the acid out so much that I partially dried out the cotton causing it to be very sensitive, as it hadn't been neutralized with a base yet.
or.
The glove reacted with the acid forming some organic nitrate that under the heat of its own nitration ignited itself.
Just wondering if any of you had any input on what happened chemically?

I'd say acid reacting with the glove rubber.
What kind of 'rubber' are these gloves? Latex, nitrile, butyl, neoprene?

They where latex. What should I use in place of them?

Something other than your hands, perhaps? ;)
Press it in between 2 blocks of wood.

God that was stupid choice of gloves...oh well we all learn sometimes by mistakes. IIRC ACS president several years ago make a (false) press statement about condoms aren't
safe because size of the pores on the latex they are made of (like on gloves) is larger than the size of the AIDS virus causing the turmoil among the sheepish population. While
that was true for the gloves which was made (at that time - I'm not sure how do they make them today) by one-layer process, it was false for condoms which are always
made by two-layer process. While this seem like OT...point of the tale is...you choose the thinest and least protective thing to do the job.
Hell I have seen some nasty mustard like substance/solution easily pass through neoprene/nitrile gloves so you can't be 100% safe ever but I hate latex as to prone to
leakage, solvent penetration and mechanical instability upon the contact with some solutions.

Latex is solidified tree sap, so how good can that be against fuming acids?

Well these where 4 ply so I thought that they could handle the job. They weren't like medical exam gloves, although they where latex :( ....
I am defiantly going to go pick up some more industrial gloves!
Live and let learn. It wasn't smart in the first place to wring it out by hand, I just didn't want to have to waist so much base in neutralizing all that acid. I am a cheapskate :)
Bert February 11th, 2007, 10:49 AM

Go to your hardware store and tell them you're acid washing concrete. Get the rubber gloves masons use for that job- Not good for jewelry work, but very strong & acid proof.
It is not uncommon for guncotton to ignite in the acid removal centrifuges in industrial plants- Just the moisture in the air on a humid day can raise the temperature of the acid
damped fiber enough to cause ignition.
SafetyLast February 28th, 2007, 05:33 PM

Use nitrile gloves, nitrile is synthetic latex. They contain no latex proteins and are resistance to punctures and tears. They are resistant to many types of chemicals. PVC gloves
also work good, I used to have a really good pair of high cuff pvc acid gloves.
I personally use tongs for squeezing my wet nc.
I've never had good success from the AN nitrating method the dry product burned slowly, taking about 3-4 seconds for a thumbnail sized wad to burn! It left a lot of black ash
as well leading me to believe that it was only slightly nitrated like the celluloid that ping-pong balls are made from.

a n d I m provised C hemistry > Sulfuric Acid
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209 February 27th, 2007, 09:24 PM

T h e o t h e r d a y I was at the BIG Hardwa re store and was looking around for som e stump re mover, it's a sham e b e c a u s e I c a n
get m y h a n d s o n l a b g r a d e s t u f f a n y m ore. Anyway, I happend to walk down the cleaner section and found a 5.5 kg bag of Lye.
I h a d t o s m ile to m yself because I had such a bitch of a time buying 200 gram s of lye at the pharm acy because the guy
thought I was trying to m ake crystal m eth :rolleyes:.
R i g h t n e x t t o t h e b a g of lye was a bottle of "industrial d rain opener". It was enclosed in a plastic bag thingy. I read the
ingredients and its said "caution, contains sulfuric acid". Being that the last of my Sulfuric was used up in a failed Picric Acid
synth, would I be able to somehow use this drain opener for the sulfuric used in many HE synths?
I s t h e r e s o m e m ethod of extracting the acid out of the drain opener or is it just a waste of m o n e y ?
Shalashaska February 27th, 2007, 09:40 PM

Hardware grade is about 93-94% Sulfu ric Acid, which is about 3x the am ount from battery acid, which ACB o r other sites tell you
is th e best place to get it from .
I suggest fro m now on you do n't waste other m e m b e r s ' t i m e a n d u s e t h i s -

http://www.roguesci.org/theforum/search.php
... so that yo u can fin d threads like this

www.roguesci.org/theforum /archive/index.php/t-1835-p-2.html
Or this
www.roguesci.org/theforum /archive/index.php/t-3692.htm l
Or this
www.roguesci.org/theforum /showthread.php?t=3124
Or, m ost im portant of all, this, the legendary "Great OTC Survey.
chemdude1999 February 27th, 2007, 10:33 PM

You know, I usually ignore this stuff being relatively new, but this irritates me. I read the rules thoroughly before joining. They
m a d e g o o d s e n s e a n d e x i s t f o r a r e a s o n . U T F S E i s w h a t s o m e m ight consider a cardinal rule along with a few others.
From my observations, Mega and NBK have this rule in place to m inimize repeat of inform a t i o n . T h e f o r u m s a r e m a n a g e a b l e
with out a ton of useless and repetive threads. I wish m ore forum s were like this.
The OTC thread is the main one for this particular inform ation. Why don't you try to use the stuff on a synthesis or analysis
that is relatively safe and inexpensive to verify if it m e e t s y o u r n e e d s . T h e n p o s t a b o u t i t u n d e r t h e O T C t h r e a d . I t h a s b e e n
discussed, but you might discover a nuance that could be enlightening. Just m y 2 cents.
I'll now go back to som e O C R i n g a n d p o s s i b l e t r a n s l a t i n g f o r m y s e l f a n d t h e f i n e m e m bers of this forum as repaym ent for the
excellent info this site provide s.

T h e o t h e r d a y I was at the BIG Hardwa re store and was looking around for som e stump re mover, it's a sham e b e c a u s e I c a n
get m y h a n d s o n l a b g r a d e s t u f f a n y m ore.
CAN means you are able to obtain the material, but CAN'T m eans you are NOT able to get the material, wh ich is what you
m eant.
G r a m m ar is important, as the lack of 't from one word com pletely changes the m e a n i n g o f a s e n t e nce.
I've noticed this similiar gramm atical failing in another m e m b e r . B o t h n e e d t o i m p r o v e A S A P .

a n d I m provised C hemistry > Fertilizer ---->phosphorus pentoxide
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DONMAN March 11th, 2007, 07:11 PM

I just picked up som e 0 - 4 5 - 0 a l s o k n o wn as (C alcium d i h y d r o g e n p h o s p h a t e ) . I t d e c o m poses at 205~ centigrade. I expect it
would go something like this?
2 C a ( H 2 P O 4 ) 2 + O 2 - - - > 2 C aO + ?? HPO3 or P2O5 with som e H 2
My ultim ate goal is to m a k e p h o s p h o r u s p e n t o x i d e . C a n y o u g i v e m e s o m e input. I know it would be best if I could get m y

h a n d s o n s o m e a m m onia phosphate... but I cant... I could synthesize it ....but that's annoying..

You will end up with p h o s p h o r u s o x i d e s , n o t n e c e s s a r i l y a l l p h o s p h o r u s p e n t o x i d e . P 2 O 3 , P 2 O 5 , H 3 P O 4 , a n d who knows what
e l s e m ay form d e p e n ding on the conditions of your hea ting, how m uch oxygen is available, and th e m oisture in the
environm ent.
W ith am p l e o x y g e n a nd low m oisture I would say you would get predom inantly P2O5.
kurtz March 12th, 2007, 12:43 AM

I will go out on a lim b and propose that there is absolutely no chance whatsoever to obtain any P oxide from a n y p h o s p h a t e
unle ss transient reduction of the phosphate with whatever reducing agent occurs first.
C a ( H 2 P O 4 ) 2 - H 2 O -> CaH2P2O7, calcium dihydrogen pyrophosphate/calcium acid pyroph o s p h a t e / C A S # 1 4 8 6 6 - 1 9 - 4 .
DONMAN March 12th, 2007, 01:19 AM

Is there an easy test to find o ut which P oxide have created? All P oxides look the sam e. I guess I could try reacting it with
s o m e alcohol and seeing if it oxidizes it....... Stupid non-ionic, n on-organic reactions..... * m u m b l e * * m u m ble*...
knowledgehungry March 12th, 2007, 01:26 AM

W ith enough heat I would im a g i n e t h a t i t w o u l d g o t o P h o s p h o r o u s o x i d e s , b e c a u se of entropy and such. C a O h a s m uch lower
entropy(or m ore, m o m entary brainfreeze on whether high amounts of entropy have more energy or low am o u n t s h a v e m ore
energy)than CaH2P2O7.

Pretty sure high am o u n t s o f e n t r o p y h a v e m o r e e n e r g y . L i k e w h e n y o u h e a t s o m ething up you increase entropy.

If you can find a single reference to the production of any P oxide from any alkali/C a phosphate by heating in air below 1200C
without reducing agents, in an y sort of reference (handbook, database, journal, b ook, patent), in any language, let us know.
Until som e o n e f i n d s t h a t s u c h a t h i n g h a s b e e n d e m o n s t r a t e d t o b e p o s s i b l e , i t s e e m s s a fer to assum e that you don't have
one. That's just m e , I g u e s s .
Frunk March 12th, 2007, 07:03 PM

Pretty sure high am o u n t s o f e n t r o p y h a v e m o r e e n e r g y . L i k e w h e n y o u h e a t s o m ething up you increase entropy.
No, actually when you h e a t s o m ething you increase the level of order, therefore you decrease entropy. Things tend to go
towards entropy, things tend to cool down.
Absolute Zero is absolute entropy.

I found several MSDS sheets yesterday for this stuff that stated phospho r u s p e n t o x i d e s a r e p r o d u c e d a s d e c o m p o s i t i o n
products over 200 C. I could give you several references, but you can find them .
Lets start with the Merck index first... The entry for calcium p h o s p h a t e , m o n o b a s i c s t a t e s " d e c o m p o s e s a t 2 0 0 d e g r e e s . " T h e r e
you go kurtz my boy. Merck goes on however... "The products obtained from com mercial processes are not pure m o n o b a s i c
calcium p h o s p h a t e . T h e s u p e r p h o s p h a te obtained from the H2SO 4 treatm e n t i s a b o u t 3 0 % C a H 4 ( P O 4 ) 2 . H 2 O , 1 0 % C a H P O 4 ,
4 5 % C a S O 4, 10% iron oxide, silica, alum ina, etc., and 5% water; it contains 18-2 1 % a v a i l a b l e P 2 O 5 . "
That's a nasty m ix there, and most likely what your fertilizer grade is.
On the other hand the fertilizer code you provided could be triple superphosphate fertilizer, which is formed from a different
m anufacturing process and is much pu rer containing 43-50% P2O 5 and no calcium sulfate .
Here is a PDF with m ore than I wanted to know about th e stuff... http://www.am s.usda.gov/NO P/Na tionalList/TAPReviews/
m onocal.pdf
You guys arn't m ixing up your entropy and enthalpy are you? Irregardless, who cares? Your not helping the thread with a
pedantic discussion of physics. I am afraid DO NMAN that your topic is so esoteric no document on the Internet is going to
contain this information. This is a prob lem long relegated to the shelves of forgotten 19th century chem istry. Heat fertilizer,
h o w d a r e y o u ? a m o d ern chem ist would say...
i doubt anyone alive could actually answer your question. W hy? Because they don 't teach practical information like this
a n y m ore, no industry would bother actually doing this process so it won't appear in any m odern reference, and there is nothing
free on the Internet that would tell you. I hate to say it but it looks like experime ntation with a good deal of chemical analysis
is re quired to really answer your question. That would require a well established laboratory.
kurtz March 12th, 2007, 08:18 PM

The entry for calcium p h o s p h a t e , m o n o b a s i c s t a t e s " d e c o m p o s e s a t 2 0 0 d e g r e e s . " T h e r e y o u g o k urtz m y boy.
And I told the product in the above post. The a ction of heat on phosphates is not a mystery, and in fact the old references are
often not the best source in this case, as the identification of the products is not easy and the products them s e l v e s
complicated.
Ya'll aren't actually going to com e right out and say that you think that the %P2O 5 m eans that it actually contains P2O5, or
that you can just heat it up and m agically get P2O5 (m p 3 3 0 , s u b l i m e s @ 3 6 0 C ) a r e y o u ?

h m m... looks like I have my work cut out for m e. I will tinker for a few days and report m y findings....

T o o k o n m y own challenge and I did find some oxide from phosphate in a search. There were four conversions of phosphate
t o a n o x i d e ( a l l t o P 2 O 5) in the literature up to 1970 or so. One of them doesn't count because it involves transient reductio n
with carbon. A Polish article claim s form a t i o n a t t h e a n o d e d u r i n g e l e c t r o l y s i s o f N a m e t a p h o s p h a t e a t 6 4 0 C . A French article
h a s A l P O 4 h e a t e d t o 1 0 0 0 C . P2O5 vapor form s starting around that tem perature, and Al2O 3 r e m a i n s . T h i s i s C o m p t. rend.
234, 1777 (1952), which is fre ely available at Gallica. And a Berichte article has phosphate, pyrophosphate, and
m etaphosphate heated a little with SO3, all with the form ation of P2O5; i.e. 2 K3PO4 + 9 SO 3 -> 3 K2S3O 10 + P2O 5. I have
this article if anyone gives a shit and if there is a thread for it, but it is of course in Germa n.
I should have a thick enough skin to ignore the cries of bullshit upon sta ting widely accepted facts, but even so I tracked down
an article on this for proof of what I said above; and I'd still like to m e e t R o s c o a n d s m a c k h i m ( s e e f o r m a m i d e ) .
" A c i d P y r o - a n d M e t a p h o s p h a t e s P r o d u c e d b y T herm al Decomposition of Monocalcium Pho s p h a t e "

IEC 39, 1667 (1947)
http://www.box.net/shared/ze6pu5janz
DONMAN March 21st, 2007, 01:04 AM

That is awesom e, tha n k y o u s o m uch. Where in the hell did you dig that up!

a n d I m provised C hemistry > C hemical Inform a t i o n O n S o l u t i o n s
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View Full Version : Chemical Information On Solutions
prufrock March 12th, 2007, 06:31 AM

THE CONCENTRATION OF ACID OR BASE SOLUT IO NS IN MOLAR AND NORMAL CONC ENTR ATIO NS CAN BE DIFFICULT TO MAKE
F R O M S T O CK SO LUTIONS. HO PEFULLY THIS TABLE WILL HELP THE CHEMIST IN MAKING SOLUTIONS OF A SPECIFIC
CONCNETRATION.
Hydrochloric Acid
Concentrated 12 Molar; 444 gm . HCl p er liter, specific gravity 1.19
37.5 percent HCl by weight.
Dilute 12 Molar to 6 Molar or 6 Norm al Dilute 500m l. conc. HCl to 1 Liter

5 Molar or 5 Norm al Dilute 420m l. conc. HCl to 1 Liter
2 Molar or 2 Norm al Dilute 164m l. conc. HCl to 1 Litre
or Dilute 1 volum e 6M with 2 volum e s
water
20 Percent Approx. 6M or 164 ml. conc. HCl to
1 Liter
1 Percent Dilute 1 volum e 20 percent HCl with
19 volum es of water
Nitric Acid
Concentrated 16 Molar; specific gravity 1.42, approx. 71.5 percent by weight.
Dilute 16 Molar to 6 Molar or 6 Norm al Dilute 375 ml. co nc. HNO3 to 1 Liter
3 Molar or 3 Norm al Dilute 188 ml. con c. HNO3 to 1 Liter
Sulfuric Acid
Concentrated 18 Molar; 1762 gm . per Liter; specific gravity 1.84, 96 percent H2SO4 by weight.
Dilute 18 Molar to 6 Molar or 12 Norm al Dilute 334 ml. conc H2SO4 to 1 Liter
3 Molar or 6 Norm al Dilute 167 ml. con c H2SO4 to 1 Liter
2 Molar or 4 Norm al Dilute 111 ml. con c H2SO4 to 1 Liter
Glacial Acetic Acid

C o n c e n t r a t e d 1 7 . 4 M o l a r ; 1 0 4 6 g m . per Liter; specific gravity 1.05, 99.5 percent by weight.
Dilute 17.4 Molar to 6 Molar or 6 Normal Dilute 345 m l. to 1 Liter

5 Molar or 5 Norm al Dilute 287 ml. to 1 Liter
5 vo lum es 6 M with 1 volum e water
0.1 Molor or 0.1 Norm al Dilute 5.75 m l. to 1 Liter
Am m o n i u m H y d r o x i d e
Concentrated 15 Molar or 15 Norm al, 28.0-30.0 percent NH4OH by weight.
Dilute 15 Molar to 6 Molar or 6 Norm al Dilute 400 ml. to 1 Liter

5 Molar or 5 Norm al Dilute 333 ml. to 1 Liter
For 2 liters of solution, 6 Molar
Acetic Acid 1310 ml. water and 690 ml. Acetic Acid
Hydrochloric Acid 1000 ml. water and 1000 m l. Hydrochloric Acid
Nitric Acid 1250 ml. water and 750 m l. Nitric Acid
Sulfuric Acid 1667 ml. water and 333 m l. Sulfuric Acid
Am m o n i u m H y d r o x i d e 1 2 0 0 m l. water and 800 ml. Amm o n i u m H y d r o x i d e
Alwa ys use distilled water, and add the acid/base slowly to the distilled water.
Moderator, I submitted this to pic in the waterco oler because I am not sure what forum this inform a t i o n c o u l d b e b e s t u s e d o n
your web site. I used this information extensively while working as a chem ist and had to m ake up a lots of different solution s
and reference standards.
Frunk March 12th, 2007, 07:54 PM

Textbook and/or website rip? A sim ple google would get m e this information...
Even then, I'm h a v e n 't even finished High School yet but I can make solutions of any concentration and m olar concentration
with a periodic table...

a n d I m provised C hemistry > S o d i u m P e r b o r a t e
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View Full Version : Sodium Perborate
Bacon46 March 21st, 2007, 11:38 AM

I was doing some work in a local dry cleaning shop and ran across a 2lb (.9kg) container of Technical grade NaBO 3.
It is used a spot stain rem o v e r a n d c a n b e p u r c h a s e d O TC at the dry cleaning supply distributor. I found 81.80% NaBO3 online
$2.05 a pound in 8 pound pails at http://www.chem istrystore.com/sodium _perborate.htm
A c o u p l e o f t h i n g s I r e a d d i d m a k e m e wonder if it had any use in pyrote chnic or explosive com positions.
1. NaBO 3 releases oxygen rapidly at tem peratures over 60 C

2 . U n l i k e p e r c a r b o n a t e a n d p e r p h o s p h a t e , p e r b o r a t e i s n o t j u s t a n a d d i t i o n c o m p o u n d o f p e r o x i d e , b u t c o n tains true
p e r o x y g e n b o n d s . T h i s m a k e s t h e m a t e r i a l m o re stable, safer for handling and storage.
References:
http://en.wik ipedia.org/wiki/Sodium_perborate
It is m entioned briefly in a thread in 2001 titled Powerful oxidizers & reducing a g e n t s . h t t p : / /www.roguesci.org/theforum /
showthread.php?t=29 9&highlight=Perborate
T h e r e i s p r o b a b l y a g o o d r e a s o n w h y I h a v e n e ver seen NaBO3 called for in any pyrotechn ic com positions. All I have found is
this s tatem e nt by Ezikiel in th e a b o v e m ention ed threa d , P o t . p e r b o r a t e O x i d i z i n g p r o b e r t i e s S U C K . This could b e true but it
d o e s n t really go on to explain why.
Does anyone out there have any experience with NaBO 3 in pyrotechnic or explosive com p o s i t i o n s ?
cracker March 21st, 2007, 12:32 PM

Patent #RE 26,1088 m entions its use in a Rubberized Explosive. Use a series of search words including Sodium
Perborate,Sm o k e , E x p l o s i v e , C o m position,pyrotechnic. Enter them into the Google Patent Search and you will get a few hits.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Home Production of
Bases
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View Full Version : Home Production of Bases
PeterB2 April 9th, 2007, 01:57 PM

I've been experimenting lately with producing bases at home. From what I've read, pratically any base can be produced from Ca(OH)2 (pickling lime, hydrated lime), baking
soda, and ashes. Allow me to elaborate: heating baking soda (even on the stove in a sausepan) drives off H2O and CO2 leaving Na2CO3 (this can also be purchased cheaply
as washing soda at a grocery store; I got mine locally at Kroger).
By taking advantage of potassium carbonate's solubility in water, K2CO3 can be separated from ashes. Add hot water to ashes, let sit to separate, decant, filter, recrystallize.
Dissolve this crude product in hot water again and repeat the process to produce purified potassium carbonate. It requires a lot of ashes to get much though, but I tried it and it
works quite well!
After a bonfire, I collected all the ashes and put them into a 5 gallon bucket "for use at a later time".
Sodium and potassium hydroxide can be produced from the metathesis reaction between Ca(OH)2 and the carbonate salt. Since the Ca(OH)2 is not very soluble in water, only
sodium or potassium hydroxide will be left in the solution which can easily be filtered and recystallized.
Be careful what kind of lime you get though: limeSTONE is CaCO3, QUICKlime is CaO, and HYDRATED lime is Ca(OH)2. I bought it as pickling lime at the local Kroger for a
good amount (probably about a pound). I think you can also get it in larger quantities at the hardware store for garden use.
Most of the information I found was from http://cavemanchemistry.com/oldcave/. (Although its apparently the syllabus for a college class, this site has some great proceedures
and ideas for a home lab, everything from the production of sulfuric acid to making purifying potassium carbonate from ashes. Most of the "lab equipment" is 2 liter soda
bottles :D) Scroll down to the "Projects" section of the page, about half-way down.
Please excuse me if this is common knowledge, but trying some of this really excited me!
EDIT
I tried the link, and it works but takes a while. If it doesn't work, you might try copying and pasting the address into the URL...
DONMAN April 10th, 2007, 04:08 AM

Hah, I actually own that book. It has a very novel approach to explaining chemistry and its history.

The information is derived from even earlier works, like "The Golden Book of Chemistry Experiments." My copy dates from 1960.
Indeed the preparation of many bases can be accomplished just as PeterB2 has said.
Sodium hydroxide (lye) is made from the reaction between calcium hydroxide (slaked lime) and sodium carbonate (washing soda).
Potassium hydroxide can be made by reacting potassium carbonate (potash from wood ashes) with calcium hydroxide.
Magnesium hydroxide can be made by mixing hot solutions of magnesium sulfate (epsom salts) and sodium bicarbonate or carbonate. The reaction only happens when heated.
Magnesium hydroxide precipitates from the solution, carbon dioxide is given off,and sodium sulfate is left behind along with one of the reactants unless stoichiometric quantities
are used. If you don't have a scale try to form saturated solutions of both reactants, look up the solubility data at room temp, calculate the volumes of saturated solution to
mix to achieve a stoichiometric ratio, and commence reacting.
My parents use their fireplace quite regularly, and I can get a heap of ashes by the end of winter. It takes many hundreds of pounds of wood to fill a 5 gallon bucket with
ashes. The extraction process can be messy and dirty, but it does yield a good bit of product. I soak my ashes in hot water for a long time, filter off the charred wood bits and
insoluble mud that remains with a shop towel, filter the solution again with paper towels or coffee filters to remove small particles, boil down the filtrate to get a crop of crude
crystals, recrystallize, and filter again with filter paper to get an "acceptable" product. ACS purity this is not, but it good enough for certain applications.
I have read sodium bicarbonate (baking soda) can be converted to sodium carbonate (washing soda) by boiling a solution of the bicarb. You can just as easily buy washing
soda, but I think it may be somewhat cheaper to get baking soda in the long run; I need to check on that.
Be careful using garden lime as it is commonly a mixture of calcium oxide, calcium carbonate, carbon hydroxide, magnesium oxide, magnesium carbonate, and magnesium
hydroxide. Real lime, that is pure calcium oxide, seems to be something of a rarity around where I am. You can transform calcium carbonate (marble, chalk, seashells,
limestone) and calcium hydroxide into calcium oxide by calcining at over 1000 C.
I was reading an old analytical chemistry book last week about separating magnesium and calcium ions for the analysis of lime. Since I can get a lot of garden lime that's nice,
but with its impurities it is less than useful. Peter2B's suggestion of using pickling lime might be a better way to go since it should be pure calcium hydroxide. Calcining this
would lead to pure calcium oxide.
asilentbob April 28th, 2007, 05:03 AM

I was considering making sodium hydroxide last year via calcium oxide. I never got around to it though and ended up finding a local pure OTC source.
I was going to make the calcium oxide in an electric pottery kiln by decomposition of calcium carbonate. The main thing that set me back was possible splattering of the
calcium carbonate / calcium oxide. I didn't want to ruin the expensive kiln refractory. However, looking back this was pretty stupid as it would be contained in a covered
ceramic crucible. (Hand thrown to boot.) Sodium carbonate would be store bought for "pool maintenance."
Keep in mind that hydroxides react with CO2 in the air:

ex.
NaOH + CO2 ---> NaHCO3
NaOH + NaHCO3 ---> Na2CO3 + H2O
So if your trying to get CaO from ashes make sure to burn the fire very hot and save the ashes in an air-tight container unless your going to process them shortly. Otherwise
you might just end up with alot of carbonates.
It would be nice to see someone write up a tutorial or their experiences going from calcium carbonate all the way to around soap or technical grade sodium hydroxide.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > More powerful
Chlorates?
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View Full Version : More powerful Chlorates?
Shalashaska April 14th, 2007, 01:08 AM

While I was on Wikipedia poking around various explosive precursor files, I came across Rubidium Nitrate as a cation of KNO3.
This interested me enough to do a search for Rubidium Chlorate, for which there was no file, but there was a file on Rubidium PERchlorate.
I did some Google searches, and it turns out some rubidium chlorate is on eBay for $25 for 5 grams. Even though this would be completely financially infeasible, would
Rubidium Chlorate, Caesium Chlorate, or even (impossibly) Francium Chlorate theoretically be much more powerful oxidizers than KClO3 or NaClO3, since there is a difference
in power between the former and latter?
Ygarl April 14th, 2007, 04:03 AM

Never occurred to try elements farther down the chart. I'm not convinced that Francium would be a good choice as fooling with radioactive ingredients which are also explosive
chemically is more than a little worrying.
Of course getting it could be a more serious problem. It's usually only found as a decay product of another element
A runaway reaction of 5 grams of KNO3 + [X] may be somewhat dangerous, but Fr has a half-life of something like 22 minutes in its most stable isotope. It decays via alpha
and beta particles and at that half-life must be SERIOUSLY radioactive.
Cs could be fun though... I have seen the classic Na + water reaction any number of times of course, as well as K and Rb. Only had one chemistry teacher hard-core enough
to mess with pure Cs, and something like .05g of Cs can easily destroy a 5 litre plastic tank of water - no worries.
I'm better on the physics side personally. Anyone sharp enough at the chem side to work out the theoretical energy budget of CsNO3 (I assume...) used as an ingredient in a
simple explosive?
CsCl looks entertaining as well... Wonder if it can be used as a precursor to nerve agents.
nbk2000 April 14th, 2007, 08:12 AM

Francium is impossible to get.
Cesium is obtainable, but the cost...
Selenium has been used to make analogs of VX, replacing the sulfur, and increasing toxicity by a third.
crazynlazy April 22nd, 2007, 12:20 AM

Well, in answer to your question, yes, by moving down the periodic table you get to heavier elements. However, there are better choices than rubidium.
If by "more powerful oxidizers," you mean a more explosive compound involving a chlorate bonded to a metal, there are much better choices than those from the alkali earth
metals group. If you look at potassium chlorate there are two reasons for the stability of the compound. Firstly, potassium is a relatively light metal. Secondly, potassium
makes close and strong bonds, it being one of the least electronegative elements.
If you want a chlorate that is more energetic than the conventional potassium and sodium compounds, simply choose an element more electronegative as well as heavier than
potassium. Silver comes to mind given its weight and relative ease in obtaining. Iron and copper would probably form interesting and powerful oxidizers to a lesser degree as
well. I am interested to hear more about this topic, what does everybody else think?
sdjsdj April 26th, 2007, 11:56 AM

Wouldn't using a radioactive chlorate in HE lead to instant and - if the device were large - widespread fallout?
There still exists the problem of obtaining the stuff in the first place, though, which seems fairly daunting. For prospective homicidal psychotics with a taste for the dramatic and
a death wish, that is.
Flaire October 9th, 2008, 07:18 PM

The chlorates and perchlorates bonded to a metal like Chromium (appears it would have to be Chromium III for Chlorate) or Manganese Chlorate might have some interesting
oxidizing potentials. But Silver does seem better due to the availability...
Lewis October 9th, 2008, 10:58 PM

The heavier the metal, the more "ballast" the oxidizer must carry, all other things being equal. While the metal may be more reactive, there will always be more inert product
with a heavier element.
I'm not sure why no one has pointed this out...
Cobalt.45 October 10th, 2008, 01:17 AM

I'm not sure why no one has pointed this out...One reason might be that this has been a dead thread for the past year and a half- and for good reason, it would seem.

a n d I m provised C hemistry > C hlorine gas from K M n O 4 a n d H C l ?
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View Full Version : Chlorine gas from KMnO4 and HCl?
chembio April 24th, 2007, 09:41 AM

Yesterday, I was experim enting with KMnO 4 crystals and 33% HCl. When I added the acid to the KMnO4, the test tube m i s t e d
up (but didn't heat up) and a hissing sound was heard. A brownish, shit-like gooey m ess was formed at the bottom of the test
tube.
Then, I noticed a pungent smell-not unlike that of chlorine gas-com ing out of the test tub e. It really stank, and my dog (which
was sleeping nearby, maybe three feet away) yelped and ran off while shaking her head. My nose is still slightly raw :eek:
T h e q u e s t i o n i s : S h o u l d n ' t t h e K M n O 4 h a v e s i m ply become acidified? W hy did this reaction take place? :confused:
I repeated the experiment, and got the same results.
Are there any chem ical tests for chlorine gas that do not involve litm us paper? I've yet to renew m y supply...
Charles Owlen Picket April 24th, 2007, 11:58 AM

A daitomic gas, chlorine is a h a l o g e n w h o s e o x i d e s ( t h a t are strong oxidation agents) are easily tested for. See BERTHOLITE,
t h e n a m e o f t h e g a s a s a w e a pon utilized in WW I - for ppm, general, and qualitative testing. It's a bleaching agen t of course
s o a sim ple test (outside of sm ell & taste) is the m inor bleaching of colored pape r w h e n e x p o s e d t o s a m e.
W hen I did a search for chlorine gas within the forum I found a few things, etc. You can get off to a good start that way.
Zeitgeist May 14th, 2007, 10:38 AM

Yes, this reaction will definately produce HCl, and lots of it.
The perm anganate oxidises the Cl-.
If you want to acidify a redox reagent, you'll want something like sulfuric acid, or phosphoric maybe.
Bugger May 17th, 2007, 05:54 AM

That brown stuff form ed by reaction of perm anganate with HCl, or with an acidified solution of a chloride, would be MnO2, or a
m ixture of MnO 2 and Mn(OH)3, formed by the reduction of Mn(VII) to (IV) and/or (III). Perm a n g a n a t e ( V I I ) c o u l d b e
regenerated from this, after it is filtere d out, by reaction with alk aline hypochlorite; or m ore satisfa ctorily electrolysis in a cold
strongly alka line solution, in which the Mn would dissolve as m anganites(III) or (IV), and be oxidized by a sufficiently strong
v o l t a g e a t a n o x i d a t i o n - r e s i s t a n t a n o d e i n s t e p s to the (VII) state. There is currently a thread on sciencemadness.org/talk
about this.
DF90 June 12th, 2007, 01:21 PM

As a word of warning, do not use conc. sulphuric acid to acidify permanga n a t e s . . . M a n g a n e s e h e p t o x i d e ( M n 2 O 7 ) i s p r o d u c e d .
It is a oily green liquid that is very explosive and reacts very violently with organic m ateria l. Further inform ation about it can
probably be found by doing a search.

a n d I m provised C hemistry > P e r o x i d i z a t i o n o f N a p h t h a l e n e
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View Full Version : Peroxidization of Naphthalene
DONMAN April 29th, 2007, 10:45 PM

I was wondering if a molecule such as this could exist? (click the thumb nail for a larger im a g e ) .
http://img26 4 . i m a g e s h a c k . u s / i m g 2 6 4 / 4 4 4 1 / p e r o x i d e o e 4 . t h . j p g
Maybe you could convert the Naphthalene to Naphthalene tetrachloride then do a peroxidization reaction. As the potential
electronegativity of the C-Cl bond is less that that of the C-O bo nd.
Or, would it be possible to oxidize the Naphthalene to p hthalic acid and then preform the peroxidization? This would defiantly
be a differen t molecu le, but this may be the more feasible wrought...
This is proba bly a very KEWL question to be asking. Sorry, about that. I am looking for so m e b o o k s o n o r g anic peroxides but,
they are kind of hard to come by.... if you have any references that would be nice.
suggestions?

C - C l 3 9 7 k J m ol-1 - http://www.webelements.com /webelem e n t s / e l e m ents/text/Cl/enth.htm l
C-O 1076.5 kJmol-1 - http://www.webelem ents.com/webelem e n t s / e l e m e n t s / t e x t / O / e n t h . h t m l
W ithout consulting any of m y o r g a n i c c h e m b o o k s , I ' m g u e s s i n g t h a t y o u c o u l d d o s o a n d t h a t i t i s d e p e n d e n t u p o n t h e b o n d

energy. I'm guessing that the larger the bond enthalpy, the m o r e s t a b l e t h e b o n d ?
C a n s o m e o n e s h e d l i g h t o n t h i s ? I d i d a s e a r c h f o r " p e r o x i d a t i o n n a p h t h a l e n e " , a n d a l l I c o u l d f i n d i s s o m ething relating to

the peroxidation of eye lenses by naphthalene.
Not a kewl question I don't think at all donman .
megalomania May 1st, 200 7, 12:41 AM

Eh, I can't see the thum bnail graphic, there is nothing clickable on my end...
DONMAN May 1st, 200 7, 01:09 AM

http://img26 4 . i m a g e s h a c k . u s / m y . p h p ? i m a g e = p e r o x i d e o e 4 . j p g
Does that wo rk for you?

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > DDT, The Pesticide
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inthekitchen May 13th, 2007, 09:32 PM

I apologize if this has already been asked, I searched the forum and found one thread about DDT that mainly talked about Silent Spring, I also checked the Pesticides (http://
w w w.roguesci.org/megalomania/pest.html) section of the Controversial Chem Lab but didn't find anything. A little google searching yeilded some interesting info though.
First, there was DDT's chemical formula and model, obviously really easy to find:
Model:
http://img101.imageshack.us/img101/3443/ddtnh0.gif
Formula: C14H9Cl5
I also dug up an old article from TIME magazine [LINK] (http://www .time.com/time/magazine/article/0,9171,803716,00.html)
The part of the article that caught my eye was this:
...a Sw arthmore chemist named Walter Steuber (of Houdry Process Corp.) had decided that the easiest way to get DDT was to make it himself. He was turning it out by the
gallon in his cellar. Said Steuber: any competent chemist can figure out the formula and make DDT out of non-priority materials. The ingredients are: chloral hydrate (better
known as "Mickey Finn"), monochlor benzine, and concentrated sulfuric acid.
Assuming the above article isn't bullshit, any competent chemist could easily duplicate this Nobel Prize w inning chemical w ith the help of the above information.
But for a confused laymen with only a basic knowledge of chemistry, well--they'd have no w ay of knowing the proper ratios of chloral hydrate, monochlor benzine, and
concentrated sulfuric acid to mix.
On top of that:
Chloral hydrate is now illegal in the US--a substitute would have to be found or a knowledge of how to make chloral hydrate would have to be made.
Sulfuric acid and any kind of chlorinated benzine are also hard to get. I don't think it'd be possible today for "Homemade DDT" to be made like it was back in the 40's.
Am I w rong?
Edit 5-23-08: Dichloro-Diphenyl-Trichloroethane (keyword for searching)
sirthomasthegreat May 13th, 2007, 11:10 PM

What task are you trying to acomplish? There may be anothe chemical you could use instead of DDT. I will look up on how to make each and w hat not, but I can do just as
good of a job as you w ith google.
inthekitchen May 13th, 2007, 11:58 PM

I'm just interested in knowing if DDT can be "homemade" like it was in the 40's, or if there's any kind of "recipe" for it.

There are many types of chlorinated hydrocarbons that are good insecticides, although most are also poisonous to non-target species in substantial quantities. Solomons' Organic
Chemistry has a good description of them, along w ith their syntheses and biological effects. Others, all of them non-aromatic unlike DDT (1,1,1-trichloro-2,2-bis(p-
dichlorophenyl)ethane) and its degradation product DDE, include chlordane, lindane, aldrin, dieldrin, lindane (benzene hexachloride, C6H6Cl12, by adding Cl2 to C6H6 w ithout
removal of the Hs), mirex, and kepone. These are all cyclic chlorinated alkanes or alkenes, and, except for DDT and lindane, are all made using hexachlorocyclopentadiene
(C5Cl6) via Diels-Alder addition reactions with cyclic alkenes.
Actually, chlorobenzene, used to make DDT, is itself insecticidal. A similar compound, p-dichlorobenzene, is used as a substitute for naphthalene in mothballs, being solid with a
vapor pressure and melting point similar to those of naphthalene, unlike chlorobenzene.
Chloral hydrate is CCl3-CH(OH)2. It is used as a sleep-inducing drug, probably via metabolism into chloroform, although its liver-toxicity makes it dangerous on heavy or
prolonged use. Being a gem-diol, it is not particularly stable. It is formed on dissolving chloral (trichloroacetaldehyde) in w ater; chloral can be used in the synthesis of DDT.
The driving-force of the reaction of chloral or its hydrate w ith two molecules of chlorobenzene is the elimination of tw o molecules of water between the molecules, catalysed by
H2S04 which takes up the water. It seems unlikely that there could be any substitute for the use of choral or its hydrate. A possibility could be to react p-chlorophenol w ith
1,1,1-trichloroethane, which is a very common solvent used in dry-cleaning and produced in large amounts (as a substitute for CCl4 which is more toxic), again using H2SO4 as
catalyst to eliminate molecules of water betw een the organic molecules; but I have not heard of this being successful.
P.S. SirThomasTheGreat, - what were you knighted for, or are you a Baronet?
nbk2000 May 14th, 2007, 12:23 AM

http://ww w.versuchschemie.de/topic,6629.html
Complete synthesis. :) Article is in German, so use an online translator and a good imagination. ;)
Also, by further chlorination, you get 2,4-D>2,4,5-T>Dioxin, or at least that's my understanding of it.
Also, a Google book called "The True Story of DDT, PCB, and Dioxin (http://books.google.com/books?id=HOpcT-
KtkSwC&dq=ddt+dioxin&printsec=frontcover&source= web&ots=YpNlxBowXb&sig=0ZryXyurWDPYENnyrfpO9i5qfQo)".
Paradichlorobenzene is used as mothballs. Chlorobenzene is a toxic liquid.

http://ww w.versuchschemie.de/topic,6629.html
Complete synthesis. :) Article is in German, so use an online translator and a good imagination. ;)
Also, by further chlorination, you get 2,4-D>2,4,5-T>Dioxin, or at least that's my understanding of it.
Also, a Google book called "The True Story of DDT, PCB, and Dioxin (http://books.google.com/books?id=HOpcT-
KtkSwC&dq=ddt+dioxin&printsec=frontcover&source= web&ots=YpNlxBowXb&sig=0ZryXyurWDPYENnyrfpO9i5qfQo)".
Paradichlorobenzene is used as mothballs. Chlorobenzene is a toxic liquid.
Aw e man! This brings me frustratingly close to my goal, but my own limitations have stopped me short, I'm afraid. This full synthesis (Complete with pictures!) is awesome but I
don't have the intuitive knowledge of chemistry that I would need to understand the article from the babel fish translation.
I came frustratingly close once again after I did some digging and found the first page of Preparation of Technical DDT (http://pubs.acs.org/cgi-bin/searchRedirect.cgi/iechad/
1946/38/i09/f-pdf/f_ie50441a017.pdf) from an old chem journal, I got really excited when I read this:
Typical DDT Concentration
A mixture of 200 grams of 99.0% sulfuric acid, 74 grams (0.5 mole) of chloral purified through the crystalline hydrate, and 124 grams (1.1 moles) of technical chlorobenzene
were stirred rapidly...
Unfortunately the rest of the article requires a subscription to The American Chemical Society (http://pubs.acs.org/wls/journals/query/subscriberResults.html?
line1=Preparation+of+Techni cal+DDT&op=searchJournals&yearrange4=true&field1=atl%2Ctitle&Submit=Search) w hich I don't have and can't afford.
The article looked like it was about to give "recipe like" instructions that don't require fancy lab equipment but I could be wrong.
As far as finding a substitute for chloral or chloral hydrate, I guess I can forget that, I'll just assume the stuff is available. In the meantime I wish I could find the rest of that
article or a similar article with a "recipe like" process. Poor, uneducated me.
Major Update: Made some more progress: Even though I'm a new bie I w as able to find the original patent for the stuff:
DEVTTAIJZING COMPOSITION OF MATTER (http://www.google.com/patents?id=7zRuAAAAEBAJ&printsec= abstract&zoom=4&dq=patent:2329074)
By treating, w hile strongly stirring, a mixture of 2 molecules of benzene or chlorobenzene with 1 molecule of chloral or chloralhydrate with an excess of concentrated sulfuric acid
(of 100 percent strength) heating takes place after same time, w hich first increases up to about 60 degrees C. and then slowly decreases again. Stirring is continued until the
reaction mass has cooled down to room temperature and contains solid particles. Then it is poured into much water w hereby the raw condensation product separates out in a
solid form. It is well washed out and, after being recrystallized from alcohol, it is obtained in form of white, fine crystals w hich show a w eakly fruit-odor.
Now, being the "blow your fingers off" layman that I am, I probably don't understand the above description the way a chemist would, this is what I think he is saying:
1.Rapidly Stir 2 parts benzene and 1 part chloral w ith 3 parts sulfuric acid.
2. The mixture should heat up to 60 Degrees C. Stop stirring once the mixture gets back down to room temperature.
3.Pour the mixture into a bucket of w ater, the ddt should condense out in chunks.
I don't know w hat it means to "well wash out" or "recrystallize in alcohol"
I know most of the chemists on this forum probably look upon me with contempt, and w ith good reason, but I'm begging ya for help here!
Am I completely off on the process? What does it mean to "w ell w ash out" and "recrystallize in alcohol" I thought the ddt was already crystallized after being added to the
water?
Any advice I'd appreciate!
nbk2000 May 14th, 2007, 03:55 AM

Someone here does have access, so don't be surprised if a copy of that article pops up here soon. :)

Someone here does have access, so don't be surprised if a copy of that article pops up here soon. :)
Explosives and Weapons Forum: 1

University Library: 0
Enkidu May 14th, 2007, 08:04 AM

Monochlorobenzene sells on eBay for $30 per 500mL. It has a wide range of uses as a solvent, and I do not believe it is a suspicious reagent.
On the other hand, chloral hydrate is not an inconspicuous chemical. You cant buy it unless you have a license because it s used as an anesthetic. Chloral hydrate can be made by the
chemistry hobbyist. Its synthesis is similar to chloroform, IIRC.
I dont think your yields will be good (pos sibly nonexistent, I dont really know) without oleum. You would certainly need 98% conc. sulfuric acid. With your chemical know ledge,
inthekitchen, you c ant m ake oleum. SO3 is very dangerous. (Actually, you shouldn't do any of this synthesis, noting that you do not even know what molar ratios are.)
If I have time, I will comment more upon this synthesis.
I quickly checked the following excerpt for OCR errors. I believe I caught most of them.
From Vogel s Practical Organic Chemistry:
The name D.D.T. is derived from dichlorodiphenyltrichloroethane: this is a misnomer since the name represents 27 different compounds. As commonly employed it refers to 2 :
2-bis(p-chlorophenyl)-l : 1 : 1-trichloroethane. It is conveniently prepared by the condensation of chlorobenzene and chloral hydrate in the presence of concentrated sulphuric
acid:
[Shows monochlorobenzene + chloral hydrate --> D.D.T. product]
Method 1
In a 1 litre three-necked flask, equipped w ith a thermometer, glycerine-sealed mechanical stirrer (compare Fig. II, 7, 10) and calcium chloride (or cotton wool) guard tube,
introduce successively 700 g. (380 ml.) of concentrated sulphuric acid, 100 g. (53 ml.) of oleum (20 per cent. S03), 90 g. (81-5 ml.) of chlorobenzene and 68 g. of chloral
hydrate. Stir the mixture rapidly enough to keep the materials well mixed for 1 hour: during this period the temperature rises to about 50 and some granular D.D.T. separates.
Stir the mixture for a further 1 hour in order to complete the reaction. Pour the reaction mixture with stirring into 3 litres of a 2 : 1 mixture of ice and w ater. Filter the
precipitated somewhat sticky solid at the pump and wash it well with cold water. Remove the occluded acid by transferring the crude product to a beaker containing 1 litre of
boiling water and stirring w ell: this causes the D.D.T. to melt. Decant the aqueous layer, and repeat the washing with tw o further 1-litre portions of water. To the third washing
add a little sodium bicarbonate and stir until the mixture is neutral to litmus. Filter at the pump, and dry upon filter paper in the air or in an air oven at 50-60. The yield of crude
product, m.p. ca. 90, is 90 g.; the low m.p. is due to the presence of isomers of the para compound. The pure substance, m.p. 108, may be obtained with 50-60 per cent,
recovery by recrystallization from n-propyl alcohol (5 ml. per gram).
Method 2
Place 17 g. of chloral hydrate crystals and 25.5 g. (23 ml.) of chlorobenzene in a 500 ml. Pyrex glass-stoppered reagent bottle and warm on a water bath, with occasional
shaking, until all the crystals have dissolved. Cool to room temperature and slowly add 180 ml. of concentrated sulphuric acid. Secure the glass stopper (rubber tubing over
stopper held tightly by copper wire round neck of bottle) and shake mechanically for 1 to 1 -5 hours, and then allow to stand for 15 minutes. Pour the contents of the reagent
bottle slow ly and with constant stirring into 700 ml. of water contained in a litre beaker. When cold, filter the crude D.D.T. through a sintered glass funnel and w ash several
times with water. (A further 1 -5 g. of impure D.D.T. may be obtained by diluting the filtrate considerably.) Transfer the solid to a beaker and stir it for 5-10 minutes w ith 50 ml.
of 2 per cent, sodium carbonate solution or 4 per cent, sodium bicarbonate solution. Filter and w ash with distilled water until the filtrate is neutral to litmus; suck the solid as dry
as possible. Transfer the residue to a small mortar, add 100 ml. of ethyl alcohol and triturate with a pestle for 5-10 minutes. Filter through a dry Buchner funnel, wash twice with
25 ml. portions of ethanol, and continue the suction until most of the solvent has been removed. Dry the residue at 70 in a steam oven (or on a water bath). The yield of
D.D.T., m.p. 107, is 15 g. The perfectly pure compound, m.p. 108, may be obtained by recrystallization from n-propyl alcohol (5 ml. per gram).

Drat, are there no easier to obtain pesticides that match ddt's effectiveness? Well, looks like the obstacles remaining include:
1.Obtaining choral hydrate

2.Obtaining all the lab equipment (Vacuum pumps, filter funnels, etc. aw fully pricey probably run near $100 bucks, and I wouldn't use it that often)
3.Obtaining ethanol, unless using "denatured ethanol" at 75% is not a problem.
4. Obtaining a mechanical shaker (500 dollars and up, unless I made one)
I guess when they say ddt is cheap and easy to make they mean from the perspective of an industrial chemist.
Alexires May 14th, 2007, 09:35 AM

*w histle* Hang on there inthekitchen.
Here is a little high school chem for you. It will make your life ALOT easier if you can get your mind around it.
Lets start with a nice simple equation and work from there (I'm not being patronizing).
HCl + NaOH-> NaCl + H2O
You get that right? You add some acid (hydrochloric acid) to some base (sodium hydroxide) and you get a salt (sodium chloride - table salt) and some water.
If you think about it this w ay now
1(HCl) + 1(NaOH) -> 1(NaCl) + 1(H2O)
So, we know that one molecule of HCl reacts with 1 molecule of NaOH to form 1 molecule of NaCl and 1 molecule of H2O. Normally when we write chemical equations, we just
get rid of the ones and assume they are ones unless stated otherwise.
But the problem is, how many HCl molecules are there in your 10mL test tube?
We know that every element has its own "mass" which w e call the "molecular mass" or "atomic mass". For instance, if you look at any decent periodic table, somewhere in
each element square you will see some numbers designated as the "atomic mass". Hydrogen is roughly 1.008, Carbon = 12.011, Oxygen = 15.9994 etc. You should be able to
find the number I'm talking about.
Now, here comes the mind bending bit. If you have 12.011g of Carbon, you will have 6.023x1023 atoms of carbon. If you have 1.008g of hydrogen, you have 6.023x1023
atoms of hydrogen. If you have 15.9994g of Oxygen, you have 6.023x1023 atoms of oxygen.
See the pattern?
But, I can hear you screaming, how does this help? Well, the same theory applies for different compounds. If we go back to our example of HCl + NaOH, we can now say this.
We know that HCl has a total atomic mass given by atomic mass of Hydrogen + the atomic mass of Chlorine. 1 atom of hydrogen is bonded with 1 atom of chlorine
Or, in otherwords 1.008+35.45= 36.458. This is the atomic mass of a HCl molecule. If w e relate this back to 6.023x1023 (otherwise known as Avogadro's Number), we know
that in 36.458g of PURE HCl there is 6.023x1023 molecules of HCl.
If w e now run it for NaOH, we know that its atomic mass is 39.9974 (22.99+ 15.9994+1.008) so that if we have 39.9974g of PURE NaOH, there is also 6.023x1023 molecules of
NaOH. We can also say that there is one MOLE of NaOH or HCl (because there is 6.023x1023 molecules of each)
Hence, if you wanted to completely neutralise 1 mole of NaOH (which weighs 39.9974g) you would add 1 mole of HCl (which weighs 36.458g)
Get what is happening so far?
Now, if we relate this back to the article that you posted here, w e see that it says
By treating, w hile strongly stirring, a mixture of 2 molecules of benzene or chlorobenzene with 1 molecule of chloral or chloralhydrate with an excess of concentrated sulfuric acid
(of 100 percent strength) heating takes place after same time, w hich first increases up to about 60 degrees C. and then slowly decreases again.
Ok, so 1 molecule of Chloral (CCl3CHO) is reacted with 2 molecules of Benzene or chlorobenzene (C6H6 or C6H5Cl respectively). We since we know how much of each element
there is in in both chloral and either benzene of chlorobenzene, w e can w ork out its atomic w eight.
I'm just going to use Benzene and Chloral, cause that will make it easier.
So, we now know that Benzene has at atomic weight of (6x12.011)+(6x1.008) or 78.114, and chloral has an atomic weight of 147.38. So, finally, we work out that for every
156.23g of benzene (or two moles), we need 147.38g of chloral (which is one mole) for it to react in a 2:1 MOLAR ratio.
Sounds strange huh?
It takes a while to get your head around.
I only took the time to tell you this because you look like you actually want to learn something and aren't just a kew l looking for some spoonfeeding.
If you have any difficulties, PM and I'll help you as best I can.
Anyone see a problem with my explaination, go ahead and say something.
Also, note inthekitchen, that the % of acids correspond to how many HCl or HNO3, etc molecules are in there in relation to the water. PURE HCl is actually a gas, and will
dissolve into water, but the maximum HCl acid you get is about 33% I think. So, if you needed 10g of PURE HCl, then you would need 30g of your 33% acid, or there about.
Edit: Just read your latest post inthekitchen. If you can buy the vacuum gear and you plan to continue w ith this hobby BUY IT. Vacuum pumps, vacuum traps and reduced
pressure gear is GREAT to have.
Why obtain Chloral or Chloral Hydrate? Make it. If you have vacuum gear, you can make almost ANYTHING. Same deal with the ethanol. Get your vodka or whatever you are
using, toss it into the vacuum flasks with some sulfuric and distill off the ethanol.
Improvise my friend. You have a drier? A washing machine? Make something that holds your container you want to shake and attach it (temporarily) to the drier/w ashing
machine w hile it is running. The shuddering while it is on spin cycle will shake it. You don't need to fork out money, you just need to think about it abit.

Your explanation made perfect sense, with some fervent references to a periodic table and a working calculator I should be able to determine the necessary amounts to meet
the proper molar ratios.
I was thinking of just giving up and seeing if any of the stuff was still for sale. There is a farmer selling some ddt but he is selling it for over 500 dollars a pound! I'm assuming
its stuff left over from the pre-ban days.
I guess my only option is to buy the equipment and use my dryer as a shaker (or I could tape a vibrator to a wooden plank and a slinky, that would be more cost effective).
Anybody know a landlocked (not online) store I could pick up glass supplies, like a chain or a specific type of store I should look for in the yellow pages?
In the meantime I'm off to read Process of Manufacturing Chloral (http://www.google.com/patents?id=IfhFAAAAEBAJ&printsec= abstract&zoom=4&dq=chloral)
nbk2000 May 14th, 2007, 01:19 PM

Acronyms are usually capitalized, so it's DDT, not ddt. ;)
Making chloral isn't too terribly difficult to do, as you simply pass dry chlorine gas through anhydrous ethanol, slowly warming it up to reflux, so as to replace some of the
hydrogen in the ethanol with chlorine.
You can find the process (copied from Dick's) in the PMJB, Vol 1.

I have had several methods of making DDT lying around here for a few years now; I guess it is about time I actually added the info to my website. I love pesticides and
herbicides precisely because everyone else hates them :)

You say you have "several methods of making DDT lying around". Besides the w ell-known one involving chlorobenzene and chloral, do any of the other methods include
reacting p-chlorophenol with 1,1,1-trichloroethane (a very common solvent used in dry-cleaning and produced in large amounts as a substitute for CCl4 which is more toxic),
again using H2SO4 as catalyst to eliminate molecules of water between the organic molecules, as I suggested as another possibility above? Has anyone tried this?

I don't rightly know because I have misplaced the folder that contains the references. I know that it is in my brow n leather folder, I remember putting my CW information there,
but for the life of me I can't find it.
I am in the midst of putting all of my files into a filing cabinet I purchased into distinct folders by compound. What prompted this is a massive stack of journals I requested that I
have no god damn idea why (it is not obvious what compound of interest I wanted from the article)! As of now many files are lumped into bins and folders. I have not
prioritized the CW info very high, so it is still disorganized.
In short, bugger, I can't answer your question...
Enkidu May 17th, 2007, 08:45 PM

Do any of the other methods include reacting p-chlorophenol with 1,1,1-trichloroethane, again using H2SO4 as catalyst to eliminate molecules of water betw een the organic
molecules, as I suggested as another possibility above? Has anyone tried this?
I'm sorry Bugger, but I don't think this idea w orks. Do you have a reference for it or is it something you came up with? If you have a reference, please post it; otherwise, please
explain your reasoning. For a long time I didn't know how to begin to understand what you proposed. This lack prevented me from responding to your idea.
Unfortunately, I believe the best you could hope for w ould be 4-chloro-3,5-sulfonicphenol dissolved by trichloroethane. You can't remove the -OH from a benzene ring easily.
Even if you could, the best you could hope for would be di(4-chlorophenyl) ether through the Williamson Ether Synthesis.
I will explain the current method of production of DDT. As I have never seen anyone elses mechanism for this reaction, my explanation is only as good as your faith in my
knowledge of chemistry.
In an extremely concentrated, acidic solution, H2O becomes a good leaving group. Take, for example, chloral hydrate. The H2SO4 protonates the OH on the 1 carbon, and the
OH2+ leaves (and becomes regular water), creating a carbocation. (A carbocation is a positively charged carbon atom. A carbocation has only three bonds, instead of the
desired four.) The H2O is immediately eaten by the SO3, which produces another molecule of H2SO4.
The formation of the carbocation is in preparation for the electrophilic aromatic substitution of the p-chlorobenzene. Chlorine (or any halogen) is an ortho / para deactivator, so
the substitution w ill occur at para (4) position, respective to the Cl. The pi bond on the benzene ring jumps out and attacks the carbocation. The 3 carbon on the benzene ring is
now positive. The HSO4- pulls off the hydrogen on the 4 carbon, and the electrons from the carbon-hydrogen bond reform the pi bond.
A nitration is another instance of electrophilic aromatic substitution. It uses the nitronium ion (NO2+).
The second chlorophenyl group is attached in the same manner.
Another (just as likely) mechanism involves the chloral hydrate being turned into chloral first. Its mechanism is similar to what Ive just written.
inthekitchen June 3rd, 2007, 09:22 PM

Quick Question Enkidu, do you have the page number for that ddt synthesis in vogel's? I got a'hold of the 5th edition but can't seem to locate it in the index? Are you using an
older version?
Enkidu June 11th, 2007, 03:56 AM

@inthekitchen: It's on page 1011 of Vogel's Practical Organic Chemistry, 3rd ed. I don't think the 5th ed. contains the synthesis.
junk12 June 11th, 2007, 06:47 AM

Alexires, very nice post. I appreciate an effort. For some of us, w ho are members of this forum and our first profession isn't chemistry related, here and there is useful to recall
some of high school chemistry that was forgotten.
Enkidu May 23rd, 2008, 01:47 PM

Preparation of Technical DDT.
H. S. Mosher, M. R. Cannon, E. A. Conroy, R. E. Van Strien, D. P. Spalding
Ind. Eng. Chem.; 1946; 38(9); 916-923. DOI: 10.1021/ie50441a017
Apparently the upload feature isn't working for me. I'll upload the article later if somebody reminds me (or I remember).
russoc4 May 24th, 2008, 12:15 AM

Here's a copy of that article. Not the best quality scan. This is the first time I've seen a poorly scanned ACS article, though:
http://rapidshare.com/files/117166131/ddt_synthesis.pdf.html
Maybe these patents w ill shed some light on chloral (or not)
http://ww w.google.com/patents?id=Q11vAAAAEBAJ&dq= 2615049

http://ww w.google.com/patents?id=0lFPAAAAEBAJ&dq=2702303

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > H2O2 out of a new
fuel-cell?
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View Full Version : H2O2 out of a new fuel-cell?
Saugi May 17th, 2007, 10:22 AM

A few years ago, the japans discovered a new way to produce H2O2 up to 3,5% in a new invented fuel-cell.
I wonder, if this method has established today and if we can make this work at home - which would be very interesting. Is someone here who has more informations about
that?
This is the article about the new fuel-cell:
A new fuel-cell concept for the catalytic production of hydrogen peroxide

08 Aug 2003 - Hydrogen peroxide is an important industrial reagent, which is used in such processes as the environmentally friendly bleaching of paper and wastewater
treatment. Current industrial methods for the bulk production of H2O2 are expensive, both in terms of energy and cost. A new method developed by Japanese researchers
could form the basis of a new, substantially more economical process.
Ichiro Yamanaka's team has been working on the catalytic conversion of hydrogen and oxygen into hydrogen peroxide. A mixture of hydrogen and oxygen is highly explosive.
Yamanaka and his co-workers thus chose a method that guarantees a controlled reaction, even though the two volatile reactants never come into direct contact:
electrocatalytic conversion in a fuel cell. The special advantage of this concept is that the energy released in the reaction can be captured in the form of an electric current. The
researchers have now further improved their original fuel cell concept.
The secret of their success is a three-phase interface within the cathode, the negative electrode. Rather than introducing oxygen in an electrolyte solution, as was done
previously, a stream of oxygen gas is introduced directly onto the solid, but porous, cathode. The other side of the cathode contains a dilute sodium hydroxide solution as an
electrolyte, which also enters the pores. This allows for higher oxygen concentration on the inner electrode surface, allowing in turn for a higher conversion. Hydrogen gas is
directed in a similar way onto the equally porous anode.
A further crucial improvement lies in the enclosure of the electrolyte solution within cathode and anode areas by a semipermeable membrane. This solves another problem that
plagued the previous version of the fuel cell; the hydrogen peroxide formed at the cathode no longer has access to the anode, where it would decompose to form water. Last
but not least, the efficacy of the catalytic graphite electrodes was increased by the inclusion of various additives.
Even when air is used in place of pure -- expensive -- oxygen, the output of the fuel cell is high enough. This renders the concept an economically interesting alternative for
the bulk production of hydrogen peroxide.

A very interesting find. I did a little checking on professor Yamanaka, who is an associate professor in the Department of Applied Chemistry at Tokyo Institute of Technology.
Based on his publications, all of his research is electrochemical in nature, with particular attention on hydrogen production and fuel cell technology, as well as oxidations.
He has four published journal articles about electrochemical hydrogen peroxide production, at least with English titles that I could read, only one of which I was able to
obtain, the paper that Saugis news article referred to. The latest two articles only came out last year, one in Chemical Letters, which is a Japanese publication I do not
have access to either electronically, or in the stacks, and the other has a Japanese title I can not read.
Here is the abstract from professor Yamanakas latest publication in Chemical Letters 35, 12, 1330-1331, (2006).
Electrocatalysis of Heat-treated MnPorphyrin/Carbon Cathode for Synthesis of H2O2 Acid Solutions by H2/O2 Fuel Cell Method
Ichiro Yamanaka1), Takeshi Onizawa1), Hirobumi Suzuki1), Noriko Hanaizumi1) and Kiyoshi Otsuka1)
1) Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology
(Received August 21, 2006)
Mnporphyrin supported on active carbon, which was activated by heat-treatment in Ar, electrochemically catalyzed reduction of O2 to H2O2 by the H2/O2 fuel cell
method. The electrocatalytic activities were strongly dependent on the heat-treatment temperatures. The maximum H2O2 concentration of 3.5 wt % with 47% current
eff iciency was obtained for the catalyst treated at 450 C, and a TON (Mn) for the H2O2 formation was over 1000 h1
On closer examination of the news article that Saugi posted shows a bit of a percentage discrepancy. The news article says the process can achieve a hydrogen peroxide
concentration of 3.5%, but the journal article says the maximum concentration they obtained was 7% using an improved setup. Using pure oxygen they reached a
concentration of 7% in only 2 hours at a current efficiency of 94%. Using air, instead of the much more expensive oxygen, they reached a concentration of 6.5% in 3 hours at
a current efficiency of 88%.
The setup does not strike me as something very OTC, but if one were to buy the electrodes and build the cell they could manufacture their own hydrogen peroxide in a very
compact and energy efficient setup. I imagine this would be of particular interest to model rocket enthusiasts who consume rather large quantities of hydrogen peroxide, and
who have their own distillation or concentration apparatus.
The only raw materials consumed in the reaction are air and electricity, the most plentiful OTC substances besides dirt and water. Sodium hydroxide is used as an electrolyte,
but I am not sure it is consumed.
Since I doubt my describing the C liffs notes version of the setup would do it justice, Ill just reproduce that snippet. There are no actual experimental details per se, just
a description of the setup. I dont know much about applied electrochemistry, but I gather these techniques are quite well known to the authors, so they feel no need to
describe the experimental procedures. I am trying to learn about electrochemistry in greater detail this summer, but I am having trouble finding that ultimate book where they
tell you HOW to do the reactions. I found plenty of analytical fluff and theoretical mumbo jumbo.
The article from Angewandte Chemie International Edition (the thank god they finally publish in English edition), 42, 3653-3655 (2003)
Direct and Continuous Production of Hydrogen Peroxide with 93% Selectivity Using a Fuel-Cell System
Ichiro Yamanaka,* Takeshi Onizawa, Sakae Takenaka, and Kiyoshi Otsuka
We propose a new concept and a new fuel-cell setup for the synthesis of H2O2 in order to increase the concentrations of O2 at the cathode at atmospheric pressure. Our idea is
an application of a three-phase boundary (gaseous O2, aqueous electrolyte, and solid cathode) for the formation of H2O2, (Figure 1b). If a porous membrane electrode is
used, a high partial pressure of O2 (101 kPa, 45 mm) can be applied directly to the active site at the three-phase boundary.[12]
Therefore, the reduction of O2 to H2O2 should be accelerated, and the successive reduction of H2O2 to H2O should be decelerated.
The porous cathode was prepared from carbon powder (vapor-grown carbon-fiber (VGCF), 13 m2 g_1, Showa-Denko Co.) and poly(tetrafluoroethylene) powder (PTFE, Daikin
Co.) by the hot-press method.[13] The anode was also prepared from VGCF, PTFE, and Pt-black powders by the hot-press method. Pure O2 (20 mLmin_1) and H2 (20
mLmin_1) were supplied. The yield of H2O2 was determined by titration against KMnO4, and the current efficiency was calculated based on the two-electron reaction. The
current efficiency corresponds to H2O2 selectivity based on H2.
It is well known that graphite electrodes are active for the electrolysis of O2 to H2O2 in alkaline solution.[2,3] We chose VGCF as the cathode material because it has good
graphitic structure and high chemical stability. First, the one-compartment cell (system 1) was used for the direct synthesis of H2O2 over the VGCF cathode with NaOH solutions
(2 molL_1) at 298 K (Figure 2a). The concentration of H2O2 increased with reaction time and showed an upper limit of 2.2 wt% at 2 h. The current density gradually decreased
with reaction time and was almost constant (70 mAcm_2) at 2 h (Figure 2b). Therefore, current efficiency (H2 selectivity) decreased with reaction time from 80% at 10 min to
38% at 2 h. In other words, the H2O2 yield decelerated with reaction time.
Although the one-compartment fuel cell described above (Figure 1b) was indeed effective for the production of more concentrated H2O2 solutions, the final current efficiency of
38% was not enough. We assumed that catalytic decomposition or reduction of H2O2 over Pt-black is occurring. Therefore, the electrolyte compartment was divided into two
compartments (1.18 mL each) separated by a cation
membrane (Nafion-117, DuPont) to prevent diffusion of H2O2 from the cathode to the anode sides (system 2). Cationic species can pass from one side to the other but anionic
species cannot. In alkaline solution hydrogen peroxide is present as HO2_.[2, 3] Therefore, we assumed that the diffusion of HO2_ could be controlled by the Nafion
membrane.
When we tested the two-compartment reactor the concentration of H2O2 increased with the reaction time and reached 4.2 wt% after 2 h with a high current efficiency of
93.7% (Figure 2a). The separation of the lectrolyte compartment was very effective for H2O2 production. In contrast to system 1, however, the current density in the system 2
decreased remarkably with reaction time (Figure 2 b), which is a serious problem. We have observed that the electrolyte volumes in the cathode and the anode smoothly
increased and decreased, respectively, with charge passed. It could be estimated that six to seven molecules of H2O diffused from the anode to the cathode per each electron
passed. In system 2, H2O coordinated to Na+ should be carried from the anode to the cathode. The decrease in the amount of electrolyte in the anode should cause the
decrease in the current density.
To fill up the anode, the NaOH electrolyte was injected (1.5 mLh_1) with a microsyringe pump (system 3). The stability of current density was considerably improved (Figure
2b). The concentration of H2O2 smoothly increased and reached 6.0 wt% after 2 h with a high current efficiency of 93.5%(Figure 2a). The upper limit of the concentration of
H2O2 was observed after 2 h, but the H2O2 yield increased linearly with reaction time. The upper limit of the H2O2 concentration was due to the increase in the volume of the
H2O2 solution. That is, system 3 produced H2O2 solution at a concentration of 6 wt% continuously with high current efficiencies >90%.
To further optimize the production of H2O2 the ratedetermining step in the system 3 was studied electrochemically. The open circuit voltage of the system 3 was 0.919 V
(cathode potential: _0.102 V, anode potential: _1.021 V vs Agj AgCl). The over potential of cathode was 0.550 V and that of anode was 0.230 V at 70 mAcm_2. IR drop of the
electrolyte was 0.095 V (electric resistance of NaOH electrolyte: 1.35 Wcm) and that of the Nafion membrane was 0.044 V (resistance of Nafion in NaOH: 34.6 Wcm). These
data suggest that the cathode reaction, the reduction of O2 to H2O2, limits the reaction rate of the system 3.
We have improved the electrocatalytic activity of the VGCF cathode by including several additives. We found that the addition of a small amount of carbon-black
materials, Black Pearls 2000 (1475 m2 g_1, Cabot Co) and Valcan XC-72 (254 m2 g_1, Cabot Co.), to the VGCF cathode increased the current density and the
formation rate of H2O2 by a factor of more than 1.4 with high current efficiency. We chose cathode components of VGCF (70 mg), XC72 (10 mg), and PTFE powder (7
mg) after many tests, because high activity and good reproducibility were obtained. The time course of H2O2 formation by the cell using the new cathode and anode
(system 4) was shown in Figure 3. The concentration of H2O2 increased rapidly, comparable to that in system 3, and reached 7.0 wt%with 94% current efficiency at 2
h. The rate of H2O2 formation (2.0 mmolh_1cm_2) in system 4 was 1.7 times greater than that in system 3 (1.2 mmolh_1cm_2). The current density of system 4 (100
mAcm_2) was comparable to that of the electrolysis method (80120 mAcm_2).[2,3]
In all of the experiments described pure oxygen (P(O2)=1atm) was used for the synthesis of H2O2. If we could use air (P(O2)=0.21atm), production costs could be cut
tremendously. When air was used for system 4, the concentration of H2O2 increased smoothly with reaction time and reached 6.5 wt% with 88% current efficiency at 3 h. The
formation rate of H2O2 (1.3 mmolh_1cm_2) and a current density (78 mAcm_2) were slightly reduced when air was used, but performance was still very good. This result
suggests that the fuel-cell method (system 4) has a great advantage for the industrial production of H2O2.
In conclusion, the H2/O2 fuel-cell method showed very good performance for the selective and continuous synthesis of H2O2 because gaseous O2 could be supplied directly to
the active site (the three-phase boundary) in the cathode, and the successive reduction of H2O2 over the anode could be avoided. If the apparent surface area of the
electrodes of the system 4 could be increased to 1m 2 with the same performance (current density: 100 mAcm_2 (1000 Am_2) and current efficiency: 93%), aqueous alkaline
solutions of 7 wt% H2O2 could be produced continuously at a rate of 8.3 Lh_1m_2.

a n d I m provised C hemistry > H 2 O 2 h e l p
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futuredictator May 31st, 20 07, 04:0 8 AM

Hello, I know this is my first post, and I hope I don't get banned, I used the search but couldn't find an answer. I just dropp e d
a c h u n k o f m y hom e m a d e i r o n o x i d e i n t o a c u p o f h 2 o 2 a n d t h e i r o n o x i d e b e g a n t o f i z z . C a n a n y o n e o f h i g h e r i n t e l l i g e n c e
plea s e e x p l a in to me what exactly is happening in this reaction? thank you in advance.
Cindor May 31st, 20 07, 04:4 0 AM

I think your Iron Oxide is acting as a catalyst in the decomp. of the Hydrogen Peroxide
Rbick May 31st, 20 07, 10:4 8 AM

I would recomm end reading this article (http://pubs.acs.org/cgi-bin/abstract.cgi/e s t h a g / 1 9 9 8 / 3 2 / i 1 0 / a b s / e s 9 7 0 6 4 8 k . h t m l) for
a com plete explaination of wh y this is happening. This is an entire article of a stu d y d o n e o n t h e s a m e reaction. But what
Cindor said is, in short, correct. Your Iron Oxide is a catalyst to the H2O 2 , c a u s i n g i t t o r e l e a s e a n o x y g e n a t o m a n d b e c o m e
water.
Just out of curiousity, what were your intentions of m ixing Iron O xide with H2O2? The Iron is already oxidized, and H2O 2 is an
o x i d izer. If you want to m a k e m o r e I r o n O xide, you can do the old 5th grade experiment where you put an iron nail in som e
water and run an electrical current through it. Or you could put Fe in H2O2 and add a catalyst to speed the oxidation process, I
think... Anwa y, just thought I would ask.

a n d I m provised C hemistry > Nitrowool?
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powium June 16th, 2007, 11:34 AM

Today I was experim enting with a possible way to m a k e s o m e fuse, by n itrating wool. I thought I m ight end up with a sim ila r
product to the nitrocellulose I made yesterday using a sim ilar method with absorbent paper.
5 0 m l 70% nitric acid and 50ml 98% su lfuric acid was added to a beaker. The temp rose to 40deg C. 1.2m wool in 6x 20cm
p i e c e s w a s a d d e d o v e r 2 0 m ins. The wool turned orange then disintegrated, so I was not a b l e t o m a k e f u s e out of it, but I
t h o u g h t w h y n o t k e e p g o i n g a n d s e e w h a t h a p p e n s . T h e s o l u t i o n w a s a t 3 0 d e g a t this stage, so I heated to 50deg and let sit
for 10 m inutes. The mixture was dum p e d i n t o 2 0 0 m l co ld water.
http://img2.freeimagehosting.net/uploads/c2829933c7.jpg (http://im g2.freeim a g e h o s t i n g . n e t / u p l o a d s / 6 e 6 6 c 4 e a e d . j p g )
A sticky white plastic precipitate form ed. This was extracted, washed with a hot NaHCO3 so ln, then hot water. This photo shows
the precipitate on paper towel after it was washed:
h t t p : / / i m g 2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / a d e deb3665.jpg (http://img2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / 8 2 097b4f10.jpg)

h t t p : / / i m g 2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / 3 e 5 fc3367a.jpg (http ://im g2.freeim a g e h o s t i n g . n e t / u p l o a d s / a 5 5 1 4 f a 9 f 3 . j p g )
The substance was dried in the oven, then looked like this:
h t t p : / / i m g 2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / a d 5 b633b28.jpg (http://img2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / 2 6 5 e 9 5 e 3 f f . j p g )
h t t p : / / i m g 2 . f r e e i m a g e h o s t i n g . n e t / u p l o a d s / 0 0 a ce bc3 6f .j pg (ht t p://i mg2.f reei ma geho s t i ng.net /upl o a ds /7a 8 e01517e.jpg)
I tried to ignite the substance, and while hard to ignite it did burn, but not deflagrate by any mean s, and the burn was barely
self sustaining.
Does anyone know what it is?
nbk2000 June 16th, 2007, 12:16 PM

L o o k s l i k e C r a c k e r - J a ck popcorn! :D

I h a v e h a d n itrocellulose behave in a sim ilar m anner, likely due to a low nitrogen content. The ancients nitrated everything
back in the day, according to the Encyclopedia of Explosives and Related Item s... It says they usually heated the m aterial
bein g nitrated (including wool) to boiling. It ma k e s s o m e picric acid... that m ight explain your yellow coloration in the picture.
O t h e r t h a n t h e f o r m a t i o n o f s o m e picric acid I can't find any other m ention of nitrated products from wool.
Picric acid soaked into wool so unds pla usible fo r what you are experiencing.
simply RED June 17th, 2007, 06:27 AM

W ool is a polypeptide, nitratin g it is as hard (or impossible/im practical) as nitrating a m i x o f a m i n o a c i d s .
DONMAN June 24th, 2007, 03:59 AM

I t l o o k s l i k e a b i g m a s s o f c a s e i n o r s o m e other protein as Red previously stated.
s-lab June 24th, 2007, 04:25 AM

You need to use a +75% nitric acid. What you saw was the sulphuric acid acting on its own to in a way decom pose the cotton
with a little nitration to partially nitrated cellulose, the precitipate you saw.
Cindor June 25th, 2007, 02:47 AM

s-lab the thread is about nitra ting wool not cotton.
powium why don't try renitrating it ?
The Laughing Jackal October 2nd, 2007, 10:48 PM

I think keratin is m uch too large and com plex of a molecule to be nitrated, cellulose is a sim ple hydrocarbon C6H10O5 while
keratin is a 20 am ino acid long protein. In all likelihood , the acids broke down the proteins into their basic peptides which a
s m a ll percentage of may have had a successful nitration. I think that it is more likely that the nitric acid nitrated another
component included in the wool that you used. It sound s like it burned m ore like potassiu m n i t r a t e s o a k e d paper m o r e t h a n
anything. But then again, wool is fairly fire retardant. Any particu lar sm ells that went along with the burning? (hopefully not the
horrid burning hair/wool smell.) I would like to know mo re, especially if you achieve a successful nitration. Just the name of the
explosive would strike fear into the hearts of your enem ies, NITRO W O O L!!
Charles Owlen Picket October 3rd, 2007, 10:28 AM

There was a tim e when I nitrated horn, wool, & indigo as the original picric acid experiments. I was quite successful with Indigo
(->picric acid) with virtually little adjustm ent from a nitration of p henol. However, as I rem e m ber in those in stances the
m aterial was treated w/ H2SO4 prior to the nitration - with wool and horn this technique broke them down to a virtua lly
unusable point.
I d o r e m e m ber the horn issue; I used HNO3 (@70%) and allowed it to in itially interact with the ground m aterial for 3 days (this
was from a text writte n in 1879 & reprinted). Afterward the material was nitrated in the manner typical of ph enol (w/ raised
temp & m ixe d acids). The resultant wa s picric a cid, however the yields we re quite sm all fro m the initial weight of the m aterial.
The only material tha t cam e close to p henol was Indigo in term s of weight/yeild and nitration action (the re verse; using H2SO 4
a s a starting point.
The point re; keratin is a good one as this is a very com p l e x m olecule and would exist within both. Most all organic materials
that nitrate successfully appear sim p l e m olecules at the starting point of nitration. The above wool experim ent would have
c o m e c l o s e ( I M O ) if the tem p were mo nitored and perhaps raise d in relation to the actions of the m ixed acids.
The Laughing Jackal October 3rd, 2007, 11:56 PM

T h e e x t r e m e ly low pH of the solution would defiantly denature keratin, Cellulose is a fairly sim ple organic m olecule, keratin is
a l o n g c h a i n e d ( 2 0 a m ino acids long) protein. Meaning that you would be nitrating only certain amino acid(s) and would
probably not achieve a very high yield of nitrated (m y guess is less than half of the acids would be nitrated) Even with
m onitored te mperature. IF however, this by som e way unbeknown to me works out - defin itely som ething I'd like to try.
Secong Nature Novem ber 12th, 2007, 10:28 PM

Have you tried dissolving it in acetone to try an d filter out the un-nitrated wool?

a n d I m provised C hemistry > Ignition Tem p e r a t u r e s
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dbooksta June 17th, 2007, 01:30 AM

Curious how sensitive various formulations are to heat, so I rigged up a platform outside supporting a 1/4" steel plate over a
propane torch. I put a sm all sam ple of KClO4/Al flash p owder on the plate and let it warm up. I wa s taking its temperature with
an infrared thermom eter and was surprised to see it topped out at 800F with no ignition! I'll buy a MAPP cylinder to see if I can
get it hotter.
I know the flash goes with a p yro match but I don't know how hot those burn. I also know I can ignite it with NiCr wire, but th e
m elting point for NiCr is 2500F so that leaves a very broad range!
P l e a s e c o m m ent if you have:
* Any other tricks for testing ignition or explosion tem peratures using am ateur equipm ent.
* Figures on ignition or burn tem p e r a t u r e s o f p y r o / e x p l o s i v e c o m p o u n d s .
nbk2000 June 18th, 2007, 04:20 PM

Try covering the mixture with som e insulation, to keep the heat retained within th e m ix, rather than radiating off.
Of course, th a n y o u c a n ' t u s e a n I R t h e r m o m eter....got a thermocouple?
Charles Owlen Picket June 22nd, 2007, 11:38 AM

I don't really know any "tricks" but I do know that design of the test can be a tough thing to develop. Heat and direct
stim ulation via open flam e are two differing stim ulus. As you know flame s m ay be com posed of differing fuels resulting in
differing tem ps but the flam e itself is a differing stimulus than heat radiated directly (or indirectly) upon a substance.
Testing is no t an easy thing to set up without som e thought to the design of the stim ulus. Im pact testing may contain frictio n
in it's design, etc.
dbooksta June 22nd, 2007, 12:34 PM

I imagined that would be the case; at this point I'll lim it m yself to non-reactive (i.e., not burning) heat sources.
C a n h e a t i n g e l e m ents ever ca talyze ignition at a tempe rature lower than pure radiation/conduction would? E.g., could
im m ersing a NiCr or other metal wire in the com p o u n d a n d h e a t i n g i t f r o m that give different results than som e theoretically
inert heat source in contact with the com p o u n d ?
Or can I safely ignore such "catalytic" effects if we're talking about pyro com p o u n d s a n d m etallic heaters?
Charles Owlen Picket June 23rd, 2007, 11:12 AM

Superficially (I am NO T a rese arch scie ntist) it seems th e Nichrom e wire method of heat testing would seem i d e a l . S a m e
leng th, sam e level of current/voltage, tim e during and tim e of heat transmission, etc. But to address m o s t o f t h e s e q u e s t i o n s ,
I would find a guy who did a chem thesis & have a chat. I'll bet I'm m i s s i n g s o m ething.

a n d I m provised C hemistry > C all for Papers.
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sbovisjb1 June 18th, 2007, 01:41 AM

A website called awarenetwork, is starting a zine. They are a reputed hacking group, which is now starting to write a
collaborative document. One of the options are lethal drugs. I am presenting to opportunity to all interested from roguesci.
This is not a prom otion is any way, but rather a chance to let your skills shine. Th e l i n k c a n b e f o u n d h e r e .
http://www.awarenetwork.org/etc/

a n d I m provised C hemistry > Polyhydrocarbon
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flashpoint June 26th, 2007, 10:25 AM

Ok, well I've been to several places looking for plastics, to store some m ixes in. I prefer not to use Polyhydrocarbon for the
s a k e o f b e i n g a b l e t o store wet AP and MEKP, and other stuff :eek: Any ideas or brand nam es I ca n look for? I've b e e n
everywhere looking and even fuckin' googled it. I reque sted on another forum , and they are not sure, either. Anyway hopefully
I d o n ' t g e t b a n n e d f o r this dum b a s s q u e s t i o n ; )

By p olyhydrocarbon, do you m e a n p l a s t i c s m a d e from p olymerized organics. Finding a plastic not made from a hydrocarbon
base would be a tall order. I think by definition that's what all plastics are. Maybe something old like bakelite or m e l a m ine
would fit the bill.
DF90 June 26th, 2007, 06:55 PM

If by not poly(hydrocarbon) you m ean not a plastic m ade of just carbon and hydrogen the re are a few options. There are
therm oset plastics (form a l d e h ydes) lik e b a k e l i t e a n d m e l a m i n e a s M e g a lom ania suggests... Another possibility is to use a
polyester... as you have not d efined whether it needs to be a polym er or not, another option is epoxy (ano ther thermoset).
However you will need to check the compatibility of the substance with the plastic to make sure the re is no unwanted reaction.
flashpoint June 26th, 2007, 08:52 PM

Acco rding to, http://www.roguesci.org/theforum /showthread.php?t=349&highlight=MEKP, which was orginally by Vegeta...it says
not to use th at to store MEKP.
I'm guessing because it will soften/me lt the plastic...like PVC cleaner/prim er does to PVC fittings b efore you glue th e m .
nbk2000 June 27th, 2007, 07:15 AM

Glass.
.........................
Microtek June 27th, 2007, 07:16 AM

I'd try a PE o r PP container anyway; they are quite resistant to m ost solvents. If that doesn't work you could always go for a
PTFE container which would be very expensive but is im pervious to alm ost any chem ical.
DONMAN July 7th, 200 7, 05:30 AM

W ell I have a plastic bottle that was for nail polish rem over that I am currently using to store sm a l l v o l u m e s o f a c e t o n e . O n the
bottom it says diamond plastic inc. . It seem s to work fine for m e, so if you need some thing to store non-polar liquids I would
start in the n ail polish rem ove r section and look for plastics. Glass nail polish bottles are excellent for storing MEKP. :)
stupid939 July 7th, 200 7, 04:11 PM

I would try storing your various chem icals in HDPE (high density polyethylene). Th ey are resistant to things like acetone, many
acids (including nitric) and things of this nature. I would thing these would be your best bet.
http://www.usplastic.com /catalog/product.asp?catalog%5Fnam e=usplastic&category%5Fnam e=14952&product%5Fid=14915
These bottles are nice, and if you look around the site, you will see that Nalgene is a brand nam e that is pretty well respected
and not too expensive. Take a look at those Teflon bottle prices... $53 for a 4oz wide mouth.

a n d I m provised C hemistry > Acids, Equ ations & other ba sic questions
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HVD July 25th, 20 07, 10:0 6 PM

This is a very newbie question but I'm g e n u i n e l y i n t e r e s t e d i n s o m e b a s i c c h e m istry to aid m e in the practical sense i.e.
m aking substances.
I notice sometim es an explosive nitrate is m ade using Nitric acid only (i.e. RDX) but other tim e s e x p l o s i v e s c a n b e m a d e v i a
concentrated Sulphuric acid and a nitra te (like Potassium Nitrate). W hy is this? For instance why can ETN be made with KNO3
and H2SO4 while RDX cannot (I assum e a s I ' v e n e v e r s e e n i t m e n t i o n e d ) .
Nitration equations:
I want to figure out how much (proportionally) NH4NO3 I need to add to H2SO 4 for ETN synthesis.
So, the initial reaction goes:
NH4NO 3 + H2SO4 => HNO3 + (NH4)2SO4
Yes? Now I think I need to balance the equation to figure out how m any m oles of NH4NO 3 to add to a given quantity of H2SO 4
... am I roug hly along the right lines here?
Many thanks and sorry for the basic questions.
The_Duke July 25th, 20 07, 11:2 1 PM

B a s i c q u e s t i o n s w e d o n t m ind answering, but when it is clear that you haven t s e a r c h e d f o r t h e a n s wers yo urself first, well that
we just don t like. A m e m b e r s u c h a s y o u rself, b e i n g h e r e f o r a s long as yo u h a v e , s hould know this by now... :rolleyes:
T h e s e q u e s t i o n s y o u a s k e d h a v e b e e n a s k e d m o r e t h a n o n c e , s e a r c h i n g would have turned up the answers you seek.
UTFSE first and you will find th at you receive a better response, from m yself at least.
Enkidu July 26th, 20 07, 01:4 2 AM

http://xsorbit29.com /users5/crucible/index.php?topic=1 22.0
I wouldn't trust all the inform ation in that thread.
You're wrong on one point.
H2SO 4 + XNO3 ---> HNO3 + XHSO4 (the persulfate)
akinrog July 26th, 20 07, 06:5 4 AM

H2SO 4 + XNO3 ---> HNO3 + XHSO4 (the persulfate)
It m ust be hydrogen sulfate (or bisulfate) not persulfate. Persulfate is a term used for peroxidized sulfate salts and acid.
However, if it's dehydrated it form s pyrosulfate (XS2O 7).
Regards.
stephenb25 July 26th, 20 07, 07:1 1 AM

http://www.roguesci.org/theforum/showthread.php?t=2758&
This thread is all about why sulfuric acid is used. A simp le search would h ave found this as well as a few others. I think you
s h o u l d r e s e a rch before you ask som e simple questions which have easy to find answers.
As far as how m uch to use you should just work out the equations or if you don't want to do that I can find the link to the
program I s o m e t i m es use to solve the m a n d s e n d i t t o y o u i n a P M .
Enkidu July 26th, 20 07, 07:5 9 PM

It m ust be hydrogen sulfate (or bisulfate) not persulfate.
Ah, you're absolutely right. My m istake... I som ehow mistyped that.

a n d I m provised C hemistry > chem istry books
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JohnSmith August 24th, 2007, 10:26 AM

I have starte d this topic, in the hope, that the panel will be able, to provide som e wisdom, as to where certain books can be
bought.
A lot of interesting, and necessary works, can b e had,by downloading via rapidshare, or google.books or any other "sharing"
system for that m atter.
A so lution, to be great full for,no doubt,and useful for b ooks or texts tha t aren't too long.
S o m e o f t h e s e b o o k s , n a m e l y t h e m ore scientific ones, are heavy tom es, consisting of several hundreds of pages. It is rather
u n p l e a s a n t , a t l e a s t i n m y experience, to read such a work on a CRT or flat screen.
Recently,I have been searching high and low, to find a copy of the four volumes of T. Urbanski, an author, no doubt, known to
this panel.
None of the big houses, that trade on the net, have any copies, and a local "real life search" didn't do any good either.
As this work is about 3000 pages, there isn't a hope, that I would be able to read this on a screen, without busting an vein...
So, is there any m e m ber, of this forum , that would be able and willing to advise on a vendor of these book s , a n d / o r b o o k s o f
this nature?
It would have to be som ebody who was willing to send merchandise overseas and is trustworthy.
I h a v e t h e U r b a n s k i v o l u m es on pdf, but printing 3000 pages, is not really a solution either...
nbk2000 August 24th, 2007, 10:53 AM

These people might have a printed copy:
http://rocketsciencebooks.home.att.net/encyc-explosives.htm l
Or, if that's not it:

http://www.worldcatlibraries.org/oclc/92 19102?sloc=Belgium
Go there and steal it.
Enkidu August 24th, 2007, 05:03 PM

Don't steal it. Librarie s are awesom e. :D
The first volume of Urbanski is approximately 700 pages. Here in the US, I believe a black and wh ite printout costs $0.08 per
page. Binding is an extra $5. So 700 x $0.08 = $56 plus the cost of bind i n g . Y o u h a v e a b o o k i n h a n d f o r a b o u t $ 6 5 . T h a t ' s a
g o o d d e a l , c o n s i d e r i n g the first volum e will cost you several hundred U S D I I R C .
Of course, you'd need to be a little bit sneaky. The book is still under copyright (I suppose).
chemdude1999 August 24th, 2007, 07:10 PM

If you have a laser printer, you have a nother option:
In m y experience, a normal toner cartridge will give you a good box (5000 sheets) of print-outs (text). So, for about $150 (the
cost of a cartridge) you can have the whole damn thing printed out.
T h e n t a k e t h e a d v i c e a b o v e a n d g e t i t b o u n d . Y o u c a n a l s o u s e t h e p o r t f o l i o b i n d ers that have the long m etal strap s to bind it

(sorry, I forget the proper name for those). W ith this method, only you will know you possess the "evil" information.
Good luck.
JohnSmith August 27th, 2007, 12:30 PM

Thank you all for your replies.
I haven't fou n d t h e b o o k s I w a s l o o k i n g f o r i n t h e s u g g e s t e d p l a c e s , b u t t h e f i r s t l i n k , t h a t n b k 2 0 0 0 g a v e , h a s s o m e o t h e r
item s of great interest!
As far as che mdude1999's suggestion goes,as to printing the whole thing on a laser printer...
well I guess, that I wouldn't have much other options, a s the m arket see ms 'dry' for these volumes.
I have an old 4L (HP) and two new generic cartridges, so that should be m ore the n enough, but I will end u p binding the whole
thing in about fifteen separate volume s, as m y ring binder system (punches 21 square holes,then binds the lot with one of
those plastic spines) doesn't take m ore then 200 pages.
T h e p d f ' s I h a v e a r e a g o o d a nd professional quality,so it should work,as the printer is old, and of low resolution,you need
decent file quality.
An there is indeed, a very valid point, in the rem ark, that it is nobody's beeswax, if you print it out and bind it, there being no
record of sale for the books.
Because,not before long, these things will be 'red flagged' no doubt,if they aren't already...
I was even very surprised, tod ay when I was ab le to buy a couple of litres of nitric 69%, without anybody raising an eyebrow,
are even asking a question...
That too,will not last,as I understand,that som e countries have already p ut in restrictions for this com p o u n d .
As far as books are concerned, is there no way, that we,here on the forum , can't compile a pdf library,with high quality files,and
easy downloads (as opposed to 'rapidshare')?
Surely, there m ust be a safe and discrete way?

Maybe the m oderators have som e ideas and/or suggestions?
nbk2000 August 27th, 2007, 01:50 PM

Surely, there m ust be a safe and discrete way?
Maybe the m oderators have som e ideas and/or suggestions?
W e've got a private FTP that we use fo r such th ings. :)
Ask tm p to create a folder on it for you, and upload.
If you show that you can contribute (upload) unique content (not som eth ing we've seen a hundred tim e s b e f o r e ) o f r e l e v a n c e
to E&W , you get to download as well, from over 150GB of content (and growing). :)
JohnSmith August 31st, 2007, 10:06 AM

I have been uploadin g like mad!
Since I have been in contact, with 'tmp ' a n d s o m e stuff was cleared up,I am busy trying to get som e 2 Giga on the FTP site.
Most of the stuff is of a mechanical nature, and has to do with engines, steam e n g i n e s , m achining , lathes and milling
m a c h i n e s , s o m e chem i c a l a n d s o m e o n e x p l o s i v e s .
I h a v e a c o m plete index, of what the end result should look like .

So if any of you would like a copy of this (text) file, please send m e a m e s s a g e a n d I w i l l g e t a m ail you a copy strait away.
For reasons unknown to m e, the uploa ding goes very slow at tim es,so it can be a while be fore the com plete lot is on the
server; please be patient.
If any of you would be in need of a file, that is not uploaded yet and that is on the index; let me know, and I can a lter the
uplo a d s e q u e n c e .
For now, all is to be found under "upload/library"
megalomania S e p t e m b e r 3 rd, 2007, 02:57 PM

Offe ring books for do wnload directly from the website would not only consum e vast am ounts of bandwidth due to our
popularity, but it would expose Rogue Science to the po tential legal snag of copyright violations. Due to the nature of our
discussions, and the nature of any books we would offer for download, we have m a n y e n e m ies who are actively suppressing us.
I can't give them any fuel for the fire. Any download system o f b o o k s a n d d o c u m e n t s c r e a t e d b y i n d e p e n d e n t i n d i v i d u a l s i s
entirely their affair because all we have here are links. W e are not responsible for a sim ple link, I can't vou ch for what the
REST of the Internet is doing, legally speaking, so we can't be held responsible.
sbovisjb1 S e p t e m b e r 3 rd, 2007, 03:42 PM

But remem ber. If someone in a country such as the U.S wants you . THEY WILL try everything to get you. R e m e m ber they
break their o wn laws and often are under the impression that their laws are the worlds laws.
Hirudinea S e p t e m b e r 3 rd, 2007, 08:35 PM

...I will end up binding the whole thing in about fifteen separate volum e s , a s m y ring binder system (punch es 21 sq uare
hole s , t h e n b i n d s t h e l o t w i t h o n e o f t h o s e p l a s t i c s p i n e s ) d o e s n ' t t a k e m o r e t h e n 2 0 0 p a g e s .
If you want to give it a shot m abye you can m ake your own paperback, heres a link...
http://www.m othteeth . c o m / b o o k m a k i n g / p a p e r b a c k . h t m l
JohnSmith S e p t e m b e r 6 th, 2007, 11:47 AM

T o a d d r e s s s o m e o f t h e c o n c e r n s o f ' M e g a l o m ania':
All the books under the directory Upload/Library, are fre e of copyright.
This because of their age....
'Hirudinea': Thanks for the link!

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Isopropyl Nitrite
synth gone WTF
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View Full Version : Isopropyl Nitrite synth gone WTF
Omniknight August 25th, 2007, 04:01 PM

So, usually i produce isopropyl nitrite using :
Sol A - 250gr sodium nitrite dissolved in 450ml water

Sol B - 70ml 66% h2so4 in 450ml water
And 300ml isopropanol. Sol A + ispropanol then i add sol 2 to get the iso.nitrite.
This day instead of isopropanol i used isobutanol. Instead of producing the desired yellow layer, the whole shit turned green, then a dark green layer pumping red smoke
started to form in place of the expected one.
I know the error is having used isobutanol, i'm just wondering if one of you guys could light my candle about what was that scary smoke ?
Was pretty irritant too.
Enkidu August 25th, 2007, 05:58 PM

nbk's not banned you yet? You must be favored by the gods... or his ban button is broken.
The 'red smoke' you saw was a cloud of NOx, the product of a runaway reaction. You didn't keep the reaction temperature cool enough. (You need to keep it around 0-5*C.)
It's possible to die from the inhalation of NOx; a condition called pulmonary edema that manifests itself about 24 hours after exposure is the common killer. By the time you
notice the symptoms, it's usually too late to reverse the condition.
Whether you're trying to make 'poppers' or some amphetamine analog, this board isn't the right place to ask about it.

I hope you had some logical motive in mind when substituting a different reagent into a synthesis OTHER than "if the chemicals sound the same they might react the same?"
Why has he not been banned? Well we have living (for the time being) proof of how ignorance and stupidity can lead to tragedy during chemical experimentation. The
misinformed experimenter haphazardly chucks some random reagent into his stew pot and it produces a toxic gas. I wonder if he is surprised many of us know fully well what
chemicals are drug precursors...
nbk2000 August 26th, 2007, 04:54 AM

I may not need to ban him.
If he breathed enough of the 'scary red smoke', he'll be banned from life within 48 hours. ;) :D
Omniknight August 27th, 2007, 01:42 AM

Well we have living (for the time being) proof of how ignorance and stupidity can lead to tragedy during chemical experimentation.
Let me remind you that without people who had enough balls or were curious about things you wouldn't have any of the chemical knowledge you have now.
So my suggestion to you is start behaving like any reasonable person and educate those who are still newbies.
Oh, btw, take your ego and pound it with salt while you're at it.
Enkidu August 27th, 2007, 02:02 AM

Let me remind you that without people who had enough balls or were curious about things you wouldn't have any of the chemical knowledge you have now.
Hmmm... well, nobody wants to be the first one to figure out that rattlesnakes are poisonous. I wonder who the poor guy was that did that research or if science ever properly
thanked him? :rolleyes:
The simple reaction you're doing now has been done by thousands of people before you. You don't have to be curious, because the literature (or even a texbook) contains all
the answers and is there for the taking, if you'd only do a little research.
BTW, we aren't compelled to educate anyone. My first post WAS spoonfeeding. You forgot to thank me.
Vitalis August 27th, 2007, 02:04 AM

I think they practice "tough love" around here, hence the insults.
Anyway, you already said yourself you knew the reason for the "synth gone WTF" was using isobutanol instead of the isopropanol you knew you should have used, and Enkidu
told you the smoke was NOx, what more education do you need, be sure to use isopropanol next time.
nbk2000 August 27th, 2007, 04:41 AM

Balls and Brains are often mutually exclusive terms.
Why is it that people who don't use their brains, usually accuse those who do of having no balls?
Also, why are you making IPN? I doubt you intend to use it as thermobaric fuel.

Because it's legal (at least here), cheap to make and has a resell value of ~1500% ;):p
Might use it one day if i'm making cyanide, but i don't have enough furnitures right now :(
BTW, we aren't compelled to educate anyone. My first post WAS spoonfeeding. You forgot to thank me.
Actually, lots of books/videos/whatever media state the reaction with butanol is as valid as the propanol one, so i just tried and went "uuuuuh, wtf?!" when it got out of control
:/
Thx for the answer anyway ^^

Enkidu August 27th, 2007, 07:05 AM
He's making isobutyl nitrITE rather than isobutyl nitrATE. Poppers.
Actually, lots of books/videos/whatever media state the reaction with butanol is as valid as the propanol one, so i just tried and went "uuuuuh, wtf?!" when it got out of control
:/
The reaction with isobutanol is just as valid; you fucked up when you (obviously) didn't keep the reaction cold enough.
nbk2000 August 27th, 2007, 10:23 AM

I knew what he making it for, this isn't something new.
You used to be able to buy nitrite's for use as 'Air Freshener', with names like RUSH, and such.
First amyl, then butyl, then they banned it altogether using the Analogs Act.

The reaction with isobutanol is just as valid; you fucked up when you (obviously) didn't keep the reaction cold enough.
Still doesn't explain why this whole shit turned dark green when it's supposed to go bright yellow/slightly orange.
Not cold enough ? The flask was under crushed ice, if that's not cold enough i can't figure it out...
And before you say it, both solutions and the alcohol were in the freezer for about 1 hour before starting ^__^
:confused:
Vitalis August 28th, 2007, 01:36 AM

Is the hive still around? I don't think so, too bad really, they would have LOVED to answer your precursor chemical or inhalant "synth" questions...
Gammaray1981 August 28th, 2007, 06:00 AM

If you still have no idea, UTFSE for "nitration". Most of the topics you get will (quite rightly here) be explosives related, but you'll be told what went wrong. Runaway nitrations
(nitritions?) have been previously covered in significant detail. The dark green colour accompanying it doesn't appear to be uncommon.
chemdude1999 August 28th, 2007, 08:36 AM

Oh, btw, take your ego and pound it with salt while you're at it.
You hint at your possible illegal activity and then insult the one man that might have your IP address. Use your head, dude.
Mega doesn't need your insults. He is providing a board for us (including you, for the time being) to exchange ideas and information. Show some appreciation.
And stop making drugs.

And stop making drugs.
1/ It is legal where I am located.
2/ It's not illegal to sell it, even in the united states, as long as you sell it as a video head cleaner or cyanide countermeasure.
nbk2000 August 28th, 2007, 10:08 AM

People who use inhalants tend to have gratefully short lifespans.
The guy making the inhalants seems to be on a collision course with the grave.
+++++++++
I got a PM from the disphit complaining about my warning him about i/I. Oops...seems he tripped over The Beast's tail and fell headlong into the pit. :)
Guerilla August 28th, 2007, 10:19 AM

The green color comes from N2O3 of which formation from NOx is favored by lower temps. So you obviously had cool enough solutions but it's of no use if you just dump the
IBA/NaNO2 mix into the acid all at once and/or lack decent agitation.
You should have at least said you were going to use this as a diazotization agent, when it comes to poppers they are the TOE poppers we're most interested in here.. ;)
festergrump August 28th, 2007, 03:21 PM

Aren't poppers kind of a faggot's drug, anyway? So, if you use it, you're probably a fag; if you sell it to fags you are a faggot sympathizer; and if you get busted for selling it,
you get to live with the fags and queens who'll likely turn you out while in the pokey...
Hmm...
Methinks you need to concentrate on a good dose of pussy instead of poppers, at least before all those fags "rub one off" on ya for being such a good sport to them. :eek:
Vitalis August 28th, 2007, 05:01 PM

I think the Beast has devoured and shit this poor soul out by now, so he can't reply...
Cindor August 29th, 2007, 01:59 AM

festergrump Poppers are used by gays because they have tha property of relaxing the spchincter.

Thank you Cindor, I have unwillingly assimilated this fact. I am now compelled to repeat it to strangers who will question my sexuality. Now then, how do YOU know such a
fact, eh? :D
Cindor September 23rd, 2007, 05:48 AM

Hahahaha that was very funny. A friend told me that, and I just serch it in wiki
http://en.wikipedia.org/wiki/Poppers#Effects
Inhaling nitrites relaxes smooth muscles throughout the body, including the sphincter muscles of the anus and the vagina.[5] This causes the blood vessels to dilate (which
causes a sudden drop in blood pressure), increases heart rate, and produces a sensation of heat and excitement that usually lasts for a couple of minutes.[8]
Thermiteisfun September 23rd, 2007, 11:23 AM

You know if you're not banned by now, you have provided me with the best laugh ever...Red smoke? Irritating you say?
If he breathed enough of the 'scary red smoke', he'll be banned from life within 48 hours. :D
Secong Nature November 11th, 2007, 04:18 AM

On the topic of muscle relaxants I have heard that N2O is just as useful when it comes to precursors to homoerotic adventures.
Also if the resale value he stated is true here as well then I may make this and sell it to 'connoisseurs of illicit substances'
A search of the internet later found that there are few websites stating the relaxing properties of nitrous oxide, though I did find an online document supporting this called:
'EPINEPHRINE-INDUCED DYSRHYTHMIAS:
COMPARISON DURING ANAESTHESIA WITH NARCOTICS AND WITH HALOGENATED
INHALATION AGENTS IN DOGS'
it states:
IT IS GENERALLY BELIEVED that the use of a

narcotic-nitrous oxide-muscle relaxant technique,
popularly known as "balanced anaesthesia". . .
Hope it helps anyone hoping to widen (among other things) their sexual horizons.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Why KNO3 sucks for
nitrations
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View Full Version : Why KNO3 sucks for nitrations
Rbick September 15th, 2007, 10:06 PM

I think I have finally figured out the age old question as to why KNO3 creates a thick syrup thats impossible to manage when used in a nitration reaction. No its not because
you let the temperature get to high or because you added too much Potassium Nitrate... It really seems quite simple, I just never really looked in to it. I will also being going
over a few things about nitrations that I have always wondered about. The reaction between H2SO4 and KNO3 goes as follows:
H2SO4 + 2KNO3 ---> K2SO4 + 2HNO3
The resulting compounds are obviously Potassium Sulfate and Nitric Acid. The Sulfate is not of use, and it is the Nitric acid that we are after. Now lets look at a nitration mixture
with Ammonium Nitrate and Sulfuric Acid, which is known for not becoming a thick slurry during the nitration process:
H2SO4 + 2NH4NO3 ---> 2(NH4)2SO4 + 2HNO3
These products are Ammonium Sulfate and Nitric acid. Ok Well what is the big deal? I believe that part of the answer is in the properties of the two byproducts: Ammonium
and Potassium Sulfate.
Potassium Sulfate is described as being a very hard substance. Along with that, it also only dissolves at about 11g per 100 mL of water. If there isnt enough water for the
Potassium Sulfate to dissolve into, then it will obviously come out of solution as a solid. 11g per 100 mL is very low considering if we look at Ammonium Sulfate, which
dissolves at 70g per 100mL of water. The one thing I am unsure of is how much each dissolves in Sulfuric Acid or whether they do at all. I dont think this would change my
conclusion in this matter.
Well where does the water come from? Hopefully I will be able to answer that using ETN as an example. In the process of nitration, a byproduct is often water. This can be
seen here in the following example. I will use pure HNO3 in the equation for clarity. Also, Erythritol has the formula of C4H10O4 and is a natural sweetener. Four nitro groups
replace four of the H atoms and bond to the Oxygen, creating C4H6N4O12. This is known as an O-nitration.
4HNO3 + C4H10O4 ---> C4H6N4O12 + 4H2O
The water seen in this reaction would actually be absorbed partially, if not fully, by the Sulfuric acid. In a nitrating mixture involving no nitrate salt, this is a reason for the
Sulfuric Acid (Ill get into this later). However, one thing I have noticed is that the directions for nitration reactions using a nitrating salt either dont have enough Sulfuric Acid, or
they use too much. Usually the latter. Of course it cannot be assumed that you can get everything perfect, but I sure as hell like to try. Anyway, the water from the resulting
nitration is what I assume is part of what dissolves the byproducts in the reactions. With Potassium Sulfate not dissolving nearly as well as Ammonium Sulfate, and being
classified as brittle and hard, it comes out of solution and makes a hard, thick solid mess. I also took a look at some pure Ammonium Sulfate in my chemistry class, and it
seems to be a soft, fine white powder. I assume this is why KNO3 is not suitable for nitrations. In conclusion, I would much rather use Ammonium Nitrate in my nitrating mixes,
as I prefer swirling as opposed to breaking stirring rods. But if I had no other options, Potassium Nitrate still gets the job done. You just have a little extra work to do.
Now as for the role of Sulfuric Acid: As mentioned earlier, the Sulfuric is used to absorb water from the resulting nitration and act as a catalyst, driving the reaction. Unless of
course if you are using a nitration salt, in which case the Sulfuric is also used to make HNO3 through the reaction with the nitrating salt. Sulfuric Acid is not always needed in
some reactions. For instance, RDX and PETN can use 95% or higher HNO3 alone. What happens when the Sulfuric Acid mixes with the water is as follows:
H2SO4 + H2O --> H3O+ + SO4 -
This creates a positively charged Hydronium ion and a negatively charged Sulfate ion. The two bond to form Sulfuric Acid Hydrate, or H2SO4*H2O. This is how Sulfuric Acid
absorbs the water. If you can, visualize the Water and Sulfuric Acid sharing a Hydrogen atom. Sulfuric acid hydrate can be turned into steam from the exothermic reaction
with water, which is corrosive and dangerous. Remember, add acid to water, not water to acid :D.
I think that excess Sulfuric Acid could be partially responsible for bad yields with nitration salt mixtures. In this case, the unused Sulfuric might react with un-nitrated Erythritol
(like it does with other organic substances), pulling out the Hydrogen and Oxygen to make water, and leaving a carbon byproduct.
H2SO4 + C4H10O4 ---> 4C + 4H2O + H2
Other mols of Sulfuric would react with the 4 mols of water to form Sulfuric Acid Hydrate.This is why when Sulfuric comes into contact with anything organic, it leaves a black
residue, or in the case of skin, causes a burn. This makes Sulfuric Acid useful to make compounds anhydrous. I think this is what happened once while I was making ETN. I left
the nitrating mix to go get a drink with my buddy and came back a few hours later. I didnt think Id be gone that long But the mixture turned into a clear liquid with some
black stuff floating at the bottom. This is just an assumption, but it makes sense.
So hopefully this is why Potassium Nitrate serves as such a bad nitration salt in nitration reactions. If this is completely wrong or you have more to add, by all means, correct
me. I would also like to hear any other nitrating salts others have found to work well in this type of nitration.
Charles Owlen Picket September 15th, 2007, 10:52 PM

I think you are on to something....your conclusion to the basic premise makes sense (to me).
However I would also add that there is the variable of impurities and particulate consistency. And this is an issue that occurs when working from home & not a good lab (such is
life when one is not in school :-).
I have had success with KNO3 but the material could not be impure nor in a solid crystalline form. I have had difficulty with NaNO3 but when reducing the size of the particulate
it was workable (when adjusting for weight, etc). Yet, when using NH4NO3 I have had variances that were traced to both of the above idiosyncrasies of the starting chemical.
In fact your idea was interesting me so much I re-read it a few times (good stuff). I think something is missing from the concept of the direct combination of KNO3 & H2SO4 in
a nitration....Now I could be dead wrong but would that not be potassium bisulfate? Potassium bisulphate is KHSO4 and I had thought it was also known as "pyrosulfate" -
extracted from nitrations and used for making 'blue" in some pyro-related comps. HOWEVER I could be off on this as I also remember some concept of adding potassium
sulfate to H2SO4 to obtain olium.....
Rbick September 16th, 2007, 12:36 AM

I wondered the same thing about potassium bisulfate being produced. Although after researching, all the info I found pointed to Potassium Sulfate being created when
Potassium Nitrate was mixed with Sulfuric Acid. I passed it by my Chemistry professor and they said that this would most likley be the case. Potassium Hydroxide is mixed with
Sulfuric Acid in the production of the Potassium bisulfate.
To test the idea, I may later mix some Sulfuric Acid with Potassium Nitrate and check solubility and melting point to see if I can identify the product. Potassium Sulfate has a
much higher melting point (1069 *C) than the bisulfate (214 *C).
Enkidu September 16th, 2007, 02:02 AM

Thanks for the expose.
H2SO4 + 2KNO3 ---> K2SO4 + 2HNO3
The resulting compounds are obviously Potassium Sulfate and Nitric Acid.
Doesn't sulfuric acid + potassium nitrate ---> nitric acid and potassium hydrogen sulfate (KHSO4)?
There are varying opinions on this, but I believe the above equation.
H2SO4 + 2NH4NO3 ---> 2(NH4)2SO4 + 2HNO3
These products are Ammonium Sulfate and Nitric acid.
Same idea as before; a hydrogen sulfate forms.

Also, I've heard it's possible to dehydrate(?) ammonium nitrate with sulfuric acid. I think there's a thread at SM about this, or maybe it's at the APC. I can't remember. (If you
remember, please post it.) Anyway, you end up with a partially useless nitrating mixture.
H2SO4 + H2O --> H3O+ + SO4 -
Your equation's not balanced; you need another H on the products side.
Edit: I somehow missed that Charles and Rbick already discussed what I posted...
Charles Owlen Picket September 16th, 2007, 10:20 AM

To test the idea, I may later mix some Sulfuric Acid with Potassium Nitrate and check solubility and melting point to see if I can identify the product.
Sounds right on the money to me!
I really miss having a "mentor" of sorts to go to as at university (a professor). I hope that others with interest or greater knowledge chime in here; this subject has "wings" if
applied to most every nitration.
@Enkidu - I thought it was potassium hydrogen sulfate also after a bit..... I don't have the background to say conclusively.

Sorry about the Sulfuric Acid and water, it just isn't completed. Call me lazy if you will... :o I think the correct one is:
H2SO4+ H2O H3O+ + HSO4-,
and
HSO4- + H2O H3O+ + SO4-
So the hydrogen sulfate reacts with the water to form the Sulfuric Acid Hydrate.
But after researching, Ammonium and Potassium Sulfate are produced through reacting Ammonium and Potassium Nitrate with Sulfuric Acid 2:1 moles. I wasn't able to find any
temperature specifics though. Again, the one way to make sure is by doing some tests and see what I come up with.
Charles Owlen Picket September 16th, 2007, 10:59 AM

Another thing occurred to me; we are speaking of nitric esters here when discussing ETN and related nitrations. Nitrations of polyols are usually straight forward. Nitro benzenes
like Picric Acid may yield differing side reactions when utilizing the solid nitrates.....I was thinking of the different nitration formats where a solid nitrate may be used....
Rbick September 25th, 2007, 03:53 PM

Well you guys were right. The byproduct is in fact the bisulfate and not the sulfate. So it would be
H2SO4 + KNO3 ---> HNO3 + KHSO4
Products being nitric acid and potassium bisulfate. Non-the-less, my statement still stands. The Ammonium Bisulfate is very hygroscopic and readily absorbs water, whereas
Potassium Bisulfate does dissolve in water but not nearly as well.
Charles: I think I know what you're talking about. In nitrations for picric acid and whatnot, the Sulfuric Acid is used to absorb water and act as a catalyst in the reaction,
reforming itself at some point and reacting again. With polyols it is just used for dehydration, I think...Anyone know about this? There is a chapter in one of my books at home
about this specifically. I'll have to check it out.
Charles Owlen Picket September 25th, 2007, 09:18 PM

Well, regardless of the incidentals I think the basic tenets are worth discussing and I think you're on to something here & this is a fun subject.
However to address the issue of the influence of H2SO4 on a polyol nitration to the best of my limited knowledge if we are defining the nitration's interaction we do not see a
simple NG synth using temp controlled HNO3....we see the product using "mixed acids".
Simply to dehydrate? If this were so why not just use 90% or better HNO3? {Or simply MORE HNO3?} Can this be achieved? I think it can but the dehydration alone may not
be to total answer for the use of sulfuric acid. My memory is not too good but I remember something about bonding.....and I'm going to look this up in a chem text book from
ancient times.....(I never sold back my books :-)
Enkidu September 25th, 2007, 11:18 PM

HNO3, when used by itself and especially at lower concentrations, is prone to oxidizing the alcohol rather than 'nitrating' it. You add sulfuric acid to increase the concentration of
the nitronium ion.
HNO3 + H2SO4 <---> NO2+ + HSO4- + H2O
Also, I've heard it's possible to dehydrate(?) ammonium nitrate with sulfuric acid. I think there's a thread at SM about this, or maybe it's at the APC. I can't remember. (If you
remember, please post it.) Anyway, you end up with a partially useless nitrating mixture.
Does anybody remember that or have a thread? I can't find it, but I know it's there.
The_Duke September 26th, 2007, 03:04 AM

I don't remember a thread, but the dehydration of ammonium nitrate with sulfuric acid is referenced breifly on page 370 of COPAE.
Attached to this post is the reference cited by Davis.

Thanks Enkidu and for the file Duke, it was very informative. What I got from it was that as long as the solution isn't heated too much, you wouldn't have a problem with
producing too much nitrous oxide. Generally when I make a nitration mixture with Ammonium Nitrate and Sulfuric Acid, I keep it below 30 * C, and some of my yields making
NG and ETN have been spectacular. The temp. only got to 30* BEFORE adding the glycerine or erythritol. Obviously it was cooled to 15* before addition of the material to be
nitrated.
Although I did notice that the few times the temperature of the mixture went above 30* C prior to nitration, my yields went down significantly. Could it be that when I let the
temperature get too high, too much nitrous oxide was formed, disallowing a good yield? My last two batches of ETN have been low, I'm guessing due to this. For instance, my
last batch I used 20g erythritol and ended up with 20g ETN, which isn't very good at all. So I'll have to do some tests, and be more patient during the addition of my nitrate to
the acid :o. I'll let you guys know how it goes.
Azido November 2nd, 2007, 04:29 PM

HNO3 Has the property that it acts as an oxidizer(nitrator) at high concentrations, eg 70%+, but below this concentration acts merely as an acid. Sulphuric acid dehydrates the
acid, keeping it at a higher concentration, thereby ensuring the bulk of the nitric acid nitrates, rather than just making a corrosive mess.
To the best of my understanding. :D
Enkidu November 3rd, 2007, 01:53 PM

I think you've got it backwards.
At < 70% conc., it acts as an oxidizer. (Not sure of any specific reactions... but the general idea would be an alcohol to a ketone.)
At > 70% conc., it is able to perform nitrations, IIRC.
Charles Owlen Picket November 4th, 2007, 11:53 AM

At > 70% conc., it is able to perform nitrations, IIRC.
According to Moore & Stanitski in Chemistry, A Modular Science, you are correct. {Large portion of unique Undergrad textbook w/ info related to nitrations ISBN 0-534-1735-8}
Azido November 5th, 2007, 01:48 AM

Well the point that sulphuric acid is there to keep the concentration high was made. :P

a n d I m provised C hemistry > Atm o s p h e ric Pressure?
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rasputin_ecuador October 3rd, 2007, 11:32 PM

For 3 months now I've been trying to sinthesize cyclonite. Started out and thought I had b ad NA, so I bought 98% labeled NA,
t h e n 9 9 % a n d finally 100% pure. My hexam ine was made by Am m onia and form a l d e h y d e . I followed the instructions from
m ega's site and found that every attem pt lead to the sam e result, not a single crystal pre cipitated.
I've also tried to m ake MF, no luck there either, I some times got an inert yellow powder, other times after adding the ethanol
and filtering the product all I got was what I started with , mercury.
So I thought, am I such an inept bastard?
M a y b e I a m , but all I could co me up with is tha t nothing works for m e b e cause I live 9000 f t a b o v e s e a l e v e l . T h e a t m o s p h e r i c
pressure here is a hell of a lot less than in sea level which probably im pairs m y ability to succesfully complete any chem ical
reaction.
Any thoughts on what to do?
thx..

a n d I m provised C hemistry > Looking for som e solubility info...
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jpsmith123 Novem ber 1st, 2007, 10:16 PM

Hello,
I'm wonderin g, does anyone have any info on the solubility of NaCl and/or KC l in diethylene glycol and/or ethylene glycol?
Thanks.
Charles Owlen Picket Novem ber 2nd, 2007, 11:25 AM

Y o u M I G H T b e a b l e t o f i n d s o m e from major m anufactu rers/distributors of glycol products to medical facilities or research. A
good place to start would be those large business to business web sites that are chemical specific.
jpsmith123 Novem b e r 2 n d , 2 0 0 7 , 0 8 : 1 7 P M
Thanks for the thought, but I already tried that...unfortunately with no luck.
nbk2000 Novem b e r 2 n d , 2 0 0 7 , 0 9 : 4 9 P M
Knowing W HY you are asking the question goes a long way to answering it.
jpsmith123 Novem b e r 2 n d , 2 0 0 7 , 1 0 : 3 2 P M
I recently saw something in a patent about a novel electropolishing solution that would supposedly work on m any different
m etals, including titanium (the main object of m y interest). IIR C, the preferred form ula was KCl and ethylene glycol, although
NaCl could be substituted for KCl, and diethylene glycol for ethylene glycol. In light of this, I was curious ab out the solubilities
of these salts in the various glycols.
nbk2000 Novem b e r 2 n d , 2 0 0 7 , 1 1 : 1 4 P M
Best way to find out is to buy the m aterials and m ix it u p yourse lf.
If it's a patent, surely they've included information on the ratios, right? O r a reference to somethin g?
megalomania Novem ber 3rd, 2007, 01:45 AM

O n e o f t h e b o o k s p u b l i s h e d b y C R C p r e s s m i g h t h a v e w h a t y o u a r e l o o k i n g f o r . I a m b l a n king on the title (not the Handboo k
o f C h e m istry and Physics, which m ight also have it), it is one of those ph ysical properties books on solubilities.
T o d a y I h e a r d a c h e m ist recite an anecdote about Edison: Edison asked his assistants to find out the volume of a lightbulb.
They went to work m easuring the bulb with rulers and calipers, and used all the fancy engineering equations, but every one of
them had a different answer. Edison then proceeded to snip the end off a bulb, fill it with water, an d m easure the volum e b y
d u m ping it in a beaker.
The moral of the story is sometim e s a n e x p e r i m ent can be very sim p l e , a n d n b k 2 0 0 0 a l r e a d y s u g g e s t e d t h e b e s t a n s w e r t o

the problem , do the solubility tests yourself and you will have an answer. Measuring solubility is not hard to figure o ut.
Bugger Novem ber 3rd, 2007, 06:48 AM

Here is the C R C H a n d b o o k O f C h e m istry, 87th edition:
http://rapidshare.com / f i l e s / 1 6 5 2 2 3 5 6 / C R C _ H a n d b o o k _ O f_Chem istry___Physics-87thEd_CRC-PDF-2006-7_.zip

92,362 Kb
I downloaded the International Critical Tables a year or two ago. They would certainly have the solubility da ta for salts in
glycols you require, if the CRC H a n d b o o k d o e s n o t . Y o u could try looking for it on G o o g l e a s a r a p i d s h a r e . c o m download
(include "rapidshare.com/files" and "International Critical Tables" in double quotation m arks in the search string), o r as a
BitTorrent do wnload (include torrent and "International Critical Tables" in the search string).
jpsmith123 Novem ber 3rd, 2007, 11:20 AM

T h e p a t e n t i s U S6835300. I already tried a quick test with NaCl and KCl using glycerin and propylene glycol as solve nts, to no
avail. (It didn't look like anything dissolved, and the solution m easured infinite resistance with my cheapo digital meter).
I just bought som e diethylene glycol (OTC as Sterno "wick chafing fuel"), and I'm preparing a test with that.
If th is can be m ade to work, I can see some potential use as a surface preparation for titanium , prior to cobalt oxid e plating
(for use as a perchlorate anode).
tranquillity Novem ber 3rd, 2007, 07:54 PM

I think you m a y n e e d s o m ething like a crown e ther http ://en.wikipedia.org/wiki/C rown_ether which are specifically designed to
im prove solu bility of salts in o rganic solvents. Each crown ether has a pre ference to a specific cation so you would need to
m ake a decision about KCl or NaCl.
http://www.freepatentsonline.com/4435582.htm l details the synthesis of 18-crown-6 which targets potassium ions.
jpsmith123 Novem ber 4th, 2007, 12:31 AM

That's the first I've ever heard of a "crown ethe r". Sounds interesting, but as I recall, the patent didn't men tion anything else
a s b eing required. I'll try the DEG with NaC l and then KC l tom orrow and see what happens.
nbk2000 Novem ber 4th, 2007, 01:25 AM

P a t e n t s o f t e n l e a v e o ut the im portant details, to confou nd potential copy-cats.
jpsmith123 Novem ber 7th, 2007, 10:13 PM

Just in case anyone's interested, I tried diethylene glycol with NaCl and KCl and had no luck; i.e., it appeared that nothing
dissolved, and the liq uid had no measurable conductivity. I think nbk2000 m ay be correct - som e importan t detail was left o ut
of the patent.

a n d I m provised C hemistry > Partial nitrations?
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LibertyOrDeath Novem ber 10th, 2007, 05:08 AM

As a non-chemist attem pting to learn m ore about the key reactions involved in explosives m a n u f a cture, the issue of partial
n i t r a t i o n s h a s b e e n b u g g i n g m e . I ' v e b e e n s e a rching th e w e b , t h i s s i t e , a n d l o o k i n g t h r o u g h a l l o f m y b o o k s o n e x p l o s i v e s
chemistry, but the answer is eluding m e, so I'm hoping that one of the chem ists here can enlighten m e a bit or at least point
m e in the direction of what to read.
If th is question is naive or stu pid -- or if the answer is overly complex -- then please delete this th read (an d hopefully not m e
a l o n g with it ;)), and I'll take that as a cue. On the other hand, m aybe it will stimulate som e interesting discussion, as is m y
hope.
W ith that out of the way, here's what I'm pondering:
Say you're nitrating erythritol. There's room for four nitro groups on the molecule, and your goal is to get tetranitrate rather
than tri-, di-, or m ononitrate. How can we be ce rtain that the vast majority of the product is fully nitrated?
Of course I understand that properties such as melting point, so lubility in various solvents, and even color can be affected by
t h e d e g r e e o f nitration. Certainly com pletely un-nitrated erythritol has en tirely different properties from ETN. But I just don't
know for a fact that erythritol TRInitrate has properties significantly different from those of TETRAnitrate. Can we be confident
of such a thing? Perhaps erythritol trinitrate is also explosive but has less power.
It's m y understanding that when creating a nitrating mixture, an excess of acids is used so that yo u have enough nitronium
ions floating around to attack all sites available for nitration on all available m ole cules. Stirring increases the probability of
contact between nitronium ions and sites on erythritol m olecules that have yet to be nitrated. And I suppose that tem perature
control is used to lim it com peting reactions. Yet it's very difficult for a chemistry novice like me to understand, or even
rese arch, W HY a certain temperature range is most favorable to nitration , or HOW favorable it is to nitration over other
reactions. So if I'm m aking ETN, I don't know if I'm m aking 99% tetranitrate, 80%, or 50% versus partially-nitrated erythritol. I
s u p p o s e t h e s a m e c o uld be said for NG, MHN, etc.
W ould anyone care to com ment on this issue, even if it's just to point m e t o a g o o d b o o k ? T h a n k s i n a d v a n c e f o r a n y h e l p !
nbk2000 Novem ber 10th, 2007, 07:59 AM

I'd not be too concerned about the ETN being Tri- instead of Tetra- nitrate, as the difference in VoD would only be a few
h u n d r e d m eters, I'm sure.
Charles Owlen Picket Novem ber 10th, 2007, 09:16 AM

I a m not a chem ist but I think I know what you a r e a s k i n g a s I h a v e t h o u g h t a b o u t s o m e t h i n g s i m ilar. The re is a GR EAT old
b o o k e n t i t l e d " T h e P e n t a e r y t h ritols", Evelyn & Robert Barth, John Snow. Published by Rienhold in 1958....one edition. W orth
finding! It outlines what can and cannot bind (with, in th is case PETN or ETN) and what hap pens in term s o f e n e r g e t i c a n d
polym er chem istry.
It was not lig ht reading for this old man. I had a undergrad textbook on organic chemistry available to follow up on some
subjects (Chem istry, A Modular Science; Moore, Stanitski - a very good source).
W ith the subject you're after, there is an energetic noted as PEN as well as PETN. PEN is the trinitrate and can even be found in
Ledgard's Preparatory Manual of Explosives! [See procedure 13-04]
Now, I don't trust Ledgard as his patent numbe r are not accurate (I've searched quite a bit on som e of his shit) but his
rese arch (on PEN) came from t h e R o h m & H a s t C o m pany (1969) who ma de explosives for industry during the 1960's. It seem s
that when you are dealing with com plex polyols (esters) dropping one (tri/tetra) has virtually NO effect on VoD or even
sensitivity for that m atter. That is NOT the case with oth er materials (nitric am ines for instance). So the specific m aterial to be
nitrated has a great bearing o n this su bject.
Check info on the nitration of Sorbitol, etc. If you drop from the hexanitrate to the tetranitrate, it still shoots well.
The influencing factors are tim e, temp and ratio of acid, polyol, & reaction modality. I hope I started you off in a productive
direction. {It's early and I have to go to work.}
Enkidu Novem ber 10th, 2007, 02:45 PM

I don't want to type right now... so this will be brief.
Three types of nitrations.
C-NO2 = 'true' nitration, NO2 group called 'nitro'
W ith aromatic nitratio ns, partial to full nitration controlled by molar ratios of nitronium ion. Read up on electrophilic arom atic
substitution.
O-NO2 = esterfication reaction, ONO2 called 'nitrate' (as in potassium nitrate, KONO2, ETNitrate).
W ith polyols, you generally get all or n othing, except in cases of extrem e steric hindrance. Very few % partially nitra ted
c o m p o u n d s . R e a d u p o n e q u i l i b r i u m s.
N-NO2 = an am ide, N-NO2 called nitram ine.
Not sure about nitram ines; m a y b e s o m e o n e e l s e c a n t e l l y o u .

I t s a n e q u i l i b r i u m r e a c t i o n a s e n k i d u m e n t i o n e d . U s i n g a l a r g e m olar excess of n itration acids will result in a higher proportion
of fully nitrated polyol, but note that you will never get a 100% yield due to the equilibrium. But this doesnt m atter as the lower
nitrated derivatives are consid erably m ore soluble then the fully nitrated ones thus a good water wash is all thats necessary to
isolate your wanted product.
This is most clearly seen in nitrocellulo se which cannot be washed free of the lower nitrated products as its a polym er, thats why
nitrocellulose is graded on nitrogen percentage rather then nitrate groups.
Alexires Novem ber 12th, 2007, 12:32 AM

Liberty - I think that you will find that it is the nature of chem istry. It is impossible to have a 100% chem ically pure substance.
LR chem icals are very pure, but not pe rfectly so.
So to relate back to what you are asking, yes, there will be som e other by products that you will ne ver get rid off, but if what
Enkidu is saying is correct, then I think that you can be fairly confident that your PETN is fairly pure , and that too m uch washing
will be detrim ental to your product (loss of product).

a n d I m provised C hemistry > KNO 3 solution gone wrong
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Secong Nature Novem ber 11th, 2007, 08:30 AM

As you are all aware I am a newbie who is posting a new topic and already feel as if I am skating on thin ice but I feel that
s o m e of you will find this interesting.
Tonight I decided to test various kinds of sugar fuel, not that it really m atters, just giving inform ation.
So I decided to heat a very crystaline batch of KNO3 crystals in a glass which I had previously used to m a k e a f a i l e d f u s e
(soaking string in a super saturated solution of KNO3).
To get all the crystals out of the glass I had to dissolve them in a large am ount of water (over two litres is m y g u e s s ) a n d t h e n
decided to boil it down in a steel pot; I then we nt to watch TV in the adjacent room.
After the water level went down about 5m L I b e g a n t o s m ell a halogenic sm ell and went over too see the solution slightly
sim m ering but reekin g o f s o m ething similar to brom ine.
I then turned the heat off and left it there for a few hou rs, coming back it still smelled strange so I decided to leave it and
continue nex t morning.
I'm currently in a state of a weeks worth of sleep deprivation and poured m yself a gin and tonic with a bit too much gin so am
not in a grea t mental state at the m o m e n t .
For information the KNO 3 in the glass should be aroud 100g (by guessing) which was dissolved in a cup of water and left to
crystalise by the water evaporating by itself.
This form ed two crystal layers; the bottom one being about as coarse as sugar while the top one h ad m onoclinic crystals
between 1-2cm.
The pot which I had boiled the solution in had recently been use d to m ake two 100g batches of sugar fuel, using a dextrose /
KNO3 m ix and then a sucrose/KNO3 m ix, both in a 35:65 ratio.
My main theory is that the sm ell was a slight am ount of NOx form ing from decom p o s t i o n , I h a v e m i s t a k e n t h i s s m ell for
chlorine befo re.
I d o n o t b e l i e v e c o n t a m ination to be the cause as the stuff I buy is, if not pure then very close to it.
I will take m e a s u r e m e n t s i n t h e m o r n i n g i f i t h a s n o t b e e n t o u c h e d w h e n I awake n arount m idday so that additional and

precise inform ation can be gathered.
------------------------------------------
O k t o m m orow afternoon has arrived and the only inform ation that I can get is that it weighs 1465g and has about the same
a m ount in m Ls, m eaning that it weights as much as water.
Kitchenware was used so measure this so accuracy may not be very exact.
It still sm e l l s l i k e h a l o g e n g a s .
I c a n t t e s t p H b e c a u s e I h a v e n o m e t h o d o f d o ing it, is there an ything that will form a precipitate in acid/alkaline co nditions?
Also what concentration in the air does NOx gas get to before it can be seen?
Because if m y decomposition theory is true and no brown fumes where seen then a very little amount m u s t h a v e b e e n p r e s e n t .

a n d I m provised C hemistry > Electrophoretic Coatings
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I'm wonderin g, has anyone done any electrophoretic deposition, say of T iO2 or som ething similar? I'm looking for introductory
literature, theses, etc., that would explain the general technique in some detail and shed light on the variables invo lved, but
I'm not having much luck.
LibertyOrDeath Novem ber 12th, 2007, 02:36 PM

Did you already see the following? It gives a pretty good overvie w:
http://www.m tm . k u l e u v e n . a c . b e / R e s e a r c h / C 2 / E P D . h t m
The list of references at that site is also pretty extensive, with plenty of free PDFs:
http://sirius.m tm . k u l e u v e n . a c . b e / R e s e a r c h / C 2 / p d f g u i d e % 2 0 C e r a m ics%20research%20group%20p ublicati ons.htm
Just out of curiosity, what was it you were thinking of using the p rocess for?

N o I h a d n ' t s e e n t h o s e s i t e s b e f o r e , t h a n k s f o r t h e l i n k s . T h e s e c o n d s i t e a p p a r e n t l y h a s s o m e pretty good papers available.
Anyway, I'm working on anodes for ele ctrolytic productio n of chlo rate and perchlorate. One of the things I'm interested in doing
is putting a TiO 2 coating (as a barrier layer) on to a graphite rod.

a n d I m provised C hemistry > C obalt Ox i d e C o a t e d A n o d e s
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jpsmith123 D e c e m ber 6th, 2007, 05:21 PM

For the last few weeks I've been trying to m ake a cobalt oxide coated titanium anode for chlorate and perchlorate p roduction;
so far without much luck. (There is a detailed d iscussion about it at scien cem a d n e s s ) .
Most of my attempts so far have involved anodic electrodeposition from both cobalt (II) sulfate an d acetate solutions. (If I get
any good results I will post them h e r e , s i n c e I k n o w m a n y p e o p l e h e r e m ay be interested).
The problem is that, regardless of how the surface is prepared, the product just doesn't seem to adhere very well. Most of the
deposited material can be wiped off with a rag, and if that's not done beforehand, it seem s to com e off like slim e a fter a short
period of exposure to the salt brine.
Anyway, I'm wonderin g if anyone m i g h t h a v e a c c e s s t o t h e f o l l o w i n g p a p e r s ? T h e s e s o u n d l i k e t h e y m a y h a v e s o m e u s e f u l

information.
###################################
A new cobalt oxide electrodeposit bath for solar absorbers

Sola r Energy Materials and Solar Cells, Volum e 5 1 , I s s u e 1 , 1 F e b r u a r y 1 9 9 8 , P a g e s 6 9 - 8 2
Enrique Barrera, Ignacio Gonzlez and Toms Viveros
A study was carried out in a Hull cell in order to optimize the deposition conditions of cobalt oxide (black cobalt) in an
electrolytic bath, which uses cobalt nitrate for direct obtention of black cobalt. Therm al stability of the material was surveyed on
s e v e r a l s a m ples of black cobalt prepared on stainless-steel with a thickness of approxima tely of 2.5 m . It was found that the
optical prope rties change, in respect to the initial values, with tim e of treatment u ntil an equlibrium is reached. This equilibrium
d e p e n d s o n t h e s u b s t r a t e a n d t h e t e m perature of the treatm e n t u s e d .
################################################## ############################
Black cobalt solar absorber coatings

Sola r Energy Materials, Volume 22, Issue 4, August 199 1 , P a g e s 2 9 3 - 3 0 2
S. John, N. Nagarani and S. Rajendran
A new electrolyte has been proposed for the de position of black cobalt selective a bsorber coatings. These coatings are used in
solar collecto rs for phototherm al conve rsion of solar energy. W e have studied the influence of electrolyte composition and
o p e r a t i n g p a r a m eters on the properties of the black cobalt coatings including optical ( , ;) and electcical properties. Therm al
stab ility and corrosion resistance tests showed good durability of black cobalt selective coatings for high temperature
applications.
################################################## ################################
Preparation of selective surfaces of black cobalt by the sol-gel process

Renewable Energy, Volum e 9 , I s s u e s 1 - 4 , S e p t e m ber-Decem b e r 1 9 9 6 , P a g e s 7 3 3 - 7 3 6
E. C. Barrera, T. G. Viveros and U. Morales
Black cobalt, Co3O4, thin solid coatings on stainless steel and glass substrates have been prepared by the dip coating
technique via the sol-gel route using a CoCl2 p recursor. The coa tings produced on substrates exhibit a blue to black colours
a s a function of the film t h i c k n e s s . S o l s h a v e b e e n m ade from a cobalt acetate precursor 0.1 M, and for such conditions, the
dip coating p r o c e s s g ives 0.08 0 . 2 5 m thick uniform film s per dipping, depending on the viscocity o f the sol.
################################################## #################################
Cobalt oxide thin film s prepared by chem ical vapor deposition from cobalt (II) acetate
Sola r Energy Materials, Volume 23, Issue 1, Novem b e r 1 9 9 1 , P a g e s 2 5 - 2 9
Toshiro Maru yam a a n d T s u y o s h i N a k a i
Cobalt oxide thin film s were prepared by a low-tem perature atmospheric-pressure chem ical vapor depositio n m ethod. The raw
m aterial was cobalt (II) acetate which is non-toxic and easy to handle. Polycrystalline film s were obtained a t a reaction
t e m p e r a t u r e a b o v e 3 0 0 C . F r o m n e a r - n o r m al reflection measurements it follows that the films have solar absorptance =
0.73 and the rm al emittance = 0.089.
Bacon46 D e c e m ber 6th, 2007, 09:47 PM

Im not an authority on plating but I dont think Al or Ti are good substrates. For that reason those m etals are usually painted,
p o l i s h e d , b r u s h e d o r a n o d i z e d i f a n y t h ing other than a m ill finish is desired.
The articles reference d in your post use stainless steel or glass as a substrate. In m y opinion Type 316 and Nitronic 60
stainless steel would both be good candidates for this p articular experiment. Both of these types o f stainless steel are
c o m m only used in the chem ical industry where resistance to corrosion is the m ain concern.
jpsmith123 D e c e m ber 7th, 2007, 02:18 AM

Hello Bacon4 6,
I'm wonderin g, what m a k e s y o u t h i n k t h a t T i i s n o t a g o o d s u b s t r a t e ?
Thermiteisfun D e c e m ber 7th, 2007, 10:34 AM

If you had to choose just one or two of those... W hat would it be?
T h e r e a s o n I ' m askin g is because a friend has access to the UF archives, I would not like to step on any toes
jpsmith123 D e c e m ber 7th, 2007, 11:20 AM

Thanks for the thought, but I just got them a little while ago.
I a l s o p o s t e d t h e r e q u e s t o n t h e s c i e n c e m a d n e s s f o r u m a n d s o m e o n e c a m e through.
The two papers on electrodeposition lo ok very promising.
Apparently, I was unknowingly quite close to the result I was looking for already.
If anyone is intereste d in any of these papers, let m e k now, and I will upload them here.

Hello Bacon4 6,
I'm wonderin g, what m a k e s y o u t h i n k t h a t T i i s n o t a g o o d s u b s t r a t e ?
I h a v e n o r e a s o n b a s e d o n s c i e n c e . I h a v e s e e n m any things plated with titanium nitride (drill bits etc.) but I just can't recall
ever seeing titanium plated with another metal. Then again I m ay have held it in my hand and not known it.
I m n o t s aying that you can t plate it, or that the titanium s u b s t r a t e i s y o u r problem . I was m erely throwing it out there as a
possibility, since you were having trouble and the article s in your post refer to stainless steel and glass as substrate s.
I would be in terested in reading the papers you have on this subject.

I should say that I've b e e n a b l e t o p l a te cobalt m etal onto titanium, and it looks like a million bucks; it's smooth and highly
a d h e r e n t . T h e trick is to either cathodically hydride the titanium for a few m inutes at a mo dest current density, and then
electroplate imm ediately thereafter.
I've also done it, as I recall, by putting a very thin TiO2 layer do wn by anodizing at a low voltage in 10% oxalic acid solution. I
just got two papers that claim to have developed new electrolyte solutions that can plate out an ad herent cobalt oxide layer. I'll
uplo ad them a little later.

It to ok very little research to discover that Ti is the preferred substrate for plated chlorate anodes.
O p e n m outh insert fo ot!:o
I m a n x i o u s t o s ee y o u r r e s u l t s . I m getting tired of filtering out graphite.
T h a n k s i n a d v a n c e f o r uploading the d ocum ents.

This paper describes an electrolyte comprising Co Sulfate and Am m o n i u m A c e t a t e .

This paper describes an electrolyte containing the nitrate, sulfate and chloride of cobalt and som e boric acid.
Bacon46 March 25th, 2008, 10:25 AM

Here are two patents pertaining to the application of m etal oxide coatings. They are very sim ilar m e t h o d s a n d b o t h s e e m
f e a s i b l e o n a n a m ate ur or im provised level.

a n d I m provised C hemistry > Barium Nitrate
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s-lab D e c e m ber 14th, 2007, 08:58 AM

For a while now i have been trying to find the best ways to make this good oxidiser which provides a nice green colour when
used in fireworks ect....
I h a v e t h o u g ht of one way which is quite easy to do, and produces lots of barium nitrate.
First barium carbonate ( easily purchased from pottery supply stores) is decomposed to barium o x i d e a n d c a r b o n d i o x i d e
acco rding to this :
BaCO 3 BaO + CO2
T h e n t h e b a r i u m oxide is reacted with water to produce barium hydroxide:
BaCO 3 BaO + CO2
Finally it is reacted with am m onium nitrate (easily obtainable as a fertiliser or in instant cold packs ) to produce barium nitrate
and amm onia:
B a ( O H ) 2 . 8 H 2 O (s) + 2NH4NO 3 (s) ----> Ba(NO 3)2(s) + 2NH3(aq) + 10H2O
(I hope i have balanced this right ;))
All o ther m ethods are welcom e !

Thanks in advanced
tranquillity D e c e m ber 14th, 2007, 08:11 PM

W h a t m a k e s y o u t h i n k that barium h y d r o x i d e a n d a m m onium nitrate can be m ade to react in the solid phase? If you did
inde e d m e a n a q u e o u s then you would need to use hot water as the hydroxide is relatively insoluble in cold water. After that
the water (and am m onia) wou ld need to be boiled off to collect the nitrate as barium nitra te is quite soluble in water.
s-lab D e c e m ber 15th, 2007, 09:15 AM

W ell hen you heat sodium hydroxide (s) with NH4NO 3 (s) you will get NH3 gas being given off as NH4NO3 has a low melting
poin t so they would react in m olten state.
a l s o a s y o u a r e h e a t i n g t h e m the wate r and am m onia would boil off leaving solid barium nitrate.
It was just an idea and correct m e if i am wrong but it seem e d e a s y e n o u g h t o m e
tranquillity D e c e m ber 15th, 2007, 08:12 PM

Sorry you are correct just i think the reaction sh ould then read:
B a ( O H ) 2 . 8 H 2 O (s or l) + 2NH4NO 3 (l) ----> Ba (NO 3)2(s) + 2NH3(g) + 10H2O (g)
I left the barium hydroxide as (s or l) as I am not sure of its m elting point. Another thing to consider with a reaction involvin g
m elting NH4NO3 is that it decom p o s e s n o t f a r a b o v e i t s m elting point to N2O and NOx.
This reaction m ay also work with barium o x i d e :

BaO (s or l) + 2NH4NO3 (l) ----> Ba(NO3)2(s) + 2NH3(g) + H2O(g)
Nitrato May 21st, 20 08, 01:3 8 PM

P u r e a m m o n ium nitrate really is a very good choice, sin ce it will not give any m etal cation that sucks the green colour
( s o d i u m ,etc). But you dont ne ed exactly to use oxide, hydroxide or carbonate.. You can just use BaC l2 in water (is m y source
of Barium . Technical lab grade), since the solubility of Ba(NO 3)2 is extrem ely low, favouring it to ppt. The following data,
grams of salt per 100g of water is from Seidell's book o f solubility:
B a ( O H ) 2 * 8 H 2 O : 1,67g @ 0C ; 101,4g @ 80C (!!!)
BaCl2*2H2O : 31.6g @ 26C ; 58.8g @ 100C
Ba(NO3)2 : 5g @ 0C ; 34.2g @ 100C
B a C O 3 : 1,6 x 10^-3 g @ 8C ; 2,2 x 10^-3g @ 18C ; 2,4 x 10^-3g @ 24,2C (this was take from frogfot page: http://
www.frogfot.com /stuff/soltab1.png).
BaCl2 + 2 NH4NO3 ---H2O---> 2 NH4Cl + Ba(NO3)2
I used two weeks ago to m ake a batch of Ba(NO 3)2 : a couple of gram s ( 7 0 g , I I R C ) o f B a C l 2 * 2 H 2 O w a s a d d e d i n w a t e r a n d
this was added slowly in an excess of fert. grad e NH4NO 3 solution (the stuff was still dam p, so I didn't bothered to weight it)
placed in a ice/water bath. The endotherm dissolution o f a m m onium nitrate helps to lower the tem perature still faster. The ppt
barium nitrate was filtered, the filter squezeed by hands (with gloves, of course. Most of barium sa lts are definately not
benign, especially the m o r e s o l u b l e s a lts. According with the label of m y BaC l2 bag, 0.8g of BaCl2*2H2O can kill you, if
swallowed/absorbed) and then the Ba(NO 3)2 was recrystallized from 500m L of boiling water (as you can see Ba(NO 3)2 in
boiling water is less soluble th an e.g. potassium chlorate, so funny). The Ba(NO3)2 are fine white cubic(?) crystals that
rese m b l e f i n e s u g a r g r a i n s a n d which dried with ease when spreaded in a piece of paper. Unfortunately I cant figure out how
m uch was produced since Imm ediatelly after dried I used m ost part of it, burning with sucrose (m y first Barium m ix). It burn s
slowly with a yellow/green flam e (the yellow pro bably is from oxidation of the carbon in sucrose..I'm going to try oth er mixtures
to see) and gives a b lackish mass of material, that I scraped of the ground and added to some HCl, filtere d and then Na2CO 3
solution was added, just to recover the barium values one more time .. This time the ppt wasnt that clean white stuff..W a s a
m ore im pure coloured precipitate. All my effort was due the fact that where I live Barium com p o u n d s a r e n o t O T C , a n d
s o m ewhat expensive, so I want to recycle all th at I achieve.
All the left over solutions after Ba(NO3)2 extractions/recrystalizations were combined and a solution of Na2CO 3 was added,
giving a white BaCO3 ppt that was decanted and washed several tim es with fresh water to rem o v e a t l e a s t m o s t o f s o d i u m
contam inatio n. The BaC O3 dried and it weight a few gra ms (7-10g..I have no accurate scales). I was fearing that the m ild
acidic NH4NO 3/NH4C l/Ba(NO3)2 solution was going to ju st grasp on the carbonate a n d a v o i d B a C O 3 f o r m ation, but when I did,
the precipitation was fast and nice..Pro bably the Na2CO3 turned the solution basic, since I felt a slight smell of am m o n i a a t
the end.
I'm fearing that the Na2CO3 occluded som e s o d i u m i n s i d e t h e B a C O 3 m a t e r i a l . . S o I ' m now wondering If I could not use
a m m o n i u m b i c a r b o n a t e t o m ake it.. W ell.. The re is only a good way to see =]
Bert May 21st, 20 08, 04:2 8 PM

W ith low burning temperature organic fuels such as sugar, neither Barium nor Strontium nitrate will yield all of their O x y g e n
contents. You will need a higher burning tempe rature fu e l s u c h a s M a g n e s i u m or Sulfur to reach the full potential of these as
o x i d izers. Also, with the Barium in particular you will need a Chlo rine donor to get a good green rather than the greenish yellow
you observed.
Charles Owlen Picket May 22nd, 2008, 10:39 AM

Very good stuff Bert: That tem p i s s u e w a s s o m e t h i n g I h a v e r a r e l y h e a r d a n y o n e s p e a k o f . I t h o u g h t t h a t I h a d p o o r g r a d e
BaNO3 or whatever....but I have always had to get a chlorine donor and m ake sure that the fuel was hot burning. I don't think
I even read about that previously for all the years I have been burning stuff up!
T h e o r i g i n o f M Y m i s c o n c e p t i o n ( I b e l i e v e ) s t e m s f r o m m aking tracers with Gary Purrington's stuff and barium peroxide, which
gave a decent green at oh dark hundred, when your eyes could fix on the streak of light. And not conceptualizing the needs for
chemical colours to have "their needs" met.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Excel molecular
formula subscript help
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View Full Version : Excel molecular formula subscript help

I am redoing the molecular format of the energetic materials on my website and I am running into an annoying problem. I have all of the molecular formulas properly
subscripted in word, but subscripts do not copy and paste into Dreamweaver. In Dreamweaver the sub/sup script code snippet is buried deep, so manually changing every
occurrence of a number to have a subscript tag wrapped around it is quite tedious.
What I have are a large number of formulas that have no subscript at all. I want to paste these into my excel list which I use to organize and sort data. I cant figure out
a way to write a (excel)formula that will take a number in the format of CxHyNzOw and add the appropriate tags around the number. I also tried using regular
expressions to make the replacements in Dreamweaver. I can FIND the numbers, but I cant seem to add content both before and after the number while keeping that
same number.
Not all formulas will have N or O, some have additional molecules, and the numbers can be 1 or 2 digits long, and in a few cases 3.
How can I take a formula such as C6H2(NO2)3ONH4 and using an excel formula display this in the format of C6H2(NO2)3ONH4? Obviously the example formula does not follow the usual CxHyAzBwCvDu format of an empirical formula; not all formulas I have follow the format,
so no formula can anticipate this format. I want a formula that will take digit X and make it X.
I hope I explained that clearly. I dont want a find and replace I want a find and add before and after type formula that only works on digits in varying lengths and
locations in a text string.

For fucks sake, I just wasted more time figuring this out than it would have taken to do manually, but now I have a few more mad skillz with excel...
I saved myself a good deal of time by using that "extract data and text from multiple files" program I hunted down 1.5 years ago. I was able to generate a list of every
molecular formula from my master word document and drop that in my excel file. I spent over 45 hours in 4 days completely redoing my word and excel sheets to get them all
alphabetized and organized... a good thing now because the order of extracted formulas now matches the alphabetized list of molecular names exactly.
I ended up using dreamweaver's find and replace function with regular expressions to get the job done. I used these parameters:
find: (\D)(\d)
replace: $1$2
This expression finds a letter (molecular symbol), using the \D wildcard, followed by a number, using the \d wildcard, but not any numbers that would precede a letter, such as
5H2O. The wildcards are in parentheses in order to assign them to $1 and $2; the first parentheses finds the letter, which is replaced as $1, and the second parentheses finds
the number, which is replaced as $2.
Alas, this replace operation only works on single digits, so any double digit number would only have the first digit subscripted. I ran a second find and replace operation to fix
that:
find: (\d)(\d)
replace: $1$2
This finds any occurrence of a subscripted number followed immediately by another number and moves the closing subscript tag to after the second number.
I had to manually do the tags for any subscripts using letters (indeterminate formulas) and salts that include a prefix number followed by a formula that already had some part
of the formula before it (like the pentahydrate of copper sulfate pentahydrate, CuSO4 5H2O). Doing these special cases was easy with everything in an excel list.
I would still prefer an excel formula because the code will automatically update if I make changes, or add additional formulas, but this way works.
FUTI January 23rd, 2008, 04:17 PM

Mega I think I have seen some book Excel for chemists some time ago. I haven't got time to read it but maybe the answer to your problem is there.
Bugger January 24th, 2008, 07:15 AM

Excel For Chemists
Almost a year ago, I downloaded "Excel For Chemists" by E.J. Billo (Wiley - 2nd edition - 2001), which runs to a 60 Mb PDF. Here is a current link for it, which has been going
since February 2007 with over 400 downloads:
http://mihd.net/e71glc
There were also rapidshare.de links for it, but these have expired.
See also:
http://web.uvic.ca/~berryde/chem222/Excel%20tutorial/Excel%20Tutorial.pdf
http://depts.washington.edu/chem/courses/labs/documents/Chem142_ExcelTutorialPart1.pdf
http://depts.washington.edu/chem/courses/labs/documents/Chem142_ExcelTutorialPart2.pdf

I already have the book, and I read through it before I asked the question. It did not have any answer that I could find, despite the book being the most logical choice for my
problem. The book exclusively focuses on formulas for statistics, graphs, data analysis, and more esoteric sorting of data. It is rather short on helpful hints for formatting.
Bugger February 16th, 2008, 07:00 PM

The Excel Bible (PDF):
http://rs7tg.rapidshare.com/files/62044489/073562321X.rar
73.24 Mb

a n d I m provised C hemistry > creative solution needed: seperate silver from pallad ium
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View Full Version : creative solution needed: seperate silver from palladium
pyromaniac_guy January 2nd, 2008, 02:58 AM

Hello all,
Long time no log on...
I h a v e a s m all favor to ask of the forum since there are so many uber creative fo lk here.
I have about 50 troy ounces of 77% palladium bal silver alloy. T his is 4 9's material so If I can find an easy way or rem oving
the silver I'll be left with fine palladium scrap to sell for a fair chunk of change.
W hat I would ideally like is a process such as q uartering used to refine karat gold (dilute gold to about 25% purity in copper or
silver then dissolve in nitric acid leaving metallic gold behind with very little of the gold in solution).
The material is in the form of very thin ( 1 or 2 m il) tubing so th ere is a huge surface area to weight ratio. If I could avoid
dilution in a base metal (to avoid masking) that would be great. I dont care how long the process takes, I'd just prefer
s o m ething A) easy (ideally - but not the m ost important priority) b) low loss - we are after all talking about a precious metal
here and C) give a high purity finished product.
T h e b e s t I h a v e c o m e up with thus far is dissolve in aqua regia, let the silver percipitate out as chloride, pe rcipitate the
palladium with am m o nia then reduce.
If anyone can come up with anything better I'd be forever in your debt.
TIA!
Man Down Under January 2nd, 2008, 08:53 AM

I know gold can be purified from b a s e m e t a l s b y m elting it and passing chlorine gas through the m olten mix, vaporizing off
the base metals.
Try heating your metal red-ho t in a tube furnace with ch lorine gas passing through it.
The silver should volatilize off as silver chloride , leaving palladiu m powder behind .
Presumably you will collect the silver chloride vapor for purifying as silver.

Hm m m ...
G o o d i d e a , b ut wont work. Palladium i s l e s s n o b e l t h a n g o l d a n d even with gold you can only use this proce ss to get m a y b e
99.5% purity because eventually you will start producing chloride s of everything in your m elt, including the gold, loosing it out
the exhaust.
I didn't m ention this previously as I didn't think it was im portant, but I guess it is. I'm HO PING for at least 4 nines purity so
that wherever I dispose of this m aterial it wont need to be refined again - saving me on the markup.
T h a n k s f o r t h e s u g g e stion though...
jimmyboy1 January 2nd, 2008, 04:03 PM

Silver is much more reactive than palladium - o n e o f t h e h a l o g e n s s h o u l d b e a b l e t o s e p a rate them .
Man Down Under January 2nd, 2008, 06:18 PM

Y o u s h o u l d h a v e m entioned the 99.99% requirem e n t w h e n a s k i n g t h e q u e s t i o n , s a v i n g m e the tim e of replying with a m e t h o d
that I know wouldn't m atch it.
mil&co January 2nd, 2008, 06:39 PM

P a l l a d i u m reacts quite slow with hydrochloric acid, but silver is quickly dissolved. T hat might be an idea to work out, lot less
work then with aqua regia, which should work ok.

Y o u s h o u l d h a v e m entioned the 99.99% requirem e n t w h e n a s k i n g t h e q u e s t i o n , s a v i n g m e the tim e of replying with a m e t h o d
that I know wouldn't m atch it.
in retrospect i realize this now - however keep in m ind that the palladium is already 4 9's pure. it just happens to be alloyed
with 4 9's silver as we ll. This isn't really your average refining problem , where you have a bunch of junk mixed in with a
precious m etal and you have to get everything but that one m etal out. I have a mixture of two very pure m e t a l s a n d n e e d t o
sim p l y u n m i x t h e m :D
your suggestion would have worked if it weren't for the fact that even the nobel m etals aren't really THAT nobel.
megalomania January 2nd, 2008, 09:54 PM

You may want to look at electrochemical m e t h o d s . T h e r e a r e s o m e interesting pa tents released over the la st 20 years
concerning recycling of mixed high value metals.
I was going to suggest the silver chloride precipitation route, until I saw you want som ething better than that.
pyromaniac_guy January 6th, 2008, 09:38 PM
T h a n k s f o r t h e s u g g e stion on possible electrochem cial routes. I found a reference specifically dealing with isolating silver from
palladium (in 100's of ppm Ag in Pd concentrations) for radiochemistry. I need to dig up the actual paper b ut if controlled
potential plating of the silver will work for this that will save me a heck of alot of effort!
meyer25 February 28th, 2008, 10:57 PM

Dissolve the alloy in 65 - 68% nitric acid taking approx. 8 - 10 m L acid per gram of the metal; be careful, NOx evolves (quite
toxic by inhalation, so do it in a proper fume hood or outdoors). Maybe a gentle heating would be necessary to dissolve all
rests of the m etal.
W hat you get is basicaly solution of palladium (II) and silver nitrates with some nitric acid and NOx in water.
Let all eventual dirt (insoluble in HNO3 ) settle and decant the solution. I would omit filtering unless you have a proper frit filter
(no paper or cellulose).
Now add excess saturated NaCl solution, until precipitation stops. The basic principle is sim ple: silver chloride is practically
insoluble in water whereas PdCl2 and [PdCl4]2- are soluble.
Now decant the solution from the heavy precipitate, filte r (I'd use a glass frit, but analytical (ashless) filtpaper can be used, if
not too long in contact with the solution) it and wash the precipitate back in jar with distilled water acidified with HCl to about pH
1.
Filter this also.
The filtrate contains essentialy 99% pure ionized palladium in form of dichloride and tetrachloropalladate, along with plenty of
nitrate, chloride and sodium ions.
You could reduce the volum e of this solution by boiling it down until some particulate matter begins to form (saturation).
Now adjust pH by carefully adding 4% (1M) NaO H soln d rop by drop to about 6 - 7 (not higher, if possible); add excess sodium
acetate, and reduce the palladium out by form a l d e h y d e solution .
To do this, one should place the solution in a RB flask under a reflux cooler, heat until it boils/refluxes, than adding few mLs
of standard 35 - 40% form alin. The so lution turns dark brownish -black, one should reflux it for at least 2 hours, adding som e
m ore form alin eventualy.
W hat you now got is a suspen sion of crude palladium black, after cooling the reaction m ix ture, filter it out on the finest
filtpaper you can afford (again, ashless, preferably, with high density), wash the flask with copious amouths of distilled water
and wash the Pd black on the filter with it. wash again several times. Tha n, wash it with pu re acetone twice; it helps to get it dry
faster.
Leave it to dry com pletely and...voici, you shou ld have crude Pd black. That is, pulverous Pd metal with quite high a rea pro
m ass...
If you want it as a m etal (bar, rod etc.), you'd have to melt it and pour in a conveniant form. However, it should be molten
preferably under nitrogen and requires heat source of at least 1,600 - 1,700C, which is rather tricky to afford, if you're not
working in a well-equiped facility.
Forg et the "molten re d-hot m etal-chlorine gas" crap....the wet chloride m ethod is the way to go.

a n d I m provised C hemistry > Sodium dithionite
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Sophism January 13th , 2008, 01:21 AM

I use Na2S2O4 as reducing agent for one of my reactions, all the papers i found used it as reducing agent (for nitroso uracil
derivative), i would ask if som eone use other reducing agent for such nitrosoCpd.
it need difficult conditions as m y Yields often low.
megalomania January 14th , 2 0 0 8 , 0 5 : 0 4 P M

Unless you want us to hand you a big list of every reducing agent known to man you will h ave to describe your chem ical
reaction in detail, including the conditions, and reagents used.

a n d I m provised C hemistry > O x y g e n B a l a n c e
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UnderConstruction January 13th , 2008, 02:35 AM

I n o t i c e d s e v e r a l e x p l o s i v e s o n m e g a l o m ania's website that m ention it, I've been learning about it for a couple of weeks and it
s e e m s like som ething that's worth looking into. I spent five or six hours yesterda y figuring the OB of m any of the e x p l o s i v e s
on the site. Since the forum was down it gave me time to expand it considerably. Here's a list of what I have so far, except I
fear that several of them m ay be incorrect because a m istake in finding the m ola r mass. If m e g a l o m ania's site gives a m a s s
for the compound in question, you can trust that the O B is right.
O x y g e n b a l a n c e e n s u r e s c o m p l e t e d e t o n a t i o n a n d e l i m i n a t e s c a r b o n m o n o x i d e a nd NOx gases, so it's worth expanding upo n
This is the form ula:
OB=-1600/Mol. W t . o f C o m p o u n d * [ 2 X * + ( Y / 2 ) + m - Z ]
where
X=No. of carbon atom s
Y=No. of hyd rogen atom s
Z=No. of oxygen atoms
m =No. of m etal atom s
---------------
Results:
---------------
*Urea Nitrate (0%)
*EGDN (0%)
Nitrogen Sulfide (0%)
( - )
Etha n o l a m ine dinitrate (-9.46%)

PETN (-10.1%)
HNIW (-10.95%)
Pentanitroaniline (-15.088%)
PETRIN Acrylate (-15.888%)
Silver Fulm inate (-21.348%)
RDX (-21.6%)
HMX (-21.6%)
FOX-7 (-21.6%)
Guanidine Nitrate (-26.2%)
DINGU (-27.57%)
DNI (-30.36%)
Nitroguanidine (-30.748%)
EDNA (-31.978%)
Styp hnic Acid (-35.9%)
Nitrosoguanidine (-38.07%)
Potassium Picrate (-4 1.9%)
EDDN (-42.98%)
Dinitrochlorobenzene (-43.44%)
CL-18 (-44.0 7%)
PVN (-44.9%)
Picric Acid (-45.39%)
Tetryl (-47.36%)
CL-14 (-49.8 6%)
NONA (-51.6%)
Guanidine ca rbonate (-57.7%)
DATB (-58.84%)
PYX (-60.51%)
DIANP (-69.25%)
DNPA (-70.335%)
Trinitrotoluene (-74%)
*Alu m i n u m P o w d e r * ( - 8 9 % )
Propylpicrate (-91.44%)
HMT D (-92.2%)
NPN (-98.96%)
IPN (-98.96%)
*Sulfur* (-100%)
HNO (-122.6%)
Allyl Hydrope roxide (-151.1%)
Acetone Peroxide (Trimer) (-1 51.2%)
benzenediazobenzyl
hydroperoxide (-166.5%)
*Carbon* (-266.7%)
( + )
nitroglycerin (+3.5%)
TNGU (+4.96 %)
Heptanitrope ntane (+6.19%)
Am monium Nitrate (+20%)
Barrium Perchlorate (+20.4%)
Silver Perchlorate (+2 3.15%)
Lead Perchlorate (+27.58%)
Mercury Perchlorate (+28.03%)
Uranyl Perchlorate (+30.7%)
Potassium Dinitram ide (+33.0 7%)
Am m o n i u m P e r c h l o r a t e ( + 3 4 % )
Hydrazine Diperchlorate (+34.3%)
Potassium Perchlorate (+34.64%)
C a d m ium Pe rchlorate (+35.97%)
Strontium Pe rchlorate (+39.08%)
* p o t a s s i u m c h l o r a t e * (+39.2%)
Sodium Perchlorate (+39.2%)
Trinitromethane (+42 .37%)
Zinc Perchlorate (+42.38%)
Copper Perchlorate (+42.67%)
Cobalt Perchlorate (+43.43%)
Nickel Perchlorate (+43.47%)
Manganese Perchlorate (+44.1%)
* s o d i u m chlorate* (+45%)
Calcium Perchlorate (+46.86%)
s o d i u m nitrate (+47%)
Tetranitrome t h a n e ( + 4 8 . 9 6 9 % )
Magnesium Perchlorate (+50.17%)
TitaniumTetraperchlorate (+53.84%)
Alum inum Perchlorate (+54.09%)
Lithium Perchlorate (+54.4%)
Nitryl Perchlorate (+59.46%)
Nitrosyl Perchlorate (+61.79%)
*although the compound contains carbon,

hydrogen, and oxygen, it still has an OB of zero
because the CH&O balance each other out to 0
* . . . . * d e n o t e s n o n - e x p l o s i v e m aterial
often applied to explosives
Charles Owlen Picket January 13th , 2008, 11:22 AM

If th e a m ount of oxygen, expressed in weight percentage, liberated AS A RESULT of the com p l e t e c o n v e r s i o n o f t h e e x p l o s i v e
m aterial to C O2, H2O SO 2, etc. - this is positive OB. If the am o u n t o f o x ygen bound in the explosive is insufficient for the
complete oxidation reaction - we have negative O B. Com m e r c i a l e x p l o s i v e s n e e d t o h a v e a O B c l o s e t o z e r o t o m inimize toxic
gases; this is one of the criteria for "permissab les". However I have foun d that th e statem ent: "ox y g e n b a l a n c e e n s u r e s
complete detonation" is not entirely co rrect. Exam ple would be a quality prim ary like lead azide. Hell, we co uld look at a lot of
explosives with negative O B that detonate very efficiently but leave behind toxic gases. The big ones are carbon m o n o x i d e &
nitrous oxide. A positive O B lim its that and in a m ine or closed area, that's damn im portant.
OB can start to get confusing depending on testing dynam ic & source. I rem e m ber that MHN had a positive balance according
to Federoff a s did ETN. Many energetics materials that are m fg with an active base will most likely have a positive one
obviously. Many but not all nitric esters will have a positive O B . T h e r e a r e s o m a n y v a r i a b l e s i n t h e p h e n o m e n o n o f d e t o n a t i o n
that chemical com position alone allows for effective and complete detonation but never ensures it. Thus we have the
p h e n o m enon of "over-driving" a deton ation.
UnderConstruction January 13th , 2 0 0 8 , 0 5 : 4 7 P M

You obviously know a good deal on the subject, mind you though that I said "ensures com p l e t e d e t o n a t i o n ", not that it was
dependent. I understand though that oxygen balance isn't a necessity, it still see m s l i k e s o m ething that could aid the
e x p l o s i v e c o m munity if the inform a t i o n w a s r e a d i l y o n h a n d ( I t h i n k i t m i g h t m e i n t e r e s t i n g e n o u g h f o r m e g a l o m a n ia to
incorporate it into his explosives page, but it lo o k s l i k e h e ' s h a d his hands full more than lately, lately).
Charles Owlen Picket January 14th , 2008, 09:50 AM

It's not that com plex a subject in itself but it's easily m isinterpreted. It's certainly a worthy subject for discussion. The
discussion can open new viastas by dem a n d i n g further study to grasp at the utilitarian aspects. Here are two related questions:
C a n a n e n e r g e t i c m aterial have both a n e u t r a l a n d n o n - n e u t r a l O B ? W o u ld that (OB) affect performance and under what
conditions? Many peo ple have these questions in the back of their head when they first learn abou t this subject.
Cook wrote a simple but well rounded chapter on this subject.
megalomania January 14th , 2 0 0 8 , 0 5 : 4 7 P M

I l o n g a g o m ade the decision to not in clude too much e x t r a n e o u s d a t a u n r e l a t e d t o a s y n t h e s i s , a n d a l t h o u g h I h a v e s e e n
m any occurrences of calculated oxygen balances in m y references, I dont use them . A detonation velocity is about as much
non synthesis related I get on the site. I prefer to leave inform a t i o n o n t h e u s e a n d f o r m u l a t i o n o f e x p l o s i v e s u p t o s o m e o n e
else, or else I would never have time to concentrate on the syntheses.
I do agree that knowing what oxygen balance is, how to calculate it, and how it ca n b e u s e f u l i s v a l u a b l e . I f s o m eone is willing
to write the info up I can and will incorporate it into m y website. This is part of what I want to accom plish with the user
contribution feature.
UnderConstruction January 15th , 2 0 0 8 , 0 6 : 4 2 P M

You're welcom e to do anything with the inform ation I put up there, that being why it was put up to begin with :)
Also, I found an oxygen balance calculator in the Sim ila r Threads place, here:
(look on the second page)
I also found a calcula tor for m olar m a s s :

http://www.lm n o e n g . c o m / m o l e c u l e . h t m
Here's the start of a continued list:

PGDN (-28.9%)
Dinitrophenol (-78.21 5%)
TNEF (+4.27%)
BTNEC (+15.837%)
Man Down Under January 15th , 2 0 0 8 , 0 8 : 2 7 P M

I suck at math, so I'll ask what's Tetra ethyl Leads' OB?
(CH3CH2)4Pb = C8H20Pb
MW = 3 2 3 . 4 4
If th e problem could be worke d out in a stepwise m anner, it'd clarify som e problem s I had with the original form ula, such as
what are the *? They're used in two different places and contexts. And is it NEGAT IVE 1600?
R e a s o n I a s k i s b e c a u s e I s a w a n o l d p a t e n t f o r m a k i n g a n e x t r e m ely-sensitive liquid binary explosive using TeNM and TEL,

which was stated as h aving a VoD of over 9300m / s . : e e k :
I'll have to look to find it again, but it'd be nice to know if the patent was accurate or bunk.
UnderConstruction January 16th , 2008, 12:31 AM

you don't need to be great at math if you can learn how to work the online calculators (* is often u s e d t o a v o i d b e i n g c o n f u s e d
with an x when multiplying).
A problem I found with the online calculator I gave the link to when finding your OB was that it doe sn't incorporate any m e t a l s
present, do not use it in any metal-containing explosive.
Use this for m etal-containing explosives, though it is less user-friendly:
http://www.m ath.sc.edu/cgi-bin/sumcgi/calculator.pl
Insert -1600/MW [(2X)(Y/2)+m -Z] into the calculator of the above link and replace the variables listed in my first po st.
Also yes, it is negative 1600. Also / is divided, * is multiplied, - is negative and then subtracted (-Z).
the O B of Tetraethyl Lead is -133.56%
dhemor_ July 8th, 200 8, 08:39 AM

Hey, while I think of it, here's an oxygen balance calculator I coded a few days ago. It's program m ed in c++, and both the
source + an executable are available for download.
http://twitch.uflox.com/?page_id=13
I hope it's of som e use.

a n d I m provised C hemistry > Industrial Solvents Handbook
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View Full Version : Industrial Solvents Handbook
a3990918 March 5th, 2008, 11:07 PM

Industrial Solvents Handbook
"Keeping pace with current trends in solvent production, this volume builds upon its previous edition with broader coverage of
s a f e handling practices, health effects, physical properties, and chemical synthesis routes to some of the m ost im portant
organic solvents used in the chem ical and allied process industries. This handy re ference features a glossary of solvent
term i n o l o g y a n d a n e asy-to-reference index of synonym s for chem icals and solvents. The Second Edition features new and
updated chapters on the major classes of organic solvents, descriptions for general use, a nd the chem ical form ulation,
therm odynamic properties, he alth and toxicity, and com bustible characteristics of solvents."
http://rapidshare.com /files/97393049/Industrial_Solvents_Handbook.rar.htm l
ISBN: 0824740335 | 344 pages | PDF | 15 MB
No Pass.:)

a n d I m provised C hemistry > Sodium hydroxyde purity
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View Full Version : Sodium hydroxyde purity
TheBlob March 10th, 2008, 10:32 PM

Recently I've b o u g h t s o m e lye crystals at Hom e D e p o t ( C a n a d a ) e x p e c t i n g s o m e s o d i u m hydroxyde crystals. The problem is:
The ''Crystals'' appea r to be tiny tiny b alls and (correct m e if I'm wrong) pure crystalline structures never ever appear in the
s h a p e o f a b a l l . I ' v e h e a r d t h a t i n C a n a d a , s o m etim e s t h e n a m e lye is u sed to refer to Sodium carbonate so I'm pretty
confused right now, although I have dissolved som e in water and it seem s to react with alum inum foil. form ing tiny bubbles of
flam able gas (hydrog en from what I know), which proves the presence of NaOH.
Is there a way to check for impurities in lye crystals?
ETCS (Ret) March 14th, 2008, 09:32 PM

Due to the worldwide "war on drugs" it is getting increasingly difficult to find pure Sodium Hydroxide at the retail outlets.
Fortunately, there are som e rather easy m e t h o d s t o m ake your own Caustic Soda from So dium Bicarbonate (Sodium Hydrogen
C a r b o n a t e ) o r S o d i u m C a r b o n ate which will be sufficienty pure for most a pplications and considerably m ore pure than the retail
brands.
Pure Lye is u sually in the form of flakes; the tiny prills that you have found are probably a m i x o f S o d i u m C h l o r i d e a n d S o d i u m
Hydroxide. For cleaning drains pure Lye isn't necessary.
How much Sodium Hydroxide are you in need of? More than it would be convenient to m a k e y o u r s e l f ?
Silent Freedom March 15th, 2008, 12:36 AM

Lowe s ha s a drain o p e n e r c a l l e d " R o e b i c C r y s t a l D r a i n O p e n e r " a n d i t a d v e r t i s e s r i g h t o n t h e b o t t l e t h a t i t i s 1 0 0 % l y e .
TheBlob March 15th, 2008, 03:42 AM

W ell I would need about m a y b e 5 g s o I g u e s s I c a n m ake it myself. Tho ugh I no w n e e d t o f i n d a n o t h e r h y d r o x y d e t o m a k e
s o m e NaOH.
ChippedHammer March 15th, 2008, 06:56 AM

Its pure, its in a form called 'pearls' which are much like prills.
S o d i u m h y d r o x i d e o n l y c o m es in two forms, flakes and pearls. Its probably 98-99% pure.
http://www.tradekey.com/ks-caustic-so d a - p e a r l s /
Charles Owlen Picket March 15th, 2008, 10:08 AM

On -=some=- MSDS for technical grade chem icals there exists a CAS level of purity code. This unfortunately, has not been
stan dardized but if it exists fo r your particular chemical you can find a few items of worth.
Generally, ch emical wholesalers like to keep to three gradations (of technical, rea gent, & analytical purity). The problem exists
with "W HAT" THE MAR GIN OF IMPURITY CAN C ONTAIN. One issue therefo re is: - "would an ything be totally inert?" [CAS seem s
to feel that "inert" is som ething that can be quantified.] I like it when desiccants are considered inerts, whe n in fact they are
reagents in various other field s, etc.....<sigh>
So far TTBoMK, technical can drop down to as low as 63% labeled purity....That's pretty da mn poor; but tha t what's term e d
technical. However, m ostly it's 93% like in H2SO4 and b etter. An alytical has to be better than four figures (>99.9999%). This
m ay change as the various EU countries are getting involved in guidelines for precious me tals and chem icals.
Enkidu March 15th, 2008, 03:45 PM

See attachment for details on how to standardize your NaOH soln. This is probably out of your reach, as it requires a primary
stan dard, as Charles was saying, and high precision glass like burrets. However, because you don't need to know EXACTLY
what the concentration is, you could just do a couple of rough titrations with m uratic acid and that purple cabbage indicator
(http://chem istry.abo ut.com /library/we e k l y / a a 0 1 2 8 0 3 a . h t m ).
TheBlob March 15th, 2008, 04:32 PM

W e l l I h a v e s o m e 3 1 , 4 5 % p u r e H C l a n d s o m e litmus papers, I could make a rough titration, pretty easy since they're both
strong acid a n d b a s e , a n d t h a t would give me an approximate concentration of m y NaOH (should have thought of that before).
Only question now is: Usually, does 31,45% pu re means weight of the HCl/weight of the solution, or by volum e ?

W eight. Grams HCl / gram s solution
Setharier July 3rd, 200 8, 12:35 PM

Is it phossible to concentrate 10-15% drain opener NaO H by boiling water out and get 99% crystals? I mean I tried to do so,
but actually just got the room e x t r e m e NaOH sm ell and the stuff didn't seem to boil m uch at all, even placed into sand filled
pot over an gas heater.
Btw, does pyrex glass flasks and other ware stand direct heating from ethanol heater nor blue flam e " s c h o o l c h e m l a b h e a t e r "
- thing?
russoc4 July 3rd, 200 8, 09:17 PM

Is it phossible to concentrate 10-15% drain opener NaO H by boiling water out and get 99% crystals?
I've never tried, but solid NaO H is very deliquescent (it will absorb water and turn into a solution in a norm al atm osphere). So it
m a y t a k e a d e c e n t a m ount of energy to evaporate all o f the water.
Btw, does pyrex glass flasks and other ware stand direct heating from ethanol heater nor blue flam e " s c h o o l c h e m l a b h e a t e r "
- thing?
Pyre x can withstand direct heating. It is one of the qualities of Pyrex to be able to expand/contract quickly without shattering,
but it if the flame is hot enough, Pryex will m e l t l i k e a l l g l a s s e s . T h e g l a s s w a r e d o e s n o t n e e d t o b e e n g u l f e d b y t h e f l a m e . I t
should be raised above the flam e and just close enough to be h eated.

and Improvised Chemistry > Iodine production
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Roy Paci March 20th, 2008, 09:04 PM

Hi everyone,
as always, I apologize if thi is being discussed somewhere else round here. Couldn't find.
Issue is:
I was dreaming of me having a hydroalcoholic solution of I and KI.
It is 50 ml containing:
- 3.5 g of I
- 2.5 g of KI
In the dream i didn't know about the alcohol ratio. So I figured I would just boil it out.
Then I dreamed I wondered If I could convert the KI in I via electrolisis.
Two bechers, one with the I/KI solution with the anode in it.
A saline bridge connecting this beaker to the second containing water with NaCL. And the Catode.
In my dream potassium was moved to the catode, passing in the second beaker. I- and Cl- moving to the anode, in the first
glass. Cl2 thus formed flying away.
Would it work, in your dreams?
Thanks

If you can get bleach and hydrochloric acid, that's your best bet.
Boil off the ethanol. Add bleach, then hydrochloric acid SLOWLY.
NaOCl + 2HCl ---> NaCl + Cl2 + H2O
2KI + Cl2 ---> I2 + 2KCl
The iodine will precipitate.
If you are dreaming, you are better off on a different forum.
Masonjar Chemist March 20th, 2008, 11:54 PM

I used the NaOCl + HCl method with success. IMHO this is method with KI is so easy that it would be wasteful to try anything
else. http://www.dererumomnis.org/bbs/index.php?topic=293.0
Roy Paci March 21st, 2008, 04:46 PM

I read the thread you linked.
questions:
i read twice your post, enkidu, are you suggesting me to add bleache to the KI/I2 solution and then add to the bleach/KI/I2
the HCL? Or rather you are suggesting to flow Cl2 through my solution?
second:
if the solution contains I2 + KI one could simply add KCL to precipitate the already present I2??
thanks
Enkidu March 22nd, 2008, 09:32 PM

Please use proper capitalization. Also, the proper nomenclature is HCl and KCl, not HCL and KCL, respectively.
"Add bleach to the KI/I2 solution and then add to the bleach/KI/I2 the HCl." That is correct. You are generating chlorine in-
situ. It's the same thing as bubbling chlorine into the KI/I2 mix.
You won't precipitate I2 by adding KCl to your solution; it's a byproduct in the reaction that forms I2.
Genocyde March 22nd, 2008, 10:28 PM

You are better off using H2O2 & HCL. add a little water to the iodine solution, about 25 percent of the solutions volume. thenn
add a few milliliters of HCL. then slowly add 3 percent H2O2 while stirring until the solution starts to look milky. Let it sit for
abou 45 minutes and the iodine will have precipitated.
It's pretty easy to screw up with bleach.
Roy Paci March 22nd, 2008, 11:17 PM

Enkidu, so the elimination of the I3--- from I-salt is the key for precipitation, right?
It is not the action of the byproduct but the removal of iodine salt to get the I2 off the solution... Am I correct? There was not
capitalization to be written wrong, this time... :-)
Genocyde, I was not able to understand your issue.. 25% of what?solutions? What solutions?
thanks
Enkidu March 23rd, 2008, 12:15 AM

Yes, as the potassium iodide is converted to iodine, the solubility of the iodine in solution will decrease. Be sure to boil off all
the ethanol first.
I don't understand how it's 'pretty easy' to screw up with bleach... ?
Genocyde March 23rd, 2008, 07:03 AM

Sorry... I shouldn't post while stoned.
Boil off the ethanol? You realize that I2 sublimates at room temperature don't you? There is no need to boil off the ethanol
anyway.
Take the tincture of iodine, add water. The amount of water you add should be about 25 percent of the volume of iodine
tincture that you are using. 100ml tintcure add 25ml of water. Then add a few ml of HCL (muriatic). Now slowly add 3 percent
H2O2 while stirring until the solution looks milky. Let this mixture sit for 45 minutes and your I2 will precipitate. A big beautiful
pile of long skinny I2 crystals will be laying on the bottom of the container.
Decant all the liquid down the drain. Add a little fresh water and pour the I2 into a filter. Now rinse the I2 well with fresh water
while still in the filter. The best way to dry the I2 is to twist the filter, squeezing out most of the water. Now put the filter right in
the middle of a whole newspaper and squeeze the hell out of it. Keep moving the filter around in the newspaper and
squeezing until the filter no longer leaves a wet spot on the newspaper. Put the I2 in something airtight, and place it in the
freezer.
Piece of cake.
Roy Paci March 23rd, 2008, 10:53 AM

I will try to dream about both methods. And I'm trying to guess the chemestry behind H2O2 method... but no idea!
Gembli March 24th, 2008, 02:41 PM

Roy, I think he means:
H2O2 + 2 HCl - - - > Cl2 + 2H2O
Then the Cl2 reacts with KI as stated before;
2KI + Cl2 - - - > I2 + 2KCl
Pretty interesting idea there, as the chlorine stays (or should stay) as an aqueous solution eliminating the need to work with
toxic chlorine gas.
I hope this helped. :)

Sublimation of the I2 will remove any chlorides formed by the bleach method... even then, if you get the 'ratios' right, you
won't have many chlorides at all.
Roy Paci March 27th, 2008, 11:09 AM

I dreamt i tried the H2O2 method. Maybe too much HCl or too much H2O2... Obtained a poor yeld and I think lots were lost
during filtration process.
A bit of theory would improve this process. I don't like to dream to put something into something else without having at least
a clue on what I am doing. I'm still looking around to find something.
Nevertheless, if someone knows something, he could advice us...:confused:

Why not just do what I suggested? Masonjar did the experimental work in that thread on DRO. If you need a 'recipe' then
search the net... there are lots of recipes for both the H2O2 and the NaOCl methods.
blast_audit March 27th, 2008, 09:57 PM

Ive wade allot of I2 via the oxygenation method
Detailed Here on Frogfot's site
http://www.frogfot.com/synthesis/iodine.html
10KI + 2KMnO4 + 8H2SO4 ==> 5I2 + 8H2O + 2MnSO4
I can retain 90%+ yields using this method, I have tried many other methods but I find them tedious and I tend to like
avoiding the exposure to CL2 gas when H2O2 is added to HCL (but that's just me)
I would strongly recommend sublimation at least twice! A few reactions I have ran with I2 seem to react with let over chlorine
acid so I like my product clean
Secong Nature March 28th, 2008, 01:08 AM

Here (NZ) our iodine tinctures use a PVP (liquid polymer?) solvent which, after one try with possibly decomposed H2O2 i had
no yeild even though it was left overnight.
Is this because of the different solvent or just crappy H2O2?
Also the reaction with H2O2 doesn't involve chlorine AFAIK, its a textbook redox reaction: 2H(+) + H2O2 + 2I(-) --> I2 + 2H2O
So basically acid catylises an electron swap between peroxide and iodide, taking it out of solution as iodine.
Bugger March 28th, 2008, 04:59 AM

You probably used bad H2O2; and besides you should have used KI or NaI, not alcoholic tincture of iodine. However, there is
some tendency for liberated I2 to re-enter solution as the I3- anion.
BTW There is a current thread on this subject going on http://www.sciencemadness.org/talk .
blast_audit March 28th, 2008, 05:07 AM

Just thought you mite find it Interesting
I get my KI from horse specialists It is a supplement they give race horses.
Its expensive $55 for 500grms but per mol its still cheaper then I2
And if NZ is anything like Australia...

I would say that the Iodine tincture you are talking about (beterdine) is provodone Iodine which is 10% v/v but provedone only
has like 10% v/v I2
And afaik you cant extract I2 from provedone or its very inefficient
Thats just how it is here...
Roy Paci April 3rd, 2008, 12:25 PM

In my country I can only find iodine tincture. It is 7g of KI and 5g of I2 in water/alcohol solution (couldn't find the ratios). By
boiling of the alcohol (at 78C) until the T restared rise I obtained 2 things:
a harsh soring in my nose and eyes, and 20ml of solution with I2 precipitating out by itself.
I will perform the Cl2 method of course. I have to admit that the H2O2 method has the strong advantage of not needing a
toxic gas flow.
Was PVP Iodopovidone?
Bugger April 4th, 2008, 10:55 PM

Just thought you mite find it Interesting
I get my KI from horse specialists It is a supplement they give race horses.
Its expensive $55 for 500grms but per mol its still cheaper then I2
And if NZ is anything like Australia...(cut).
That KI given to horses is probably either analytical grade or pharmaceutical grade (USNF or BPC), which would also be
veterinary grade. As such, it would be far more costly, involving recrystallization, than reagent or "technical"/industrial grades
which may have bromide or chloride or other impurities. I wonder if farm supply stores have cheaper grades of the stuff, used
as a supplement for animals other than racehorses in iodine-deficient areas.
I think that most NaI and KI probably comes from the sea, along with the bromides, as a byproduct of common salt
extraction, being much more soluble than NaCl, but they would be very impure to begin with. The iodine and bromine are
probably obtained from the brine left over by oxidation. There are also deposits of NaIO3, mixed with halides and nitrates, as
caliche in the desert areas of northern Chile.
bobo April 6th, 2008, 06:10 AM

Iodine can be extracted from formulations (aka, stuff that contains unwanted crap) using copper (II) sulfate or similar copper
(II) salts. In order to do this, the iodine needs to be in the I- state.
From wikipedia:
# In the laboratory, copper(I) Iodide is prepared by simply mixing an aqueous solutions of sodium or potassium iodide and a
soluble copper(II) salt such copper sulfate.
# Cu2+ + 2I CuI2
# The CuI2 immediately decomposes to iodine and insoluble copper(I) iodide, releasing I2.[2]
# 2 CuI2 2 CuI + I2
This means that you need to add potassium sulfite or similar agents (many ways of reducing I2) to an aquous solution of
'contaminated' iodine until colorless, and then some. The insoluble CuI comes out as a dirty grayish salt but this is OK, even
ACS reagent CuI seems to have this color. This salt is collected and the solution (once depleted of iodine) is discarded.
CuI cannot be dissolved in water but it can be oxidized in water regardless of this fact. I once added H2O2 and H2SO4 to CuI
and iodine appeared, but there are really tons of ways to make I2 from I-.
russoc4 April 19th, 2008, 12:24 AM
I have seen bromine generated in situ in order to brominate stilbene. To 10mL of ethanol with 0.5g of stilbene dissolved in it,
1.2mL of HBr was added to the and then 0.8mL of 30% H2O2 was added. The method described above should work in a
similar manner to generate Cl2 in situ to precipitate iodine.
Intrinsic July 9th, 2008, 01:14 PM

Here is a link to a video showing the H2O2, KI, HCl process:
http://www.youtube.com/watch?v=CLhwkFKLdPA
Seems pretty straightforward and simple. (BTW thank Charles for the link, he referenced it in another thread).

This process is a plug for the new book by Make Magazine titled "The Illustrated Guide to Home Chemistry Experiments" by
Robert Thompson. This book is perhaps the book I would have written had I written a book. Thompson is a man whose views
closely parallel my own concerning the demise of chemistry in today's society. Check out his speech on the demise of the
chemistry set here: http://blog.makezine.com/archive/2008/07/robert_bruce_thompson_on.html
Back to the iodine, there is a direct link to download the video from the publisher here:
http://cachefly.oreilly.com/make/WeekendProject10Chemistry.mp4
There is a page devoted to the video, and to plug the book, at the Make website in the weekend projects section:
http://blog.makezine.com/archive/2008/06/weekend_project_home_chem.html
Not only is potassium iodide an uncontrolled and unrestricted substance, but the fedgov actually gives samples away if you live
with, I think, 50 miles of a nuclear power plant. You can also buy KI pills from a number of companies that sell it as pills for
emergencies, although you will pay a premium price.
What the video did not show is how to purify the iodine to get actual crystals. This depends on what kind of reaction you need
the iodine for, of course, but usually you don't want hydrochloric acid, hydrogen peroxide, and potassium ions contaminating
your reaction. Filtering through a coffee filter will only be marginally effective as you would lose a considerable quantity of
iodine. However, it works, and that is what really matters.
phrankinsteyn July 12th, 2008, 04:13 PM

Megalomania, thanks for your opinion of the book "The Illustrated Guide to Home Chemistry Experiments" by Robert
Thompson. I have been thinking about buying this book (I have only read online reviews from others) but was unsure if it was
worth the price and contained good/proper information. I will buy it now.
I uploaded the MAKE- Blog (iodine video) Weekend Project- Home Chemistry.flv to the ftp.
It is in folder: UPLOAD/Phrankinsteyn.

I almost bought the book last week myself, but I thought about it later that evening while taking a walk and ran a prime
projection... After I shell out my $30 of money I could better use elsewhere, I would just toss it on my stack of papers and not
get around to reading it for a few months. I also know as soon as I buy it an ebook version will appear on Gigapedia, although
I would prefer to have this in printed form. I will wait to buy this book until I have the time and inclination to actually read it.
There is now 1 copy available via interlibrary loan, checked out and reserved for months in advance, so that might be an
option once the dust settles and people stop reserving it.
The book is actually much larger than I thought. I saw the author flipping through the pages of the copy he was clutching in
the iodine video. That thing is as big as a phonebook!
If anyone has a line on where a ebook copy can be obtained, let us know ;)
Cobalt.45 July 25th, 2008, 09:53 AM

No ebook source, but the printed version can be had for $17.30 + $3.99 S&H from Amazon.
Thanks to the positive review, I just ordered it. Can't wait.
ChippedHammer July 27th, 2008, 11:03 AM

Just purchased a copy off eBay, looks like a great book :)
phrankinsteyn July 28th, 2008, 10:04 PM

Received the book today, has a few experiments I must try. :)
Here are a few links from the book that may be of interest to some of the members here.
http://www.homechemlab.com/
http://forums.homechemlab.com/
newsletter address: [email protected]
The book states that the newsletter is published sporadically and if possible subscribe using a "real" (ISP) email address
rather than an email address from Yahoo, Gmail, or a similar free email service. If newsletter email to your address bounces,
that address is removed automatically from the mailing list.
Smokey0541 July 28th, 2008, 10:49 PM

I read the thread you linked.
questions:
i read twice your post, enkidu, are you suggesting me to add bleache to the KI/I2 solution and then add to the bleach/KI/I2
the HCL? Or rather you are suggesting to flow Cl2 through my solution?
second:
if the solution contains I2 + KI one could simply add KCL to precipitate the already present I2??
thanks
I think you should confirm this with Meg or COP. Something doesn't sound right here to me. And those guys are pretty sharp.
My knowledge is on a need to know basis. But it just doesn't sound right
phrankinsteyn July 29th, 2008, 02:21 AM

This along with his video should do it (help people like me). :)
Here is the link and procedure (copied from) to Robert Bruce Thompson method of iodine production:
http://forums.homechemlab.com/viewtopic.php?f=8&t=3&sid=50e56bb635fd5d6f9ceb83825ac18e93#p3
Isolating elemental iodine from potassium iodide
Iodine crystals are used in a couple of the experiments in the book. When I wrote those sections, iodine was freely available,
but the DEA recently moved iodine to List I, which means it now requires completing paperwork and showing ID to purchase
iodine. Fortunately, there's a very easy way around this problem. You can isolate elemental iodine from potassium iodide,
which is included in one of the chemical kits. To do so, take the following steps:
1. Weigh out 2.0 g of potassium iodide and transfer it to a test tube.
2. Add about 1.5 mL of distilled water to the test tube and swirl to dissolve the potassium iodide.
3. Add 1.5 mL of concentrated hydrochloric acid (or about 1.8 mL of hardware store muriatic acid) to the test tube and swirl to
mix the solutions.
4. Add about 10 mL of drugstore 3% hydrogen peroxide. The solution immediately turns dark brown as the iodide ions are
oxidized to elemental iodine, which precipitates out.
5. Swirl the test tube to suspend the iodine and pour the liquid through a funnel with a folded piece of filter paper to capture
the iodine crystals.
6. Rinse the iodine crystals on the filter paper several times with a few mL of distilled water. The rinse solution appears brown
from dissolved iodine, but iodine is not very soluble in water, so you're not losing much of your yield.
7. Spread out the filter paper on a watch glass or saucer and allow the crystals to dry thoroughly. Iodine gradually sublimates
(passes directly from solid to gaseous form) at room temperature, so don't leave the crystals exposed to air any longer than
necessary to dry them.
8. Once the crystals are dry, transfer them to a sealed storage bottle or vial.
These quantities produce a gram or so of iodine, which is sufficient for the experiments that require it. If you need more
iodine, simply increase all quantities proportionately.
Robert Bruce Thompson

thompson (at) homechemlab (dot) com

Ah ha, I have been to that home chem lab forum. I thought it was just some spammers trap with all those numerous empty
sections. This is the latest spammer trick, making fake blog comments and bulletin board posts on sites they created that
makes it look like people are talking about the product. Porn sites are the most prolific in this regard.
Poor iodine. Now I have to jump through fedgov hoops and convince them I need iodine to kickstart Grignard reactions, not to
dominate the world as a meth cook. Time to start buying sea weed...
Enkidu August 1st, 2008, 02:50 AM

Time to start buying sea weed...
Hahahaha... next you'll be trying to isolate a certain amine from gallons of your saved piss.
If we ever get a user-submitted content thingy working, I2 should be one of the tutorials.
Cobalt.45 August 1st, 2008, 08:49 AM

I also just received "The Illustrated Guide to Home Chemistry Experiments" by Robert Thompson. It's laid out something like
a course text in that it has a quiz at the end of each lab along with "Required Equipment and Supplies", "Substitutions and
Modifications" and "Optional Activities" that delve a bit more into the lab at hand.
Interestingly, the individual labs are in many cases designed to give a useful result, like molar solutions, etc., that can be
kept for supplying your home lab and not just tossed out at the end of the lab. It's a good idea to read ahead to the next lab
before disposing of the previous lab's results because sometimes the results are used in the next lab (reminds me of my old
Gilbert chemistry set in this regard).
Most if not all of the Guide's info can be found online but this has the advantage of being progressively ordered and all in one
place.
But make no mistake- this is aimed squarely at the beginner, and you will find no labs for pyrotechnic devices or HE's, et al.
It advertised that the completion of this guide would be the equivalent of a first-year college general chemistry lab course, and
is probably an accurate assessment.
jarynth August 3rd, 2008, 11:48 AM

Hey, for US residents the link below might contain useful for those intending to buy iodine legally, including pretexts for the
purchase and warnings about suspicious behavior.
"The Comprehensive Methamphetamine Control Act of 1996 identifies iodine as a List II chemical. DEA mandates that detailed
records be kept for sales of iodine crystals that exceed the threshold of 0.4 kilogram established in 2000. Anyone who sells a
total of 0.4 kilogram (13.98 ounces) of iodine crystals to an individual, corporation, business, or other legal entity in a 2-
month period must obtain data identifying the purchaser, keep records of the transactions for 2 years, and report any
suspicious transactions to DEA. This rule does not apply to iodine tinctures or other iodine mixtures."
http://www.usdoj.gov/ndic/pubs1/1467/index.htm

Small irony here is, I just learned (from the above link) more about meth production than I knew previously!
If I were contemplating making this shit, I would be investigating "cold-cook" methods as well as having learned all I need to
know in regards to research to prepare myself for scrutiny from a supplier of iodine.
Truth be known, I actually wish that meth could be eradicated. Too bad that the powers that be decided to make everything
but the kitchen sink regulated towards that end- w/o actually removing the scourge.
Just saw 100g go for >$20/oz on eBay, even potassium iodide has gone through the roof. And just when I really need iodine
to do some legit chemistry labs with:mad:...
jarynth August 4th, 2008, 03:06 PM

This police site with suggestions on what clues to look for in spotting meth labs...or amateur chemistry labs for that matter. It
can be reverse-engineered to provide security hints for the amateur chemistry on how not to arouse too much suspicion. Cops
should be proud of their work, they're teaching us a lot.
http://www.qccrimestoppers.com/projectX.shtml
"Methamphetamine Labs
Quad City MEG Teams up with Crime Stoppers

August 16, 2004
Quad City Metropolitan Enforcement Group announced a new partnership with Crime Stoppers of the Quad Cities to locate,
eliminate, and arrest those responsible for methamphetamine labs.
Methamphetamine is one of the most dangerous drugs officers encounter. This is due to the hazardous materials that are
used to manufacture meth, along with the volatile environment a lab creates. Officers who respond to labs place themselves in
an unstable environment that has the potential to injure them.
In response to the recent increase in labs, Quad City MEG and Crime Stoppers have started this awareness campaign. Billboars
were put up in six locations around the QCA. hen a person chooses to start up a meth lab, he/she places the public,
neighbors, children, the environment, and law enforcement officers in danger. Meth cookers need to know that law
enforcement has a zero tolerance and that IF THEY COOK IT - WE WILL COME!!!!
If you have any information concerning a possible Methamphetamine lab, call the Crime Stoppers tip line, 309-762-9500. If
your information leads to a felony arrest, you'll receive a cash reward of up to $1,000.
What are indicators of a clandestine methamphetamine laboratory?
* Little or no traffic during the day, but lots of traffic at extremely late hours.
* A strong smell that might resemble urine, or unusual chemical smell like ether, ammonia, or acetone.
* Extra effort made to cover windows or reinforce doors.
* Residents never putting their trash out or burning all trash.
* Lab materials surrounding property (lantern fuel cans, red chemically stained coffee filters, clear glass jugs, and duct tape).
* Vehicles loaded with trunks, chemical containers, or basic chemistry paraphernalia like glassware and rubber tubing.
* Laboratory glassware being carried into residence.
* Inhabitants smoking outside due to the fumes.
* Dying grass or plants in a particular area.
Business owners should be aware of customers who purchase or steal an excessive amount or a combination of the following
items. Any unusual pattern of purchases of these items should be reported to police.
Acetone Aluminum foil

Anhydrous ammonia Brake cleaner
Camping fuel Coffee filters
Denatured alcohol Drain cleaner
Engine starter fluid Ether
Ephedrine/pseudoephedrine Products Funnels
Gasoline additives Iodine
Iodine crystals Iodine prill
Iodine tincture Lithium batteries
Lye Matches
Methanol Muriatic acid
Paint thinner Propane tanks
Red phosphorus Rubber tubing
Rubbing alcohol Sodium hydroxide
Sodium metal Sulfuric acid
Table or rock salt Toluene"
Intrinsic August 4th, 2008, 03:57 PM

If the information in the last two posts is accurate, then that is a potential way to generate some income.
There is a legal 2 month, 0.4kg (about 14oz) limit to selling iodine (per buyer) - without needing any substantiating buyer
information. Iodine sells on ebay for $20oz. Some additional number crunching is needed, but it sounds profitable. You would
need to factor in the prices of potassium iodide, and H2O2, and the HCl. Set up a few shell e-bay accounts, and you're ready
to go!
I just did a quick ebay search for crystal iodine, it seems the average price is about $30 for 100g. One guy has for sale 200g
at $150! It says he ships daily (with the tracking info in 2 hours :rolleyes:), I wonder how much business he gets at that price.
I have to wonder if any of the sellers are fevgov in disguise looking for meth cooks.

I just did a quick ebay search for crystal iodine, it seems the average price is about $30 for 100g.
A quick look shows the $28 price is for 28g! A cool C-note/100g.
The only "deal:p" is BIN for $53/100g, others are auctions that haven't ended. These auctions have been going for as much
as $70/100g, as I indicated earlier.
I have to wonder if any of the sellers are fevgov in disguise looking for meth cooks.
Now, do you really have to wonder?;)LOL
One guy has a "newbie" icon w/a feedback score of 2 and NO other items for sale. Now if that doesn't send up a red flag...
jarynth August 5th, 2008, 08:51 PM

Contributing to the resources on controlled substances, I'm submitting this list of prescribed quantities of precursors (status
2007):
http://www.dms.dpc.vic.gov.au/Domino/Web_Notes/LDMS/PubLawToday.nsf/b12e276826f7c27fca256de50022686b/
db5b889aaa4657c3ca2573230000d01f/$FILE/07-84sr001.pdf
PS: Maybe this thread isn't the most appropriate place for the legal stuff I've been posting about controlled substances, but
several searches didn't turn up a current ad-hoc thread.

and Improvised Chemistry > Hexamine Synthesis step by step w/ pics
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View Full Version : Hexamine Synthesis step by step w/ pics
Rbick March 22nd, 2008, 01:47 PM

Over the last couple weeks, I have taken an interest in producing my own hexamine. The precursors are cheap and not
watched too much by big brother and the procedure is simple. I saw there are a couple old hexamine threads, but they were
unorganized and offered conflicting opinions. I will post my lab notes from my experiments starting with the concentration of
the ammonia solution. I also have a few pics I will provide along with some of these steps. Also note that all of this was done
with OTC products. I will describe where and how I purchased all the materials used in the text.
I realize hexamine can be bought through ebay or chem suppliers. At first I just wanted to produce hexamine for the
experience, but after determining that I can make 500g of very pure hexamine for about 6 or 7 USD, I decided it might be a
better idea to make my own. This will also help avoid unwanted attention, as hexamine itself is a precursor to many drugs
and, obviously, explosives.
For this lab you will need:
100mL 10%+ ammonia solution

50mL 40% formaldehyde solution
Beaker
Thermometer
Ice Bath
Hot Plate or some type of heat source
Lab safety (goggles, gloves, lab coat)
Hexamine is produced via the addition of ammonia solution to a solution of formaldehyde. It is important to use the most
concentrated ammonia you can achieve, as this will have an effect on your yields. It will also decrease the amount of water you
need to evaporate in the end and save you time. So first I will go over how I concentrated my ammonia. I should also
mention that I received much information from Charles Owlen Pickett, who communicated with me through PMs to give me
advice on how to perform this experiment. Thanks Charles :cool:
I started with household 5% ammonia solution bought for 2.99 per gallon at the local hardware store. Now the way to
concentrate it is to bubble ammonia gas through the solution. The set up for this is very simple, as you can see in this picture
(http://i164.photobucket.com/albums/u6/pudgedog69/DSC00215.jpg). You don't need a flask, just another bottle would work
just as well. The polyethylene tubing was about 15 cents per foot. The whole setup would cost about 3.50 for the soda bottles,
the tubing and the hot glue. The water bath is to keep the solution cool, as more ammonia will dissolve if the solution is
cooler. Remember that with gasses, solubility goes up as temperature goes down. This is needed as the reaction in the flask
is highly exothermic, which I will now discuss.
The contents mixed in the flask are anhydrous Sodium Hydroxide (NaOH) or what is commonly known as lye. This was bought
at the hardware store for 3.79 per pound (454g) listed as a drain opener. Note that any metal Hydroxide can be used in this
reaction. The other substance was Ammonium Nitrate. Now before you flip out, just hold on! The AN can be replaced by any
Ammonium salt. Ammonium Sulfate, which is a very easily found and cheap fertilizer, can be found at most hardware stores in
the spring. (EDIT: I just purchased 15 pounds or 6.8kg of AS at Steins Garden and Gifts for $12.06) I am awaiting my
shipment of AS as I am too inpatient to await the spring to come. I found mine for 4.10 per 5 pounds on ebay. This is just
one Ammonia salt that can be used, any others are acceptable. I chose Ammonium Sulfate due to the fact it has two
ammonia groups bonded to one sulfate group, whereas many ammonium salts only have one. Just make sure to adjust
quantities appropriately. When these two are mixed, a single displacement reaction takes place. *SEE NOTES AT BOTTOM*
NH4NO3 + NaOH ---> NaNO3 + NH3 + H2O.
This makes it pretty simple, as the molar ratio is 1:1. This would mean 80g of AN mixed with 40g NaOH would yield best
results. You will notice that the resulting water will cause the mixture to clump. Just shake every now and again to loosen it
when the reaction starts to slow down. In this reaction, you see that Sodium Nitrate is evolved! I need to find a way to extract it
from the unreacted NaOH and AN so I can use it again... Also remember that this reaction is highly exothermic, so be careful
with it and use an ice bath if you must.
You should notice gas start to bubble through the solution. Remember to check the bottle for excess pressure to ensure
nothing explodes on you. If the bottle is gaining excess pressure, slowly open the top to relieve it. I found that bubbling 1
mol of AN and NaOH through 100mL of water yields a good percentage. 1/2 mol of each through 100mL yielded a solution that
left quite a bit of excess formaldehyde after the reaction, which really stinks up the place when evaporating for your product.
The yield was decent however, about 12g as opposed to the 15g achieved with the latter. If bubbling the 1/2mols per 100mL,
perhaps 125mL should be used instead. More on that later.
Now that you have your highly concentrated ammonia solution, you are ready to add it to the formaldehyde. Formaldehyde is
used to a great extend in agriculture. Therefore, it can be bought at many agriculture stores, for a cheap price. I found mine
for 14$ per gallon, and they told me if I ever wanted it in 55 gallon drums, the price would be reduced to 6$ per gallon. I was
only asked for ID when I purchased this. Remember that social engineering plays a huge role in obtaining materials without
making people suspicious. Since the production of hexamine is not illegal, I went ahead and told them what I planned to do
with it and gave them a little chemistry lesson. I think they were really amused and liked it.
Anyway, place 50mL of 40% formaldehyde in a beaker. Place that in an ice bath. Slowly add 100mL of your ammonia while
stirring. Note that the ammonia will be in excess for this reaction. You will notice a large increase in temperature. If it gets too
hot, sparks and smoke may result. After addition, stir well and let the solution stand for 24 hours. It is probably not necessary
for 24 hours, but I do it to ensure completion of the reaction.
Note: When mixing with 5% ammonia solution, I noticed almost not rise in temperature. The yield was also horrible, barely
any crystals to scrape off the side of the beaker. This shows the importance of having concentrated ammonia. The yield could
have been fixed by adding much more 5% ammonia, but the evaporation that would have to be done later would not be worth
the effort in my opinion. While evaporating the solution, it also smelt horribly of formaldehyde. So badly I had to go and get
my gas mask.
After the solution has stood for 24 hours, get your hot plate ready. Your solution should still be crystal clear, as seen here
(http://i164.photobucket.com/albums/u6/pudgedog69/DSC00217.jpg). Heat your solution to about 90*C and allow the water
to evaporate. Note the only byproduct of this reaction is water. Seen below.
6CH2O + 4NH3 ---> C6H12N4 + H2O
There will of course be some unreacted products, so evaporate in a well-ventilated room or outside. When all of the water is
evaporated off, you will be left with a cake of wet hexamine crystals. You can dissolve these again in distilled water or alcohol
and recrystallize if you wish.
Place your crystals on a glass plate or something that can withstand heat in an oven. Put your oven to 100* C. Don't worry
about the hexamine, it will only start to sublime at 280* C. When they have dried, remove them and allow the crystals to cool.
You should have a product of nice white crystals, like this (http://i164.photobucket.com/albums/u6/pudgedog69/
DSC00216.jpg). My yield from the quantities used in the above experiment resulted in 15g of hexamine. This is a picture of
the hexamine burning (http://i164.photobucket.com/albums/u6/pudgedog69/DSC00220.jpg).
I hope this information was useful. If anyone else has had experiences with making hexamine or concentrating ammonia, I
would love to hear it. Critism and corrections are welcome too.
NOTES:
*Remember that the two compounds being mixed (the hydroxide and the ammonium salt) must be in powdered form to
achieve max surface area, resulting in a faster, more efficient reaction.
*I would also like to mention that ammonium sulfate, formula (NH4)2SO4, will require a molar ratio of 1:2, as sodium sulfate
has the formula of Na2SO4. Sodium sulfate is actually a hydrate, which will absorb water and turn blue. This could be useful as
it will absorb water from the reaction and the color may give an indicator as to how complete the reaction is. These are just
ideas as I have not used ammonium sulfate yet. I'll let you guys know.
Shadowmartyr March 23rd, 2008, 07:24 PM

Wow this is great I've been looking all over for a detailed hexamine synth. Well written, good instructions, nicely done!!
Barnacles March 24th, 2008, 12:27 AM

Thanks alot for the information. And props to COP(Charles Owlen Pickett) for helping you. Sorry if the short title offends you or
irks suspicion from others. Looks like you probably save heaps of money making it rather than buying camp stove fuel I get
77gs for ~5-7$ most likely it is. My friends uncle owns a funeral parlor and it services bodies there. I am going to mention my
need for gallons of Formaldehyde for this purpose, hopefully he doesn't think I am nuts. lol. When people these days here
chemistry or chemicals, they immediately think drugs, bombs terrorists. and that no person should be doing experiments at
home , like why would they need to. :rolleyes:
I have a question though sort of off topic, you claimed the reaction was not illegal, is there a site where I can find information
on what type of reactions are legal and what are not? Is it illegal to make black powder for instance. My main illegality
question would be is it illegal to produce Nitrocellulose? I wonder because I know you can buy it as magicians paper or flash
paper, but it is prohibitively expensive, something like 300$ for 30grams if I remember correctly... I actually do some "magic",
I am starting out. So you can see why I would ask.
And as we all know just because you can buy something does not make it legal to produce. Thanks in advance.
Shadowmartyr March 24th, 2008, 09:38 AM

I have a question though sort of off topic, you claimed the reaction was not illegal, is there a site where I can find information
on what type of reactions are legal and what are not? Is it illegal to make black powder for instance. My main illegality
question would be is it illegal to produce Nitrocellulose? I wonder because I know you can buy it as magicians paper or flash
paper, but it is prohibitively expensive, something like 300$ for 30grams if I remember correctly... I actually do some "magic",
I am starting out. So you can see why I would ask.
And as we all know just because you can buy something does not make it legal to produce. Thanks in advance.
I am pretty sure making homemade black powder is not illegal, at least not in the state I live, as such theres probably
different laws for different states regarding blackpowder rather than heavy explosives with the federal government (thats how I
understand it anyways, anyone feel free to correct me on that).
Anyway, Barnacles, there is a text file of a list of explosive materials that are regarded as "watched" by the ATF.
Included on this list is black powder based explosives, nitrocellulose, and HMTD (Hexamine being a common fuel for small
stoves would obviously not be on the list, however, they probably keep a watch for large quantities of the stuff being ordered
like they would anything else).
The ATF list file is outdated, but I don't think that would matter, if anything they have added material instead of taken
anything off :( . You can get it on the FTP under "UPLOAD\Mr Science\The Disease FTP\Explosives\Law".
Hope that helps.

[The chemical watch list issue & the ATF are mostly contextual.] In that, there does not seem to be a great deal of intense
scrutiny for Joseph Blow but if someone has caught their eye (ATF) for other issues then the list and chemicals, generally -
make for a report within a report. This is often used to "prep" a case for the Prosecution & made available to the defense
upon discovery. Juries like to ogle chemicals and the more they have, the more they have....it's show-biz for a court-room.
Unless you have a lab with drug precursor chemicals in it, there is generally little interest outside local fire ordinances.
Hexamine is a very flexible material and this lab illustrates how materials that utilize hexamine are VERY inexpensive from a
manufacturing perspective. Often it's said how cheap RDX is....and you can see that with a production mechanism with a great
deal of ammonia & formaldehyde; the stuff could be dirt cheap. No matter how you cut it, PETN will never have this
inexpensive of a precursor, etc.
This is a valuable thread as it opens itself to a variety of synthesis of hexamine. It's also important to remember that no
hexamine (or R-Salt) wash water / synthesis water) is ever wasted. It can always be evaporated and the last bit made
available. There is very little waste in these synthesis!
Oss March 24th, 2008, 11:53 AM

Rbick - nice post; straightforward and simple, even for me who forgets everything...
One question however: as you spent the time calculating ammonia output from the NH4NO3/NaOH mix, why didn't you just
bubble it directly through your formaldehyde solution?
This would mean less water to evaporate, a cooler reaction temperature and one less step.
(The ammonium solution concentration step could be useful for other reactions, of course)
Rbick March 24th, 2008, 11:57 AM

Excellent idea! I never even thought about this. I would have to do some experimenting with it though to see how easy
temperature is to control, ratios, ect. Anyone have any experience with this method?
Charles Owlen Picket March 24th, 2008, 12:06 PM

NOW...YOU HAVE GROUND BREAKING STUFF AVAILABLE. I looked this up while I was reading it and couldn't find a thing on
going direct. The only thing to do is try it! Keeping in mind molar ratios you may want to attempt a 50% level at starting. My
reasoning is that the most common industrial ammonia is around there. Remember that you are dealing with a flammable
material in this as there will be no water to minimize that hazard. Additionally you may want to keep temps within 80 C so you
don't loose a yield to fumes.
Use a "deep" container; so as to allow fullest contact with the gas. Just as the best yield of Silver Acetylide is achieved with a
deep flask or even test tube rather than a beaker you want contact with the gas to be as long as possible. You may even want
to maintain a slow-bleed exhaust system to maintain gaseous contact longer, etc.
Rbick March 24th, 2008, 12:31 PM

Yes, I will be trying this soon.
I should also mention the results of using Ammonium Sulfate. I mixed it with NaOH and no gas was produced. This was
strange, because with AN, simply mixing the two solids resulted in ample gas production.
Without thinking, I quickly added about 10mL of water. Ammonia gas was VERY rapidly produced. I had to go grab my M-40
gas mask and run outside with it. Stupid I know, but the little added water started the reaction which continued through until
completion. It seems the water is needed to "jump start" the reaction. Next time, I will try adding 1mL through an eye dropper
and see how it works.
The resulting ammonia solution was highly concentrated, and I'm assuming is better than with AN/NaOH. The mixture also
bubbled gas through the solution much longer than AN/NaOH. My molar ratios were 1:2 SA to NaOH and I used 66g/40g per
100mL of 5% ammonia solution. This may actually be too much, I'll calculate it and make a prediction later. I will also gather
experimental results first, as those are obviously more trustworthy than theoretical :)
Oss March 24th, 2008, 12:57 PM

Rbick, fast moving today..
I'd wonder if some of the energy for the reaction came from the NaOH giving off heat as it dissolved, bumping the reaction
temps up and speeding your ammonia production?
I had in my mind a setup with your flask - a outlet for the ammonia with tube, going into the formaldehyde solution as you
have and an inlet with a funnel inserted. (Referring to your first posted image might help with the visuals here!)
The ammonium sulphate could be already in the flask as a solid and a sodium hydroxide solution could be poured in as
required (ie as the production of ammonia slows). Note to anyone - perceived or real danger of overpressure in flask forcing
caustic NaOH up and out of the funnel onto hands/into face of the operator before it completely drains into flask? Perhaps just
removing the stopper temporarily and pouring in a small amount at a time would be sensible.
If I was to do it myself, I'd aim for an excess of ammonia to be made to allow for some escaping. Once the ammonia/
formaldehyde reaction is complete, any excess dissolved ammonia should be dispersed while one evaporates the water.
I'm conscious of Charles' references to flammability and your own experience of the overpowering encounter with ammonia
gas. Safety first and slow but steady gas production is likely good advice.
The above is all subject to hearsay as I have no hard facts to hand. Am tempted to go and establish some personally though.
Open to comment.
ProdigyChild March 25th, 2008, 09:57 AM

I would prefer using lime - either Ca(OH)2 or CaO - for NH3 production. Due to ist poor solubility in water the reaction rate
should be lower - especially when using (NH4)2SO4. Its low price is hard to top.
I'm not a chemist. Perhaps theres a downside unknown to me?
Rbick March 25th, 2008, 12:29 PM

If lime is more accessible to someone, then yeah I would use it too. Solubility in water doesn't play too much of a role in the
method that I use, I just need to add less water and at a slower rate to ensure my reaction doesn't run away on me and fill
my house with ammonia gas. I may try lime however, as I believe I can get it for far cheaper than NaOH and in bulk. Thanks
for throwing that idea out there.
There is actually a thread out there on the production of ammonia started by mega a few years ago. He does in fact mention
Ca(OH)2 as being a good material to use. A quick search of the forum will find it. The only problem I can see is that since it
has two hydroxyl groups, it will probably produce a lot of water byproduct, which could be detremental. But if you don't mind
the extra water, it doesn't sound like a bad idea.
Jetex Kid March 25th, 2008, 11:27 PM

This post's heading is from a headline in the Health section of the March 25 NY Times, and they are talking about
formaldehyde. Seems only industry people and forum members like the stuff.
"Formaldehyde" searches in Google tend to discover formaldehyde-free items. "Formaldehyde" plus "garden" doesn't produce
much. It is not easy to find, so I appreciate the agricultural angle.
"Get it while you can" might be good advice.
Rbick March 26th, 2008, 10:35 AM

I read that article. Carcinogen my ass, chances are they are just looking for a reason to ban it.
Unless you order from a chem supplier, chances are agriculture stores are the only place you are going to find formaldehyde.
I'm going to find some Ca(OH)2 today btw :)

Exposure levels are basically the determinate of any level of toxicity simply be definition. Who in their right mind would would
stuff a fucking panty liner with formaldehyde? Idiot hippies, would would ban water if given half a chance (through ignorance)
vote in elections in Northern Kalifornia are responsible for this crap. But realistically, if a fume hood or other measures are
being used that should not be an issue.
Formaldehyde IS really a very common chemical and it would impact our economy greatly if it were banned, etc. What
generally takes place is that the targeted material is pulled from common domestic supply and the individual needs to find
the industrial supply for purchase.
There is a very simple way to archive industrial purchase (PM me if interested). Once that is surmounted, the rest is a question
of how much is needed and means to buy no more than necessary.....That is sometimes a real challenge. Unfortunately some
of the best & most workable techniques were burned down by teens attempting a half-hearted version of the above. That is
why (once again) I caution all of you, if you have some good sources, not to let them get into public domain.
M16Rifle March 30th, 2008, 05:30 PM

Hi all,
Wouldnt it be much safer if I add some sand to the AN/NaOH mixture ,since the
reaction is exothermic (the name caustic soda scares me :o).
Next week I will try to synthesize some ammonia through dry distillation.
Formaldehyde (they call it formol) is very expensive here , 250ml for 3 USD :mad: (the same for ammonia) ,and since
Ammonium Nitrate and Caustic Soda are sooooo cheap ,i think to make it by myself would be better for my pocket :D
Bert April 2nd, 2008, 10:57 PM

What exactly is formaldehyde used for in an agricultural context??? I've NEVER seen it at Fleet Farm or the garden store, nor
the feed mills and elevators where I get cotton seeds and rice hulls. But then I never asked for it by name either!
Charles Owlen Picket April 3rd, 2008, 10:09 AM

In fish farms, it is used to treat several types of fish scale disorders similar to "Ick" in an home aquarium. Often a variety of
poisons are used for topically presenting disorders in veterinary medicine.
Rbick April 3rd, 2008, 10:34 AM

Where I am, farmers have lots of cattle. Formaldehyde is used in foot baths for the cattle due to its anti-microbial properties.
Its sold in 37% concentrations.
THe_rEaL_dEaL April 15th, 2008, 05:57 AM

Instead of venting off the ammonia gas if the pressure gets too much why not have multiple bottles linked togetrher so the
excess from one is bubbled to the next. Fish tank bubblers could be used to give more surface area.
RBIK the formation of ammonia gas from NH4+ salt and a base occurs in aqueous conditions (in water). AN is very hyrdoscopic
(absorbs water) which means when you mix it with the caustic soda there were allready NH4+ ions in solution to react with the
OH-
Sulfate isnt as hydroscopic so would need water to make NH4+ ions avalable.
FUTI April 15th, 2008, 09:05 PM

I have some experience with hexamine preparation. Be carefull not to heat it to much when you remove excess water (I even
used rotary vacuum evaporator once and it works) since if you overheat that mixture hexamine decomposes.
Also in a completely diferent experiment I used ammonia generation described above and...well it works but it is a bitch. I had
to use couple safety bottles in line since bubbling ammonia isn't that simple as it may look at the first look. My solution had
constant wish to jump toward the ammonia reaction system through the pipes I used due to great hygroscopic properties of
ammonia (I should probably use term "solvoscopic" since I used methanol solution but...).That reaction made me tired like
nothing else since I had to take care of it and nourish it constantly.
I would like to use CaO or Ca(OH)2 but I fear that it will perform poorly since CaSO4 can trap Ca(OH)2 inside CaSO4
precipitate formed during the mixing inside ammonia generator.
Gerbil April 18th, 2008, 12:16 PM

I tested a similar method of producing ammonia using Ca(OH)2 and NH4Cl with small quantities heated in a test tube (0.005
and 0.01 mol respectively, bubbled into 100ml of water). As FUTI said, it's a bitch, and I wouldn't want to use this method for
large scale production unless I had to- anyone doing this should seriously consider getting proper glassware if they don't
already have any. I'd recommend a flask and tubing.
According to a test kit ammonia was present at 0.2%. Therefore for 50% concentration of 100ml, roughly 90 grams of
Ca(OH)2 and 130 grams of NH4Cl would be required. As it's designed for aquariums, the kit may be inaccurate though.
Nitrato May 18th, 2008, 08:53 PM

Yes, I also agree totally with FUTI, since I've tried before making ammonia from slaked lime and (NH4)2SO4 grade fertilizer
and the reaction was a real pain in the ass and very slow even if you add more water; After this painfull experiment I always
used NaOH, even though is much more expensive than lime. However using AN (or other salt than ammonium sulfate) with
Ca(OH)2 the reaction will be much easier, but you will certainly need add small amounts of water and heat the contents to
speed up the reaction, otherwise dont spect any decent yield.
Also, like FUTI stated, the ammonia absorption in water can be cumbersome, since is so highly soluble in it that is prone to
lower the pressure inside the apparatus, causing suckback which is part of the forming ammonia solution going up the NH3
tube and ending to fall in your generation vessel causing a great mess.. I have actually tried (2 years ago when I was still
using PETE bottles and kid toys to build my home lab :rolleyes: ) to bubble ammonia directly in 37% formaldehyde solution ,
in a try to get less water to evaporate, like Oss wondered, but the end was that the suckback occurred even more fast.. What I
think is that the suckback will be strong not only because of the great solubility of NH3 in water but in situ react with
formaldehyde, what cause furter 'demand' of NH3, creating faster suckback; at other hand the heat generated during this
reaction can counteract somewhat this suckback... So maybe would be a very good thing if you put a 'trap bottle' between the
generator bottle and the absorbing one.. even better if instead you use tube directly in the solution you use an inverted funnel
just a few cm down the liquid and that in a serie of absorbing vessels to dont lost too much ammonia..
Rbick: in the very first pic were you bubbling ammonia through a small PETE bottle? If yes, be aware, since PETE is prone to
decompose to ammonium terephthalate and that not only may cause contamination of the aqueous ammonia but also erode
and fragilize the bottle so your solution will go away through leaks created by the ammonia.. This last situation is much more
prone to actually happen if you try to store your ammonia in it.
Anyway this is a very great work and certainly greatly help to people that actually dont have any OTC source of hexamine (like
I), being the only real way make it from OTC precursors.
FUTI May 19th, 2008, 08:33 AM

I have one other thing to add about generating a gas. Fact is that you could generate the gaseous HCl from NaCl and H2SO4,
but you will always see chemist use H2SO4 and concentrated hydrochloric acid instead. That is enough to support my
reluctance to use any system where phase separation can occur.
About suckback...does anyone know good way to prevent that...maybe some pump like does used for aquariums to generate
constant overpressure?
The_Duke May 19th, 2008, 09:15 AM

There are many ways to deal with suck-back. For this situation I would suggest a simple intermediate isolation vessel (a flask
trap along the gas line between the gas generating mixture and the solvent...)
FUTI May 19th, 2008, 09:55 AM

I used three wash bottles in line as Duke proposed and I'm still unhappy with that solution. Maybe something like some of
those anti-splash adapters used on rotary evaporator could do the job also?
I know the bubbling of air in hexamine synthesis reaction flask is bad idea as it could decrease the yield, but I'm not making
that. That is why I'm looking into mixing the generated ammonia gas with other gas to produce a constant pressure stream. I
guess that a mercury filled bubbler after the reaction flask can prevent the overpressure climb to a 3atm where my flask turn
to shrapnel granade or maybe even before reaction flask attached sideways with T-type tube just in case. Any ideas?
Nitrato May 21st, 2008, 12:04 AM

I always have wondered if I could use other reagent than ammonia to produce hexamine with less cost. Also, in my country
the strong ammonia is banned of the shelves, and very watched. The only thing that is sold to commom people is the shitty
stuff, 2-4%, used with H2O2 to discolor hair(even this I noted disappearing of the market :mad: .. They clam that "it is too
dangerous".. Like formaldehyde, it is only a poor excuse to remove it from OTC )..I have made hexamine with it before and is
needed a lot of it. Its weird, but the hexamine yield based on formaldehyde seems to be really poor with these dilute
solutions, as cited in this thread. Another reason is that absorbing ammonia in water isnt so simple, as also discussed here.
So I was wanting a way to generate NH3 in situ with the formaldehyde to produce hexamine. I based this in the fact that in
some synthesis the hexamine appear to be really made in situ, needing only anything that can drift to right the possible
equilibrium .. One of these is HMTD preparation with (NH4)2SO4, that was the original synthesis of it (IIRC). The way I
encountered was to dissolve (NH4)2SO4 in formaldehyde solution, the add a thing that binds to sulfate and which could be
removed with relative ease. Two years before I used slaked lime and very raw materials (brown fert. grade ammonium sulfate,
with iron). Today I tried to repeat this experiment, but with some more care (In advance you will see that I still wasnt that
patient :cool:) and more pure reactants. I also replaced the slaked lime by CaCO3 which was a byproduct of sodium sulfate
production using frogfot method, described in his page. I used it for several reasons: seems to be much better than lime
(slaked lime usually contain Mg(OH)2 and other things that sucks, and also appear to be more "bulky", what means more
mess); CaCO3 is much less soluble than Ca(OH)2, so any excess of the first will probably not be a problem; and also I was
using CaCO3 since I was wanting to just put it in a good use :) ..The only drawback is that CaCO3 will cause foam and this isnt
good to be done with a stinky substance like formaldehyde. Also, my CaCO3 actually contain a small amount of CaSO4, from
the procedure I made it (from plaster and Na2CO3 in water), but I dont think it being actually a problem. The ammonium
sulfate and CaCO3 were used in excess of theory , especially CaCO3.
But anyways I plan to still repeat it , with more care and patience, until works, in some way or other.
6 CH2O + 2 (NH4)2SO4 <----> 6 H2O + 2 H2SO4 + (CH2)6N4
CaCO3 + H2SO4 ---> CaCO3 + CO2 + H2O

----------------
6 CH2O + 2 (NH4)2SO4 + 2 CaCO3 ----> (CH2)6N4 + 8 H2O + 2 CO2 + 2 CaSO4
82mL of 37% formaldehyde was measured and placed in a 500mL polypropylene kitchen cup. 50g of pure (NH4)2SO4 was
measured and mixed with the formaldehyde in the cup, until almost all dissolved. 50g of dry and fine powdered homemade
CaCO3 was slowly added and strong swirling to avoid any CaCO3 clumps and excessive foaming in solution. Initially the
CaCO3 reacted nicely , but the formaldehyde started to goo too much and become yogurt like, difficult to swirl.. This seems to
be para-formaldehyde forming, so I added the contents in a bigger container (3 L plastic bottle) and more 400mL of water
added (part of this used to remove the rest of the goo from the cup). In the much less viscous liquid, CaCO3 was slowly
added with the same strong swirling and reacted nicely. Until all the addition (that tooks 10-15 min), the smell of
formaldehyde become weak. More 20g of CaCO3 was added and then more 10g of (NH4)2SO4. Finally, after swirling the
contents for some minutes, more 10g of CaCO3 was added and the container swirled for more 2 mins. During the slow
additions the liquid did not appeared to be visible warm at any momment. The lid was loosely put on the container and the
milky liquid was left to stand 30 mins..When I opened the container a noticeable smell of ammonia comes, what is a good
indication. Then was filtrated using a square piece of synthetic cloth.. Then the cloth with CaSO4/CaCO3 was squeezed by
hand to free most of the intersticial liquid, then some water was added to the improvised filtrating cloth to extract the rest left.
The liquid was filtrated again using two coffee paper filters and some cotton stuffed in a 1,5 L vol polypropylene funnel. The
filtrated liquid was pale blue. I'm almost sure that this is due of the synthetic cloth I was using, that is blue. Weird that the
ammoniacal solution just leached some of the dye. Next time I will use other thing to filter.
Anyway I was wondering that if I add HNO3 to this solution, some HDN ppt out.. So I added 40g of KNO3 to 65mL 30% HCl and
plus 45mL water and mixed for some minutes until almost all dissolved.. The KNO3 was very slow to dissolve, even though the
solution wasnt apparently very cold. Next time I will try NaNO3 or NH4NO3.
I added this to the pale blue liquid obtained before, without any cooling since I was without ice (again: patience usually isnt
my strong point), expecting any HDN ppt, even in small amount, but instead a unknow pale white smoke was produced and
the pale blue color disappeared, giving a clear solution.
Failure.
Do you guys think that if I modify my procedure I will get anything good?
I just thinked about HDN since might be a way to see if hexamine is present ( I hate evaporate solutions to dryness and all
that involves liquids being heated for more than some minutes. hahaha).
FUTI, I like your idea of using aquarium pump to generate constant overpressure.. Mine is small and rated at 4 L air/minute,
but that probably isnt enough to water hungry ammonia...Maybe more similair pumps together to give more air..What you
think?
Nitrato May 22nd, 2008, 08:44 PM

Well, I just repeated the experiment I did, more two times, modifying it a bit.
In these two new tests I just used the same amounts of reactants [ CH2O (82ml), (NH4)2SO4 (60g), CaCO3 (80g) ] and
changed a bit the other reactants ; the goal was to use the minimum amount of water and have minimum liquid loss (this
unfortunately I still dont reached a good way).
second test:
The formaldehyde was mixed with 100mL of water in the 3 L container and in this was added the ammonium sulphate, all at
once, and well swirled for one-two minutes until almost all dissolved. So I started to add the CaCO3, in the same fashion I did
before. All was did in backyard.
After all the CaCO3 added, the mix was left stand for 15 mins ; then most of the goo was filtered through a simple coffee
filter paper, and the filter was slow and cautiously squezeed to not leak. The residue was put back in the 3 L container and
70mL of hot water was put in and well mixed and filtered again using other paper filter and added on it slowly more 30mL of
water and finally the filter was squezeed. The filtrated liquid was still with some insoluble matter so I used another fresh filter
and filtrated again. The resulting liquid was clear and I measured as ~221mL (basing in formaldehyde + water total volume,
about 61mL was lost.. Probably the most part of this the CaSO4 grasped forming the dihydrate). This was put in a bucket with
ice/water.
At same time ~65mL of 30% HCl was measured and in it 40g of NH4NO3 was added.. It not dissolved very fast , even with
stirring, and gaves a repulsive smell, mist of HCl and chlorine (as in homemade aqua regia! :rolleyes:) , so I added 50 mL of
an OTC brand of muriatic acid, market as 10% HCl but this did not seem to help too much, so I added 50mL of water. With
this the AN dissolved quite fast. Then the glass container with this mix was put in another ice/water bath.
After 30 mins the temperature of contents of both containers was 0-5C. I added the cooled HCl/AN mix , all at once, to the
cooled 'hexamine' solution.
Nothing really interesting happened.
FAILURE AGAIN; at least a very very small (even difficult to see well) amount of crystals actually have formed in solution and
quickly redissolved, this was or was not HDN, I really cant say.
============================================
The 3rd test was done today and in this, the total final water was further reduced by simply dissolving the ammonium nitrate in
the 'hexamine' solution rather than in HCl, then adding this, straight concentrated HCl, directly in HMTA/AN solution. Both
solutions well cooled by a good salt/ice bath, rather than ice/water bath.
re-typing some parts from 2nd attempt, since this one is fundamentally the same I used in the above test, but with some
minor modifications far than cited:
The formaldehyde was mixed with 50mL of water in the 3 L container; and in this was added the ammonium sulphate, all at
once, and well swirled for one-two minutes until almost all dissolved. So I started to add the CaCO3, in the same fashion I did
before.
This time I tried to use less water (50mL instead of 100mL used in 2nd attempt) to dilute the formaldehyde in an attempt to
reduce still more the final water content, but this wasnt so good since the mix started to become very viscous and foam much
more difficult to break down. So I added more 30mL.. But even so I needed to add more 20mL.. So I ended with the same
100mL of the 2nd attempt and this amount appear to be the approx. minimum with 82mL formaldehyde to give good (less)
viscosity of the mix. Maybe using larger volumes of reactants the water ratio needed may be less.
All was did in backyard.
After all the CaCO3 added, the mix was left stand for 15 mins ; then most of the goo was filtered through a simple coffee
filter paper, and the filter was slow and cautiously squezeed to not leak. The residue was put back in the 3 L container and
60mL of hot water was put in and well mixed and filtered again using other paper filter and added on it slowly more 30mL of
water and finally the filter was squezeed. The filtrated liquid was still with some insoluble matter so I used another fresh filter
and filtrated again. The resulting liquid was clear and I measured as ~186 mL (basing in formaldehyde + water total volume,
about 86mL was lost.. Probably the most part of this the CaSO4 grasped forming the dihydrate). But comparing with 2nd
attempt this liquid lost was much more severe, Maybe partially is because I added portion wise water to dilute formaldehyde
instead of adding straight 100mL (???), or just something goes wrong and I was not too cautiously like in 2nd attempt . This
was put in a bucket with salt-ice bath, and 40g NH4NO3 added in the 'hexamine' solution, quickly dissolving and helping to
lower the temperature of the solution still more quickly.
At same time ~65mL of 30% HCl was measured and put in a glass cup with a plastic lid and this was put in another salt/ice
bath.
The temp. of both solutions after 20min was below 0C (-10C for HCl and -15C for HMTA/AN mix). The HCl was then added ,
all at once, in the HMTA/AN solution (standing on the salt-ice bath) and immediatelly a white smoke comes from the container
(probably, at least in part, this smoke could be NH4Cl formimg in air inside the container, since the HMTA/AN have a weak
smell of ammonia and almost no bubble in solution was noticeable).
At the start nothing more than the smoke formed, and I was considering this a total failure. I just have left standing on the
salt-ice bath 2-3 mins and then, for my surprise, small brilliant crystals started to appear. After more 1-2 mins the container
was with a good amount of the white ppt; I then let on the salt-ice bath for just more 5 min and then filtered, washed on filter,
with 50 tap water. Then put the funnel with the paper filter/ppt on another flask to receive the ethanol which was the next step
(I always use 'waste' alcohol, like in this procedure, in my alcohol burner, just to save a little more money ) . 70mL 92%
ethanol was added slowly and then 50mL of anhydrous ethanol. The filter was squezeed and the ppt is drying under
incandescent lamp now.. They look like HDN (since I have made it before), nice shiny white crystals. =]
The most weird part, definatelly, was that these crystals took a time in solution before forming and precipitating.. When I
made HDN these crystals formed in solution almost instantaneously! But this may be just the time of the HCl displacing
NH4NO3 in solution , since in my commom HDN preparations I use Mr. Cool method in which nitrate dissolved in HCl.
If my precipitate is really HDN I will be just amazed! An OTC route to HDN that does not require HNO3 nor hexamine as direct
precursor ! And this last in turn not requiring ammonia to synthesize it! I dont know if a member here made this procedure
before, if yes, tell me here (PM me, if you prefer)!!! Also, if any member is going to test this, please lets all of us know!!!
"quick 'n' dirt" way to HDN :D
Before euphoristically confirming the abovementioned, the next obvious things which I will do is to see if is really HDN (burn
test/ detonation) and reporting here.
I dont know how much was produced and the respective overal yield, though. Also, my scale isnt that great (500g range
kitchen scale), and so not very accurate..
So, to become more 'in tune' with the issue of this thread I will do the most obvious thing, which is trying again the procedure,
but evaporating the solution to dryness to see if hexamine was really formed and purifying it, if necessary to remove any
impurity calcium salts or other crap.
I just did a very quick search to see info on hexamine solubility in water, ethanol, etc..This will be useful to my next
experiments and may be also with the issue of this thread..
From Seidell (grams per 100 grams solvent):
water : 81,32g (12C ... This source seems to be wrong, by a zero: http://www.sinachem.com/hexamine.html )
anhydrous alcohol (does not say what alcohol, but I just guess, the author is reffering to ethanol): 3,22g (12)
chloform : 8,09g (12C)
100 cc of 90% alcohol : 12,5g (15-20C)
Have anyone real good data about solubilities of HMTA or a 'magic' link to it ?
Thanks!!
EDIT: One thing I forgot to mention is that all the left over liquids ('hexamine' + nitrate + HCl) after some hours have a very
strong smell of formaldehyde. Since hexamine and compounds (HDN, etc) tends to decompose in water (especially acidic
solutions) to give up formaldehyde..So its another , but not very accurate, indication..
The almost dry powder have a weight of about 15g.
I did the burning test now and I fairly certain that is really HDN.. Burns with ease and giving a smell similair of burning
hexamine. Tomorrow I will try to detonate it.
Setharier July 6th, 2008, 03:47 PM

Formaldehyde isn't hard to find due to it's dangerousity because of junkies and terros, but to it doesn't have everyday
commoner purposes. Shops doesn't keep in shelf stuff that anybody usually buys in quantities smaller than container.
I have my own "common supplier" which sells very wide category of chems, including stright from shelf substances like picric
acid. :eek:
I'm going to make hexamine by myself, even if there are many suppliers, including my own which sells it even relatively cheap
(15 euros/kg); I JUST recently bought HNO3&H2SO4 from them and their eyes would blink of explosives warning if I suddenly
come back asking for some hexamine and at this, I really can explain them where I need ammonia and formaldehyde, but no
idea with hexamine but RDX.. :confused:
Oh by the way, is it phossible to use paraformaldehyde in hexa synthesis?
Rbick July 6th, 2008, 05:22 PM

I think I remember reading a post in one of the hexamine threads about someone using paraformaldehyde in the hexamine
synthesis. From what I remember, it worked but the yield was a bit lower. Don't take my word for it though, I know it is in one
of the hexamine threads on the forum here. Is there any particular reason you want to use paraformaldehyde, or are you just
curious?
I used some (20g) of my homemade hexamine a few days ago to make a batch of HMTD. The product turned out great. It is
kind of a sense of pride making energetics from homemade materials. You really get to to see the fruits of your labor,
marked with a big BOOM! Sorry, had to brag a little ;)

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Chlorine gas storage/
methods of use
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View Full Version : Chlorine gas storage/methods of use
Horus April 17th, 2008, 10:23 PM

So I have about 2 grams of Chlorine in balloons (weight determining by weighing empty balloons, then weighing the full ones and doing subtraction), which I plan to use to
make POCl3. I need the Chlorine to react with Phosphorus (from matchbook strikers) to produce PCl3, which will ultimately be reacted with O2 gas to produce the phosphoryl
chloride.
My main question is how I can pump this chlorine gas into the red phosphorus solution? If I had the chlorine in a gas cylinder, it'd be easy to just submerge a tube from the
cylinder in the solution and bubble it through, but I don't know how to get the chlorine from balloons into the cylinder, or is there some other way to do it? I could envision
attaching a hose to the balloon and then squeezing the chlorine out; would that work? I don't have much experience working with gases, besides the occasional reaction under
a nitrogen atmosphere, so sorry if this question is overly basic but I couldn't find any info on it.

I proposed a ghetto gas recirculation system some years ago in this thread: http://www.roguesci.org/theforum/showpost.php?p=38864&postcount=14. This system uses an
aquarium pump to continuously circulate gasses other than air to save on wasting precious chemicals, and to protect from releasing hazardous fumes. Why waste your precious
chemicals and contaminate your lab if you dont have to?
To expand upon this idea, you use an inexpensive aquarium pump or air compressor enclosed in a plastic container with inlets and outlets to circulate the gas. Get a plastic
Tupperware container large enough to house the pump and drill 3 or 4 holes into it. The holes can be in the lid, or the container, or both. Two of the holes are for attaching a
hose barb, they are the gas inlet and outlet respectively. The third hole is for the pumps power cord. You may be required to remove the electrical cord from the pump to pass
it through the hole, otherwise you have to make the hole large enough to fit the plug head through (in which case I recommend slitting the plastic in a plus (+) shape rather
than cutting a massive hole. The fourth hole is optional; it is also for a hose barb to be used as a pressure regulator.
The inlet hose barb can be a Y or T fitting, and the outlet and pressure barbs are just straight tubes. The outlet should have the barb extend inside and outside the
container. You can get plastic hose barbs at the hardware store, or you could use short lengths of glass tubing. The hose barbs can be sealed with silicone caulk for a good
airtight fit. Ideally the holes in the container should only be as large as needed to fit the barbs. Insert the power cord through its hole, place the pump inside the container, and
attach the air outlet of the pump to the outlet hose barb on the inside of the container with a short length of tubing. The lid can be permanently fused to the container at this
point. If you have a container with a nice tight fit, possibly a rubber gasket, you will not need to permanently affix it, but there is really no need to service inside this container
except to replace the pump if it dies, or to clean out any condensed chemical nastiness if you do not filter your inlet gas. You will get a better airtight seal by caulking the lid on
permanently (the silicone can be razored off if need be).
For the optional pressure release system, a balloon is wired onto a barb sticking out from the top of the lid. This acts as a gauge to determine how much gas in being put into
the system, an early warning system in case of rising pressure, and an emergency pressure release valve (i.e. the balloon pops before your glassware does). If your gas
generating system is continuously putting more gas into the circulator, but your reaction is only consuming a small volume of the gas, you will blow a gasket somewhere when
the pressure gets too high. Best to pop the balloon instead of something far more expensive.
When you hook the gas circulator up, connect you gas generator (in whatever form it may be) via a length of tubing to one of the barbs of the inlet. The outlet is connected by
a length of tubing to your reaction system (in whatever form it may be). The gas that exits the reaction system is then connected by a length of tubing to the other inlet hose
barb. If the pressure starts to get too high, shut off your gas generator and just let everything recirculate.
I leave it up to you to determine how to safely operate this system for now. I think I will start a new thread to expand on this design. Keep in mind that it is dangerous to run
certain flammable gasses through this system because the aquarium pump is electrical. With all of the air fully purged from the system, there is little explosion hazard. Certain
gasses may corrode and damage the pump over time. Moisture traps, filters, etc. should be used in conjunction with the circulator as per normal laboratory procedure to
preserve its life.
There are certain aquarium, compressor, and vacuum pumps that have both an inlet and outlet. If you are lucky enough to get one of these you dont need to build the pump
enclosure. The point of putting the pump in the container in the first place is because most pumps do not have a dedicated inlet. Indeed by reversing the connections of the gas
circulator it can serve as a vacuum pump too, albeit a weak one. Just hook up the inlet to your system instead of the gas generator, and vent the outlet to the open air. There
is a thread on instructables.com about modifying cheapo tire compressors to add an inlet making them suitable as vacuum pumps (http://www.instructables.com/id/convert-a-
tire-inflator-type-air-compressor-into-a/).
Now then, if you are not looking to get this complicated, you can use an aspirator to pull air (or your gas) through your reaction system. There is also an illustrated description
of a gravity aspirator in volume #1 of the Poor Man's James Bond (from Dick's Cyclopedia of Recipes and Process if I recall correctly) that uses siphoning to produce suction. A
jug is filled with water and capped with a two hole stopper, a length of glass tubing is inserted in one hole almost to the bottom of the jug and a short length of glass tubing is
inserted into the other hole, a length of hose is attached to the tops of both tubes. To start the siphoning you suck out the water from the end with the tube near the bottom of
the jug until it flows on its own. Set this jug up somewhere high so it can drip down and connect the other hose to the system that needs air pulled through it.
Another way with just balloon of gas is you could connect it to a two hole rubber stopper, a long length of tubing goes all the way into the balloon through one hole, a short
length of tubing goes into the other hole, and you use an aquarium to force air into the balloon through the long tube.
You do realize that you will get only a very small amount of PCl3 from 2g of chlorine right? If you do not recirculate the gas your yields may be nonexistent if you do not
already have some PCl3 to seed the reaction because the initial rate of reaction is extremely slow.
I have been designing a DIY UV photochemical reactor that I believe can greatly improve the synthesis of phosphorus trichloride. The ancient chemists used sunlight because
they did not have UV lights (electric arc systems would have been quite exotic back then).

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Salicylic acid
synthesis by hydrolysis of asprin
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View Full Version : Salicylic acid synthesis by hydrolysis of asprin
DONMAN April 18th, 2008, 09:53 PM

I am attempting to perform hydrolysis on Acetylsalicylic Acid (asprin) to create salicylic acid. I am wondering if 31.45% (by mass) HCl is strong enough to dissociate
Acetylsalicylic Acid into Acetic acid and salicylic acid. I have also heard that Acetylsalicylic Acid can also undergo autocatalytic degradation to Salicylic acid in the presence of H2O.
Can any one give me some insight into the situation....

I would think that HCl would be a strong enough acid to hydrolyse ASA into Salicylic acid and Acetic Acid.
I've found a few interesting journal articles (none of which I can read all of) that mention accelerating the hydrolysis of ASA by using a hydrocarbon/H2O mixture. I'm trying to
find a copy for you.
Hmmm, no luck.
As I understand it, ASA will by hydrolysed by water, but I would imagine as the acidity of the solution rises (from the acetic acid), the solution would approach equilibrium. I'd
just hit it with some HCl, or you can try water and use NaOH to raise the pH.
Hinckleyforpresident April 19th, 2008, 02:06 AM

I achieved a >80% yield simply refluxing tap water with ASA for 8 or 9 hours. As the ASA breaks down the pH drops due to AcOH formed, this in turn catalyzes more
breakdown in a self feeding process.
At the end of the reaction you will have a flask filled with SA crystals. I recommend recrystallizing from boiling acetone.
kurtz April 19th, 2008, 08:37 AM

And the solubility in strong acid is?
Using base works great from pills.
Hinckleyforpresident April 19th, 2008, 12:20 PM

And the solubility in strong acid is?
Using base works great from pills.
To my knowledge, the solubility of SA in water isn't good no matter what the pH.
FUTI April 19th, 2008, 02:28 PM

Hm, and what was the SA needed for? I was shocked to find out that some of the reaction of SA actually work better if you use ASA instead (e.g. less oxidation or aromatic
substitution). It is more expensive for the industrial purposes as it would mean 1 more synthetic step (acetylation of SA), but for hobby type chemist availability of the
compound means a lot;-). HTH
Hinckleyforpresident April 19th, 2008, 02:32 PM

I used my salicylic acid to make methyl salicylate. My house hasn't stopped smelling since!
JouMasep April 19th, 2008, 03:41 PM

For esters, the rate for base hydrolysis is much better than for acid hydrolysis. It is the preferred route in this case.
So I would propose use of a 10N solution of KOH (or NaOH).
You add one equimolar amount to neutralize the (very) acidic hydroxyl radical and then an equal amount plus a wee bit of excess- to quantitatively hydrolyse the
methyl ester.
The reaction is carried out at room temperature. At first the reaction goes very fast (may even get slightly warm I reckon); but in order to go fully to completion, it needs to
stand for a few days.
Then acidify with dilute sulphuric acid to pH around 1 and re-crystallise from a suitable solvent (mixture) Acetone or isopropyl alcohol and the like.
This is not a truly catalyzed hydrolysis as the hydroxyl ions get consumed in the reaction. When half-decently carried out, the yields should be quite better than for acid-
hydrolysis
kurtz April 19th, 2008, 07:06 PM

To my knowledge, the solubility of SA in water isn't good no matter what the pH.
I thought that it was obvious that I was talking about the subject of the thread, acetylsalicylic acid and conc. acid, which is a practical consideration. Of course both SA and ASA
are perfectly soluble in equivalent bicarbonate (foam and spray) or hydroxide solution, etc. if acetylsalicylic acid remains that way for any length of time in the presence of
base that is. The solubility of SA in boiling water is high enough for it to be my preferred purification method.

JouMasep - Perhaps I have missed something, but wouldn't attempting hydrolysis with a base lead to a salt being formed instead of the desired product? I see that you acidify
with H2SO4 but would it not just be easier to use an acid in the first place, or merely refluxing with water as Hinckley suggests? Or reflux with acid?
JouMasep April 20th, 2008, 05:18 PM

The first equimolar amount of base will indeed neutralize the proton on the (very) acidic hydroxyl group. (It will not really form a salt as all is in solution -but I get your
drift and you are thinking right here.)
The second (again equimolar) amount of base will hydrolize, split or saponify the methyl ester group. The rate for saponifications of esters is way better than acid hydrolyses.
I see that you acidify with H2SO4 but would it not just be easier to use an acid in the first place, or merely refluxing with water as Hinckley suggests? Or reflux with acid?.
Well, if easy is the objective, chucking a load of aspirin tablets into boiling water would be the ticket.
But if optimal (close to quantitative) yield would be ones goal, then base hydrolisis would be best.
And besides, I feel that a lack of need for boiling, refluxing for many hours counts for something too.
It is not a big deal: add base, stirr, walk a way. Come back in two days and acidify. Easy as well methinks.
Nitrato May 18th, 2008, 07:41 PM
Long time ago I made my SA doing the basic hydrolisis then adjusting with H2SO4, exactly like JouMasep have said in this thread and IMHO is better than refluxing (I hate
reflux!) ASA with water or HCl, although acidic hydrolisis isn't seem to be really slow (I have not tried direct acidic hydrolisis, but here http://www.crscientific.com/article-
aspirin.html is claimed that at 60-85C you need at least one hour of reflux).
But since I discovered a place where methyl salicylate is real cheap and OTC, I discontinued to hydrolise ASA to get SA.
FUTI May 20th, 2008, 09:53 AM

Nitrato I would appreciate if you send me a private message with source for that OTC methyl salicylate since forum practice is not to publish it where three letter agencies can
see it.
Barnacles May 20th, 2008, 06:38 PM

Nitrato I would appreciate if you send me a private message with source for that OTC methyl salicylate since forum practice is not to publish it where three letter agencies can
see it.
You have private messages off. so pm me and I will give you a source...
Skean Dhu May 20th, 2008, 11:59 PM

Methyl salicylate AKA Oil of Wintergreen is available as a topical pain releif rub for sore muscles in many pharmacies as well as places that sell essentail oils for flavoring.
Should you be located in a particularly draconian area it is found naturally in Eastern Teaberry(Gaultheria procumbens) and Sweet Birch(Betula lenta) plants.
megalomania May 22nd, 2008, 05:02 AM

The concentration of methyl salicylate in oil of wintergreen is very low. It would be very expensive, as well as time consuming, to extract a useful quantity.
FUTI May 27th, 2008, 06:40 AM

I can confirm Mega's word as the products contain methyl salicylate in my part of the globe up to 3-10%, although net info about percent in some USA products is up to 50%.
tapira1 September 6th, 2008, 07:10 PM

Another good source of SA is the natural one. Salix trees. They grow here all over the land, specially near water. A decoction of it can yield several grams without too much
effort.
Regarding hydrolysis of ASA, it will hydrolize even with water, but the best method is to use dilute (not 10 N, buy 0.01 N) NaOH; solubility os low enough to allow extraction
from the acidified medium.
Hinckleyforpresident September 6th, 2008, 07:16 PM

If you use a base to hydrolyze acetylsalicylic acid, you will wind up with a salt of salicylic acid.
tapira1 September 7th, 2008, 09:20 AM

That is correct, however, 0.01 NaOH is easily neutralizable (HCl, H2SO4); then, you get your SA from an acidic medium. Overall, the process is les time and energy consuming.

a n d I m provised C hemistry > Is it possible to se parate toluene from g a s o l i n e ?
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View Full Version : Is it possible to separate toluene from gasoline?
diehazard May 5th, 2008, 11:26 AM

Hi fellas. . .
I ' v e b e e n l o o k i n g f o r a m etho d to separate toluene from gasoline via distillation.
And I found so far is that gasoline com positions contain about 2 0-40% v/v of toluene. The boiling point for toluene is 111C,
and the gasoline contains no hydrocarbons that have a boiling p oint near this (the closest hydrocarbon was within about 10
d e g r e e s o f 1 1 1 C ) .....
I a m wondering if it is possible to extract toluene via distillation, or any other method???

Y o u a r e l u c k y I h a v e s o m e tim e to kill and am in a distillation fram e o f m i n d . Y o u r g r a m m ar is atrocious, I had to heavily edit
t h i s t h r e a d t o m a k e i t r e s e m b le the English lan g u a g e . Y o u p o s t e d t h i s i n the wrong section too.
W hat you are after is a fractional distillation. The effectiveness of a fractional distillation d e p e n d s o n t h e r a n g e o f b o i l i n g
poin t s o f t h e c o m p o n e n t s b e i n g s e p a r a t e d , m e aning the farther apart in boiling point each com ponent is the easier it will be to
separate them .
W hen a mixture is fractionally distilled you have what are called "theoretical plates." A plate refers to an eq uivalent simple
distillation. T he taller the colum n, the m ore theoretical plates, and the better the separation will be.
I n p e t r o l e u m refining very tall towers are used to separate the various components of oil into useful fuel components. It is
certainly possible to separate toluene from g a s o l i n e I F y o u h a v e a l a r g e e n o u g h c o l u m n .
T h e r e a r e s o m e additional factors to keep in m ind when separating chem i c a l s . D e p e n d i n g o n w h a t s o m e o f t h e o t h e r

c o m p o n e n t s a r e i n y o u r m i x t u re you m ight form an azeotrope, a constant boiling mixture of two or m o r e c o m p o n e n ts that can
not be separated by distillation. In the se situations you can add other ch emicals to m ake a new azeotrope with the
components you do not want, or you can use special filters such as zeolites.
If you wanted to push the lim its of science further you could use gaseous diffusion techniques to slowly separate m olecular
c o m p o u n d s b a s e d o n their m a s s d i f f e r e n c e s . Y o u c a n a l s o c h e m ically react the components of the mixture into com p o u n d s
that are easier to separate, distill the compoun ds, and convert them back into the original com p o u n d . T h i s i s s o m e t i m es called
protection/deprotection.
Y o u m a y w i s h t o c o n s u l t p e t r o l e u m e n g i n e e r i n g b o o k s f o r m o r e d e t a i l e d i n f o r m ation. It is a vital area of industrial chemistry to

r e m o v e b e n z e n e a n d o t h e r a r o m atic m olecules from pe troleum f e e d s t o c k s i n c e t h e s e s u b s t a n c e s a r e a h e a l t h h a z a r d .
FUTI May 8th, 2008, 05:07 PM

You mistaken fraction with boiling poin t a r o u n d 1 1 0 d e g r e e s C e l s i u s w h i c h c o u l d a m o u n t u p t o t h e p e r c e n t a g e y o u m e n t i o n e d,
b u t a s M e g a s a i d d e - a r o m atization is standard in petroleum refining. W hile it is true that octane num ber rise with aromatic
content, why would anyone just burn very versatile com pounds like benzene and toluene? Eco-frenzy is just yet another factor
that limit its content as Mega m e n t i o n e d .
DeathWatchBerzerker S e p t e m b e r 8 th, 2008, 03:45 PM

I can think of a few reasons you would want toluene, bu t why obtain it from gasoline? It is used as a solvent in m a n y
applications, a stripper being one such . While I do not know its concentration, I was able to find it at a local hardware store.
Hinckleyforpresident S e p t e m b e r 8 th, 2008, 06:31 PM

I can think of a few reasons you would want toluene, bu t why obtain it from gasoline? It is used as a solvent in m a n y
applications, a stripper being one such . While I do not know its concentration, I was able to find it at a local hardware store.
I believe the original intent is to have a backup source for toluene in the event that hardware stores stop carrying it. Also, it
g i v e s p e o p l e i n m ore restricted countries a way to obtain toluene.
Just because it's in the store today doesn't mean it will be in there tom orrow.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Bismuth Trisulfide
Scarcity
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View Full Version : Bismuth Trisulfide Scarcity
Yafmot May 13th, 2008, 07:59 PM

One of the areas I'm looking to do business in is the field of low/no toxicity munitions. Antimony Trisulfide is used in all kinds of pyro applications but, unfortunately, its
biological effects are pretty much like Arsenic, which does some very not-nice things to people.
Bismuth trioxide has been investigated as a suitable substitute, but documentation on its use or, for that matter, sources or its manufacture, are sparse as the Salt Lake Desert.
Of course, Alfa Aesar will supply it, at their usual buttrape prices, but in a pyro application purity isn't all that big a concern (most of the time). Lorad E-mailed me back saying
they could make some on a custom order basis. I've yet to get back with them on it (I keep just missing the guy), but unless they have a little in stock at a reasonable price,
I'm afraid I'll just have to make it myself.
I read somewhere that Sb2S3 is made by commingling 50/50 Antimony and Sulfur intimately and heating, but the source said it was a very dangerous process requiring a lot of
specialized equipment. I'm thinking they mean a glove box or at least a fume hood.
Bismuth, on the other hand, isn't anywhere near as toxic. Also, I've been made to understand that quite a few metallic sulfides can be prepared in this manner. Not only that, I
have a friend with an induction heater/bell jar/vacuum pump setup that should work great for small amounts. Just pour some mix into a Carbon crucible, stick it under the jar,
pull a vacuum and hit the juice. Induction heating works real fast on small masses, so if the reaction time isn't too long, I should be able to do a half dozen runs or so in an
afternoon.
If I can find a reliable source, though, I'd just as soon purchase a couple of kilos of technical grade stuff and be done with it. Information, advice, leads, or even catcalls & jeers
would be welcome right now.
So, whaddaya' think?
Bugger May 13th, 2008, 10:26 PM

Bismuth is a somewhat rare metal, much rarer than lead. (I wonder if PbS would also do as a substitute for Sb2S3 for pyrotechnic applications, but it is still toxic). There may
be a reason for restricting the sale of Bi, in that it can be bombarded with neutrons to make polonium-210, the intensely alpha-radioactive substance used by the KGB to kill
Col. Litvinenko in 2006.
ETCS (Ret) May 14th, 2008, 05:01 AM

Weingart recommends the use of Black Copper Sulfide made by fusion. It has pyro uses as well as in detonators.
It now appears that Litvinenko may have carelessly poisoned himself. He was in Israel just before his unfortunate demise and it is probable that he got the Polonium 210 from
the Atomic Laboratory in Dimona. Probably for a "false flag" operation in the U.K. It has now been established that he was a double agent for Israel.
Bacon46 May 18th, 2008, 10:03 AM

Bismuth is a somewhat rare metal, much rarer than lead. (I wonder if PbS would also do as a substitute for Sb2S3 for pyrotechnic applications, but it is still toxic). There may
be a reason for restricting the sale of Bi, in that it can be bombarded with neutrons to make polonium-210, the intensely alpha-radioactive substance used by the KGB to kill
Col. Litvinenko in 2006.
The restrictions on Bi must either be very recent or just a New Zealand thing. I have 50lbs of 99.8% Bi that I ordered from a metal supplier in New York. I alloy it with tin and
use it for casting non toxic fishing tackle. It makes pretty good ball mill media as well. Without the tin it is too brittle
PM me if you would like to know the specifics on the metal supplier.
Yafmot May 19th, 2008, 01:39 AM

Bugger, The New Zealand government simply HAD to restrict Bismuth, what with the ready availability of TRIGA reactors and particle accellerators on the internet.
I talked at length with a gentleman at Lorad, and sure enough, I was full of shit on the process, at least as far as the vacuum is concerned. He said just put a well blended,
stoichiometric mix and put it in a crucible, or for that matter a teacup, and stick it in the oven at about 450 F, just above the menting temperature of the Sulfur, and the two
will react, but slowly. If you raise the pressure, say, in an autoclave that's been evacuated, then pumped full of N2, and then heated, you can use much higher temperatures
before the Sulfur boils and, of course speed up the reaction. I'm trying to think of what kind of catalyst would help the reaction without contaminating the product.
I'm no chemist, so if anyone sees a hole in my methods, please feel free to call me on it.
Whaddaya' think?

a n d I m provised C hemistry > Ethyl Centralite Synthesis
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View Full Version : Ethyl Centralite Synthesis
Priority August 5th, 2008, 03:33 AM

Hi everybody, great to know that you guys exist.
I'd like to kn ow if someone on the board knows how to produce ethyl centralite (3-Diethyl-1,3-diph enylurea or 1,3-DE-1,3-
DPU). I have been trying to google it, looked through this and o ther foru ms, but unfortunately my searches yielded nothing.
I s t h e r e s o m eone out there who knows how to prepare this chem ical step by step?
Alexires August 6th, 2008, 12:45 AM

Yeah, nice to know you no lon ger exist.
Go read the rules. Spoonfeeding request, first post/new thread.

The Explosives and Weapons Forum > Chemistry for Amateur Experimenters and Citizen Scientists > General, Organic, and Improvised Chemistry > Manufacture of
sodium hydroxide
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hereticalhermit August 29th, 2008, 07:10 PM

I have an old chemistry book, which describes one of the earlier methods of manufacturing NaOH. Doing a search on the manufacture of NaOH, both here and on the internet, I
am able to find information on the process using mercury ("Kastner" cells), but almost none on the older method using "Vorst" cells. What I have been able to find on the
internet are merely references to people having w orked with them in the past wherever those people may have been employed.
A "Vorst" or "diaphragm" cell is useful for making NaOH w hen electricity, water, and salt are the only items available to use for the process. It consists of one perforated cell, an
asbestos diaphragm, another metal container outside of those, and a catch-basin for the lye. The inner cell is filled with brine, electricity is applied, and a mixture of brine and
lye fills the bottom pan, while hydrogen and chlorine are produced at the terminals. The strength of the lye is low , and it needs to be further refined.
Using asbestos as the diaphragm is no longer an option, and some research has been done on other materials, but most of that research is not public information, or the
materials are either proprietary or very expensive. Class "c" fiberglass may be a possibility.
Has anyone out there had any experience with this type of electrolytic cell?

A long time ago I made NaOH by electrolyzing salt water using a terra cotter flower pot as the ion bridge, which was in turn placed inside a 5 gallon plastic bucket filled with
water. I let the thing run for weeks and I barely got anything. Worse still, because it was exposed to the air for so long I ended up with a good deal of sodium carbonate (CO2
pulled from the air neutralizes the sodium hydroxide solution slowly).
I used a low current power source, which led to such a low yield. Faraday's law tells us w hy this happens, the more electrons flowing into the system (current) the more product
you get. With a high current, low voltage pow er source I could have made NaOH much quicker.
This method is not nearly as efficient as the electrolysis of molten salt (giving sodium metal w hich is then chucked into water), but it is something people can actually build with
minimal materials.
I once read about a cell divider, I believe in one of the early 20th century technical recipe books collections. You make a divided cell out of concrete. You need a fine concrete,
like a mortar or grout even, thoroughly mixed with large amounts of salt. The salt should be a fine granulated type like table salt, not rock salt or finely powdered.
You mix up the concrete as normal and pour it into a mold. A cardboard mold shaped to fit your container would be great. For example you can glue or caulk plastic strips on the
inside of a bucket to make a channel, then the concrete plate slides in like a window slides down in a frame. The concrete plate should be thin, maybe 1/4 inch to 1/8 inch
thick.
Allow the concrete to dry fully, then submerge the plate in water for... lets say a week or tw o. The immersion leeches out the salt trapped in the plate giving a very porous
structure. This porous plate is an excellent barrier for electrolysis purposes.
I am not too sure on the granularity of the salt. It may need to be either very finely pow dered, like dust, or perhaps ground a little finer than table salt. The resulting voids need
to be big enough to make connecting channels. If the salt is too fine it w ill be trapped and isolated in the concrete, and if it is very course the voids will allow ions to just pass
right through.
Such a plate is cheap, not terrible difficult to make, and it is very effective. It may become fouled over time by undesired ions like a clogged filter. You can just make a new
one, or run the electrolysis system in reverse. This is what a big manufacturing operation would do, it is probably not worth the time and trouble considering it is easier to make
a new one if it is small.
Obviously there are limits on the size of the plate. Make it too thin and it will not stop ions from passing right through. Make it too thick and you will waste more and more
energy pushing your ions through. Since these need to be operated horizontally, making it too big could cause it to crumble. On the 5 gallon bucket scale, a quarter inch should
be fine.
rangegal August 30th, 2008, 03:07 PM

How they made soap in the old days! Hardwood ash was mixed with water and filtered, then evaporated down till it was concentrated enough to "dissolve a feather". If you
have a wood burning stove or heater you use (quite common where I live) or you just like campfires, you already have a lot of source material! I have NO idea what the yield
is like but you'll need to find a way of purifying it since there will be a mix of potassium hydroxide, sodium hydroxide, and other alkalis.
Its not the easiest method out there these days, but it worked for alchemists.

That information is already on The Forum somewhere... I think there might be something about that in the Dick's Cyclopedia, perhaps the caveman chemistry books (the old
material that was completely free before the cocksuckers turned it into a paysite).
I don't recall the exact particulars, but I know I have read this in one of the books available online, the FTP, and somew here on my harddrive: From the Poor Man's James
Bond, I think, there are the instructions about boiling and filtering wood ash to collect the potassium carbonate. Then there is something about making this into sodium
carbonate, then precipttating the carbonate with lime giving sodium hydroxide.
Hmm, I think I am referring to mixing baking soda and lime to make sodium hydroxide. That might be in the Golden Book of Chemistry Experiments... There it is, page 45:
Bases from a Salt

In a custard cup, dissolve 1 teaspoon sal soda (washing soda, sodium carbonate) in 50 mL w ater. Heat slightly. Add slaked lime mixed with water. Stir. Chemical reaction
produces sodium hydroxide and calcium carbonate. Filter. Clear liquid contents contains the sodium hydroxide (lye). The calcium carbonate is held back by the filter.
I like that writing style, very straightforward and clean. Many of my classmates would have avoided trouble if the damn writeup specified which extract or filtered portion held
the good stuff and which could be discarded. One of these days it will get me too.
You can make your own sodium carbonate from baking soda by boiling, but you can buy "washing soda" in the laundry detergent section in a large box. Made by the same
people who make baking soda... I provide this info because I don't know what the price of a box of washing is vs. baking soda. I know baking soda is very cheap, and if you
are in this game to make a ton of sodium hydroxide (literally) you may w ant to crunch the numbers and figure out if the time spent making your own sodium carbonate from
sodium bicarbonate is worth it.
Purity wise your final sodium hydroxide w ill be as pure as the lime. You can buy pickling lime of high purity, and retail baking soda and w ashing soda are already pure; all of
these compounds are food grade, which means you could make some very high quality sodium hydroxide. Even if you used construction grade lime, most of the impurities are
insoluble.
James September 5th, 2008, 11:56 AM

I was thinking a little and it occurred to me that both the molten salt electrolysis and Megalomanias' terracotta pot method might have less chance of forming unwanted
byproducts if carried out in a glove box type deal w/ say an inert (say nitrogen or argon) atmosphere. possibly w ith a small rig inside to scrub the Chlorine say bubble the off
gassing through a neutralizing solution.
I was thinking of saying something like a pressure cooker, but that would be too kewl I think.

Actually, taking a cue from homebrew ers, if you use a plastic bucket to hold this, you can attach the lid. You can improve things with one of those one w ay valves brew ers use
during fermentation to exclude air. I think there are even 5 gallon lidded buckets with those valves already attached. Wire connections for electrodes can be passed through the
lid and sealed with caulk.
You should not even need any other atmosphere. The chlorine gas, and other stinky crap the reaction can form depending on your voltage and concentration, will produce a
positive pressure that escapes out the valve. If you compartmentalize the sodium hydroxide, you can prevent chlorine from dissolving into it and forming salt + other
byproducts.
One thing I would like to try is the "solid oxide membrane" process of making metals. I collected a few nifty articles about this for magnesium production, and presumably it will
work for sodium metal too. From sodium metal, of course, sodium hydroxide can be made. These suckers use molten copper metal in a special ceramic tube immersed in
molten salt to electrochemically form the metal.
Assuming you can make or buy the special ceramic tube, this type of reaction might put molten salt electrolysis on the DIYers table.
kolraw October 7th, 2008, 09:04 AM

Megalomania,
In your description of an electrolysis cell to make NaOH you seem very intent on making a good ion bridge for your cell.
Let me first check that I have things straight.
-We're making NaOH.
-At negative cathode:

2e + 2H20 --> 2OH- + H2
-At positive anode:

2Cl- --> Cl2 + 2e
-All together now:

2NaCl + 2H20 --> 2NaOH + Cl2 + H2
-We've got some sort of high current, low voltage (~ 2.5V across cell) power source.
To my knowledge the ion bridge completes the cell's circuit, and stops the contents of the two half cells mixing, but it seems that the contents of the half cells w ouldn't really do
any strange side reactions.
So, I w as w ondering w hy this setup needs a semi permeable ion bridge, w ouldn't it function with straight electrolyte seperating the electrodes?
(By the w ay if you collected the H2 and the Cl2 you could pretty easily make HCl, couldn't you?)
kolraw October 8th, 2008, 02:42 AM

Ignore my previous post. I realised overnight that H20 is a better reductant than Cl2 so the cell would look like this:
-At negative cathode:

2e + 2H20 --> 2OH(-) + H2
-At positive anode:

2H20 -->4H(+ ) + 02 + 4e
-All together now:

6H20 --> 4OH(-) + 4H(+ ) 02 + 2H2(NaCl electrolyte)
So the ion bridge keeps the OH(-) from mixing with the H(+) produced and doesn't ruin your hard spent energy. The Na(+) moves to the OH(-) side and the Cl- moves to the
H(+) side. Correct me if I'm w rong but you get NaOH at the cathode and (it seems to me) HCl at the anode.
Idiot me! *head in hands*

I hope I have it right now .
waveguider October 16th, 2008, 02:27 AM

How they made soap in the old days! Hardwood ash was mixed with water and filtered, then evaporated down till it was concentrated enough to "dissolve a feather". If you
have a wood burning stove or heater you use (quite common where I live) or you just like campfires, you already have a lot of source material! I have NO idea what the yield
is like but you'll need to find a way of purifying it since there will be a mix of potassium hydroxide, sodium hydroxide, and other alkalis.
Its not the easiest method out there these days, but it worked for alchemists.
Wrong.
there is practically no NaOH in ashes, the majority of wood ash that is soluble is Na2CO3 and K2CO3 (more soda lime in ash at sea side and in seaweed ash). You can roast
these to produce their corresponding (oxides) then hydrate to form the hydroxides much like how lime w as made in kilns.
http://ww w.fryingcolors.com/k2co3.html
Or If you react Na2CO3 with CaOH (calcination of limestone) however you get NaOH for use in soap making. This reaction forms a precipitate of limestone which makes
purification easy. I'm not sure on this reaction, would love if someone confirmed it.
Jome skanish October 28th, 2008, 06:20 PM

Couldn't the Na2CO3 be used to oxidize carbon, such as 2Na2CO3+C ---> 4Na + 3CO2, giving sodium or, if low er temps are used, perhaps CO, CO2 and Na2O?
Found this procedure w hile searching for a plausible ancient method of producing sodium metal, I'll see If I can find a reference....
t.shonku November 3rd, 2008, 12:13 AM

Simple way of making NaOH:
It is done by adding Ca(OH)2 (calcium hydroxide) to a solution of Na2CO3 (washing soda). Then heating the entire solution. After some time the solution is allowed to cool,
filter to remove CaCO3 , then the filtered solution
is evaporated to obtain NaOH.
The equation is----Na2CO3 + Ca(OH)2=2NaOH + CaCO3.
++ ++++ +++ ++++ +++ +

You spelling and grammar is appalling. If I need to re-write your posts again, you are gone. - totenkov
tranquillity November 3rd, 2008, 11:02 AM

kolraw : You w ere actually right the first time. Cl2 is produced in saturated NaCl solutions as you would use for electrolysis. This is because reduction potentials are dependant on
concentration and are reduced as concentration increases, making 2Cl- --> Cl2 + 2e- the preferred reaction. The Nernst equation can calculate reduction potentials at non-
standard conditions.
Jome Skanish: I do not think sodium metal could be obtained by heating Na2CO3 with carbon as is used for metals like iron. I w as speaking to someone recently who is w orking
on a process for producing magnesium metal by reacting MgO with C at high temperatures. Apparently to make that process work they heat the mixture so everything is in the
gas phase as CO and Mg then have to cool it again in much less than 1s (I think he said 0.0001s but dont recall specifically) to get a useful product. If it is cooled slowly they
just end up with C and MgO again. I guess it would be even harsher conditions to get sodium.
As a side note which may be of interest to some: The Mg process I described produces extremely fine and reactive Mg powder w hich is capable of exploding w ith only air as the
oxidiser. Perhaps if it could be desensitised enough w ithout hurting reactivity it would make an excellent pyro metal powder.
fluoroantimonic November 4th, 2008, 12:14 AM

I do not think sodium metal could be obtained by heating Na2CO3 with carbon as is used for metals like iron.
Surprisingly it does work. I didn't think it w ould either, but search patents and you will find many on the subject of producing Na metal from Na2CO3 or NaOH by reduction with
hydrocarbons or coke at high temperatures. Usually around 900*C in the liquid phase IIRC. The gaseous Na must be cooled relatively quick to avoid too much Na2C2 formation
though (I think a few seconds is no problem). It is usually done by injecting a spray of mineral oil into the gas. I think this method might not be a bad way to go for the
amateur that needs some sodium. At least it's pretty simple, no catalysts or expensive reactants. Just tons of energy.. And liquid Na2CO3 is apparently pretty corrosive so a
good crucible material would have to be worked out.

a n d I m provised C hemistry > Extraction of hexam ine from Esbit?
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View Full Version : Extraction of hexamine from Esbit?
PapaMuffin Novem ber 7th, 2008, 04:05 AM

After som e thorough searching, I've noticed that we don't seem to have a finalized m etho d for extracting p u r e h e x a m i n e f r o m
Esbit tablets. Som e users (m ostly back in 2003 ) noted that their Esbit tablets were pure hexam ine, and could sim ply grind
them up. Fro m what I can ascertain, this is no longer the case, at least n ot here in the States.
The Esbit tablets com mercially available here seem to be a combination of 1,3,5-trioxane with hex a m i n e , a s w e l l a s s o m e
waxy outer layer, presum ably for the p urpose of weathe rproofing. Does anybody have a way of extracting the hexamine from
this thing? I can im agine that rem oving the wax is as easy as dissolving the tablet and rem oving the waxy layer, which I
im agine would separate out, but I'm not sure what to do about the trioxane.
Alexires Novem ber 7th, 2008, 07:01 AM

You could pe rhaps try and bre ak down the Trioxane with an acid and that hopefully that won't break down the hexam ine.
Give it a go, and after rem oving the acid hopefully you will have hexamine and form aldehyde left over.
Setharier Novem ber 7th, 2008, 02:43 PM

I actually dissolved crushed esbit tablets into denatured ethanol, filtered the liquid from the white wax and trioxidane m e s s
and left the clear solvent sit and vapor off. I am not sure were the crystals that form ed flo ating on the surface of the solvent
h e x a m ine, but believe it or not, they were indeed hexagonal form , sm all 1m m sized. I took a picture of it which is somewhe re;
I got to find it. Bad thing is, som ebody tought it was som e unecessary waste liquid(m y "la b" is in our carage's warehouse) and
poured it into sewers so I never m anaged to find out what the final product would have be en.

a n d I m provised C hemistry > Q u e s t i o n a b o u t d e com p o s i n g a m m onium nitrate
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Hematite Novem ber 7th, 2008, 11:57 PM

T h i s q u e s t i o n i s a b o u t how I can go about not detonating som e t h i n g .
For the past two months I've been trying to extract 20-30 m g of strontium from g ranite, and I've finally succeeded. How I did it
isn't relevant here, but if anyone is interested I've posted a video (http://www.youtube.com /watch?v=-1IVPv0-HJ0) of the
process on YouTube.
The final product I'm after is CaCO 3 containing a b o u t 3 0 p p m SrCO3, with the strontium com ing from the granite. T o get this
I'm going to convert the Sr to a nitrate , dissolve it in a Ca nitrate solution, and precipitate the m i x e d c a r b o n a t e b y a d d i n g
a m m o n i u m c a r b o n a t e , f o r m ing Ca/SrC O 3 a n d a m m o n i u m nitrate.
I can rem ove the carbonate by centrifuge, but som e Sr and Ca will rem ain in solution. I would like 100% recovery of the Sr, so
I was thinking of drying down the amm onium n itrate solution and heating the solid to abo ve it's decomposition tem perature,
which should leave only Ca an d Sr.
My questions are, how dangerous is this, and what is the safest way of doing it? I'll probably have about 120 grams of
a m monium nitrate to get rid of, and plan to he at it in Teflon in a hood. Could it detonate spontaneously, or is that only a
possibility in the presence of an oxidant?
Though I lurk here a lot, this is m y first post. I realize that my goal with this project is more or less the opposite of what most
people here are interested in, but I thought if anyone could give m e a good answer, it would be you guys.
I've checked the archive. If I've m issed the answer there, I apologize.

A h h , d a m nit, I just deleted my response and I spent an hour looking this stuff up :(
Lets try this again... The decom p o s i t i o n t e m p e r a t u r e o f a m m o n i u m n i t r a t e s t a r t s a t a r a n g e f r o m 1 8 0 - 2 3 0 C . D a n g e r o u s

deflagration or explosion occu rs as low as 260 C, but more typically at 325 C .
T h e g o o d n e w s i s u n c o n f i n e d a m m o n i u m nitrate is not capable of exploding at any tem perature. This means you will be quite
s a f e heating your sample, well spread out on a dish, on a therm ostatically controlled oil bath in a fume hood to 230 C . I don't
recom m e n d u s i n g a n o v e n a s a m m onium nitrate vapors could build up, and keep organic substances away from the
a m monium nitrate.
I have these two references describing the impossibility of am m o n i u m n i t r a t e e x p l o s i o n i n t h e s e c o n d i t i o n s :

"The product that cou l d n o t e x p l o d e . " F i e l d , C . C h e m i c a l Engineering, 54, 146-147 (1947)
W hetstone, J., Holm es, A. W. Industrial Chem ist, 23,71 7-723 (1947)
Good luck finding those journals, those titles threw me a curve b all when looking for them. They are out there, but I don't
recom m end searching the web for "Chem ical Engineering" or "Industrial Chem ist" unless you like lots of false positives.

a n d I m provised C hemistry > Epsom Salt -> Sulfuric Acid?
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Unsunghero Novem ber 21st, 2008 , 02:04 AM

Ok, so I discovered today that Epsom salt is essentially pure Mg SO4...if this reaction would work it seems like it'd be a cheap
way to produce H2SO4, whereas purifying battery acid or som eth i n g a l o n g t h o s e l i n e s c a n b e e x p e n s i v e . E p som salt is sold by
the pound, HCl by the gallon...
I was wondering if the following reaction would work:

MgSO 4 + HCl --> H2SO4 + MgCl2
T o m e t h i s s e e m s pretty likely because solubility rules don't apply to solids so SO 4 wouldn't be soluble.
The only thing that concerns me is that I know Mg + HC l yields MgCl2 + H2...would the H2 combine with the sulfate? I can't
t h i n k o f a n y t h i n g e l s e h a p p e n ing...
The only other thing I could thing of would be like

MgSO 4 + HCl --> H2 + Cl2 + Mg
which would be useful at least for magnesium...you'd just have to keep away from it.
fluoroantimonic Novem ber 21st, 2008 , 02:22 AM

Sadly, this will never work.. HCl is far m ore volatile com p a r e d t o H 2 S O 4 . W h e n y o u m ix MgSO4 and HCl will get you a m ixture
of of H+, Mg++, SO4--, and C l- ions. If you try to isolate H2SO4 , say by boiling o ff the wa ter to m ake MgCl2 crystallize out,
you'll only end up boiling off the HCl.
L e a r n s o m e m ore about basic chemistry.
There's a reason people buy drain cleaner or battery acid, it's pretty m uch the only way to get H2SO 4 without a lot of trouble .
iHME Novem ber 21st, 2008 , 05:10 AM

Y o u c a n g e t s o m e H2 S O 4 f r o m M g S O 4 , by electrolysis.
I n s o m e process in "Kings chemistry survival guide" H2SO4 is produced as a waste product.
But any real production using this method would be ridiculously inefficient.
Microtek Novem ber 21st, 2008 , 09:10 AM

If you had the equipment and experience for it, then it should b e possible to first dehydrate the MgSO4 an d then heat it
further to cause it to therm ally decom p o s e t o M g O a n d S O 3 (I don't know how m uch SO 2 you would get from 2 SO3 --> 2 SO2
+ O2), then cool and absorb the SO3 in concen trated H2SO4 to m a k e o l e u m and then dilute this (carefully) with water.
fluoroantimonic Novem ber 21st, 2008 , 03:37 PM

therm ally decom p o s e t o M g O a n d S O 3
That would work in theory, but it would be m assive waste of tim e a n d e f f o r t , M g S O 4 d e c o m p o s e s p retty high as sulfates go,
> 1 0 0 0 * C m eaning you would probably get >95% SO2.. Better to use NaHSO4.
Bugger Novem ber 23rd, 2008, 06:34 PM

It just m ight be possible to do it m etathetically if one could find a water-soluble acid (other than carbonic acid), which form s a
very insoluble Mg salt, and of which the Mg salt (unlike carbonate) would not be decom posed or hydrolysed b y a q u e o u s
H2SO 4. Phosphoric acid might just work, at fairly low H2SO 4 concentrations, but then it is probably too valuable for other
purposes to be used just to obtain H2SO4.

By d irect chem ical solution this is not possible, but by electrolysis it is. I have done just this while making m a g n e s i u m
hydroxide. Sulfuric acid forms at the other electrode in a divided cell. It took a very long time to get very little, and this is a
terrible way of m a k i n g m a g n e s i u m o x i d e s . T h e n all you end up with is some sulfuric acid contam in ated with m a g n e s i u m
sulfate. It is not easy to purify that.
Far better to heat a m ixture of sodium bicarbonate and magnesium sulfate in solution. This precip i t a t e s m a g n e s i u m h y d r o x i d e
while leaving sodium sulfate in solution. Sodium sulfate c a n t h e n b e d e c o m posed into sulfur oxide s far more readily than
m a g n e s i u m sulfate. I suppose if you could form iron su lfate from this mess you could directly decom pose the solid into sulfuric
acid like they did in the old days. This would involve checking so me E degree or delta G tables to see which e l e m e n t s e n d s t h e
reaction in the correct direction (if it can even be done, I dont remem ber off hand). This is old world 19th century chem istry
here; the old science books would have a lot m ore deta iled info on doing this.

a n d I m provised C hemistry > Synthesis of Potassium Nitrate KNO3
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Setharier Novem b e r 2 2 n d , 2 0 0 8 , 0 4 : 1 8 P M
Hopefully this hasn't been yet discussed around. I just feel I have responsibility of bringin g this into knowledge due to the fact
EU actually plans to lim it or even partially ban comm ercial sale of KNO3, NH4NO3, HNO 3, H2SO4, h e x a m i n e a n d v a r i o u s o t h e r
general "terrograde" chem icals due to threat of terrorism. The way to obtain KNO3 from comm ercial dozen-fertilizers is
explained in this conversation:
>> I have found a couple of methods for synth esizing

>> Potassium Nitrate from com mon ch e m i c a l s . T h i s m e t h o d
>> relies on Calcium Nitrate (fertilizer) as the precursor
>> for making KNO 3.
>>
>> The reaction is pretty sim ple:
>>
>> Ca(NO3)2 + K2SO 4 --> 2KNO3 + CaSO 4
>>
>> The molecular weight of th e s e c o m p o u n d s i s :
>>
>> Calcium Nitrate = Ca(NO 3 ) 2 = 1 6 4 . 0 8 7 9
>> Calcium Sulphate = C a S O 4 = 1 3 6 . 1 4 1 6
>> Potassium Nitrate = KNO3 = 101.1032
>> Potassium Sulpha te = K2SO4 = 174.2602
>>
>> The right percentage of chem icals required to balance the
>> reaction from a stoichiom etricly is:
>>
>> Calcium Nitrate ................... 48.5
>> Potassium Sulpha te ................ 51.5
>>
>> W hich results in:
>>
>> Potassium Nitrate ................. 59.8
>> Calcium Sulphate .................. 40.2
>>
>> Assuming you start with 485 gram s of Calcium Nitrate and
>> 515 gram s o f P o t a s s i u m Sulphate, your result is approxim ately
>> 598 gram s o f P o t a s s i u m Nitrate and 402 gram s of C alcium
>> Sulphate. Ideally, you wou ld do this by dissolving the
>> chemicals in distilled water and boiling to fa cilitate the
>> ion exchange.
>>
>> The Calcium Sulphate resultant is technically insoluble in
>> water (an d b e c o m e s e v e n m o r e i n s o l u b l e w h e n t h e t e m p e r a t u r e
>> is increased). By adding distilled water to th e solutio n you
>> can separate the Potassium Nitrate from the Calcium S u l p h a t e
>> very easily. The solubility of Potassium Nitrate in water is
>> as follows:
>>
>> 13 g/100 m l (0 C)
>> 32 g/100 m l (20 C)
>> 64 g/100 m l (40 C)
>> 110 g/100 m l (60 C)
>> 169 g/100 m l (80 C)
>> 246 g/100 m l (100 C)
>>
>> For a tem perature of 20C and a result of 598 gram s of KNO 3,
>> you would need approxim ately 186 9 m /l of water to dissolve
>> the potassium nitrate (598g / 32 = 1869 m/l), plus a little
>> bit more for evaporation. If you heat the solution slightly,
>> you should get Potassium Nitrate d issolved in water, and
>> Calcium Sulphate should precipitate out of the solution.
>>
>> Sim ply siphon off the clear solution (this is the "supernatant").
>> You may even be able to filter the Calcium Sulphate from the
>> solution by pourin g the solution through filter paper. Boil the
>> supernatant until you start to see the Potassium Nitrate appear
>> as surface tension on the top of the hot solution. Remove th e
>> container from the heat, cool the solution to 0 C, an d let the
>> KNO3 crystals precipitate o ut of the solution .
>>
>> You shou l d b e a b l e t o g e t 4 7 7 g r a m s of pure KNO 3 (calculated
>> as (1 - (13g / 246g)) x 59 8g KNO3 = 566g AN), with 32 gram s
>> left in the solution. You can repeat this process on the
>> remaining solution to get another 30 gram s of KNO 3.
Jome skanish Novem b e r 2 2 n d , 2 0 0 8 , 0 7 : 4 1 P M

This requires the fertilizer-grade chemicals to b e pure, and water free, which they usually isn't.
C a ( N O 3 ) 2 f o r e x a m ple is m ostly encountered as the tetrahydrate, C a(NO 3)2*4H2O. Here in Sweden we have two brands of
useful non-conspicuous fertilizers, one consists of AN and potassium sulfate, and one consists of mainly calcium nitrate
tetrahydrate with som e 5% of the nitro g e n c o m ing from NH4 (as AN)
Most people in here should be able to figure out the ratios to form KNO3 from t h e s e b a s e d o n t h e s t a t e d N P K - v a l u e .
In "our" case, we nee ded to first calculate the amount of amm onium ions in the fert. grad e calcium nitrate, and then these
would each g rab a -NO3 rendering it inert as the AN won 't precipitate when the supernatant is boiled down. So, here it was
" m o l e s o f n i t r a t e / k g - m o l e s o f a m m onia / kg = necessary am ount of K2SO4, which in turn was calculated after the K-value
of fert. II sin ce K forms very few insoluble salts, on the contrary to Ca.
W hat I am trying to say is, m aking a specific "how-to" writeup will not be very use ful for anyone (...) if the principles behind are
not understood.
EDIT: Tetrahydrate, it was! And the cra p is insoluble in ethanol, just as K2SO 4, meaning we have an easy way of purifying our
KNO3.
Hinckleyforpresident Novem b e r 2 2 n d , 2 0 0 8 , 0 7 : 5 0 P M
W e're dissolving the nitrate in water... It certainly doesn't m atter if it's the dihydrate, or if it's anhydrous. All that you need to
know is how m uch m ore the m olar weight of the hydrates is in order to get the proper ratios.
Lewis Novem ber 23rd, 2008, 06:27 PM

This procedure may be useful to rocketry enthusiasts or black powder m akers, bu t I don't see how KNO3 is any m ore useful in
HE production than Ca(NO3)2. (other than the hydrate issue, which I assum e can be resolved by heating th e calcium salt
carefully, but I could be wrong )
R e g a r d l e s s , i t s e e m s a m ethod for creating either am m onium or sodium nitrates would be best for nitrations or distillation o f
HNO 3. Thankfully, I don't have to worry about this sort of thing in m y location. A sim ple five minute drive to the nearest farm
a n d g a r d e n l o c a t i o n g o t m e 25kg of prilled NH4NO3, with not so much as a questioning look. (it's winter, to o)
I suppose there are advantages to living in the breadbasket of the world.
Jome skanish Novem ber 25th, 2008, 09:17 PM

Hinckley: You are assuming that the agricultural chemicals are p ure, or can be ea sily purified. That is not always the case, as
with "m y" calcium nitrate which contained both insoluble crap and amm onium nitrate. I once tried to boil it down after
dissolving and filtrating (the AN was su pposed to stay in solution) and was treated to a rather im p r e s s i v e d e m onstration of
over saturation and rapid crystallization once the solution was stirred.
If AN is desired it could be had if the calcium nitrate is reacted with am monium sulfate, precipitatin g g y p s u m . AN in stores?
Never take anything for granted...
Hinckleyforpresident Novem ber 27th, 2008, 07:01 PM

If it cam e d o wn to it, you could separate out the nitrate by fractionally distilling th e fertilizer with sulfuric acid and only collecting
the HNO 3. Unfortunately, one would need a large excess of sulfuric acid just to keep the calcium bisulfate mostly in solution.
This process would require the fertilizer to be anhydrous, which could be done by throwing a cookie sheet of fertilizer into the
oven at 200*F.
If a nitrate salt was required, it could be m ade by neutralizing the acid with the appropriate base.

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stanfield February 21st, 2003, 04:32 PM

==&gt; <a href="http://stanfield.150m.com/plastic.htm" target="_blank">Photograpy of the experiment</a>

rikkitikkitavi February 21st, 2003, 05:14 PM

Mr Cool February 21st, 2003, 06:19 PM

stanfield February 21st, 2003, 06:52 PM

How can I "grind" my PETN into fine powder ? is a mixer recommanded ?

rikkitikkitavi February 21st, 2003, 07:33 PM

Microtek February 22nd, 2003, 09:25 AM

stanfield February 22nd, 2003, 01:49 PM

Microtek February 23rd, 2003, 05:45 AM

bonnsgeo February 23rd, 2003, 06:29 AM

Mr Cool February 23rd, 2003, 06:47 AM

kingspaz February 23rd, 2003, 08:55 AM

Microtek February 23rd, 2003, 10:05 AM

Observer February 23rd, 2003, 10:20 AM

Microtek February 24th, 2003, 03:16 AM

Observer March 8th, 2003, 03:49 PM

andreas March 17th, 2003, 01:55 PM

Maybe this is a rather cheap source for PIB.

Mr Cool March 17th, 2003, 04:43 PM

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CyclonitePyro February 24th, 2003, 12:10 AM

A-BOMB February 24th, 2003, 12:45 AM

spydamonkee February 24th, 2003, 01:14 AM

EP February 24th, 2003, 01:47 AM

Nihilist February 24th, 2003, 02:09 AM

Microtek February 24th, 2003, 03:22 AM

xyz February 24th, 2003, 04:54 AM

0EZ0 February 24th, 2003, 05:51 AM

Good luck with the project.

CyclonitePyro February 24th, 2003, 07:36 PM

<a href="http://www.globalsecurity.org/m ilitary/systems/m u n i t i o n s / m 3 0 0 .htm" target="_blank">http://www.globalse curity.org/

I t h i n k a r o u n d 5 0 - 1 0 0 g o f A N N M m a k e s a crato r of the desired size for m y, err, m y friends use.

Anthony February 24th, 2003, 10:25 PM

<img src="http://www.longchengtools.com/1006c.jpg" alt=" - " />

Of course this is what you really want :)

<img src="http://www.fs.fed.us/r4/boise/m gmt/watershed/SilverCreek/media/dscn5503.jpg" alt=" - " />

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frogfot February 25th, 2003, 12:19 PM

T h e r e a r e a " s i m ple" way to produce benzophenone, by destillation of calcium b e n z o a t e . I h a v e m a d e s o m e e x p e r i m e n t s o n

Can anybody solve those problem s or give an addvice, please?

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IPN February 25th, 2003, 12:33 PM

I wo uld test this but I d o n t have any calcium b e n z o a t e .

Btw. that product looks like oily phorone...

Found this with a little search:

frogfot February 25th, 2003, 12:55 PM

==> <a href="http://stanfield.150m.com/plastic.htm" target="_blank">Photograpy of the experiment</a>

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