\ AMG PAMPHLET Ap * a ws incom jo I | ENGINEERING DESIGN ' HANDBOOK jo PRINCIPLES OF > EXPLOSIVE BEHAVIOR Sep niece tn nner net RS HEADQUARTERS, US ARMY MATERIEL COMMAND APRIL 1972‘| PAUL M. SCHUMACHER ! HEADQUARTERS, 06740-5186 | VA wire gue exe, como 92 dave pavener , frame 10 peti 1972 [BNOTVEERING DESIGN HANDBOOK ‘PRINCIPLES OF PLOSIVE BRHAVICR ~ eas ‘TABLE OF CONTENTS P traph Poe | { List oF nLusrRATions “ i . tito tases 5 1 mcrae os | Pi courrens, wtsoveron a) i Mey mat ns | : i 1 Biaatttgeestoaes IB | 1 1 ‘Types of Explosives ees seme 1D | i Ho Bonaioe 4 i Hi CHAPTERS, THEORETICAL BacKoROUND i | Bln cece eceneeetecees 84 i : i 32 Deon ib Gonpaan oH 5 , 23 The Laws of Thermodynamics 2.002... ccies } } 24 Geert Temecula TS Bh ‘ 23 Soult bea ' Tepsieornetog oe 4 24 wyantmener otha ol 00 BS | Meaty top owls Olina 2000. ; 2 Comal cms Deo : ) ‘hep banen sar nse Fesuc 7100 ‘TABLE OF CONTENTS (Conta) - Prapoh Pe CHAPTER 2. ENERGY OF EXPLOSIVES ’ ql | { | oe ee i { 32 Hestof Detonation... aerate { 1 meet i i Se eee ee eee oes A ds. : Seen sneeas i aa i , unin rau omeneceinon oF noes . pe sseaas nae en Meets 8 feria cote tt esta a fea croutons im eee oats 20 atten i se a ate (CHAPTER 5, MEASUREMENT OF DETONATION PROPERTIES $1 Inteoduction pee eee 82 Detonation Vac. ssc. Ba 521 Higeapeed Photoraphy 8a 522 Photooptica Systems o4 523 Beet Sytem. 54 524 D'Autche Method 56 5 53 —_Delonaton Pewure 55 4 53.1 Presaure in Adjacent Plates 58 : 581.1 Plane Wave Explosive Syrtems 50 ' 581 PromureTransdvoer.. s10 4 5313, Particle Velocity Messirement as ‘ 53.2 Xray Fash otogaphy 518. ‘ 54 Bae Wave Preaure 519 55 Detonation Tempertice n 5a ‘ 58 Blectce Conductivily Inthe Detonation ane vss... RBnena { | PAUL M. SCHUMACHER 06240-5486 HEADQUARTERS. UNITED STATES ARMY WATERIEL COMMNO 10 Apett 1972 . itbtikcn, De oaks hy ‘ ‘AMC PAMPHLET: } No. oer 4 ENGINEERING DESIGN HANDBOOK } ; ebtoras oF buastve saavioR i i if oa ! s . ? i TABLE OF CONTENTS. 4 et tn v1 LIST OF ILLUSTRATIONS wi ; UIST OF TABLES Ff ‘i PREFACE . - ot i u CHAPTER 1. INTRODUCTION ° ee) ; Poe Introductory Remarks: . eee coe ia 12 Batre G 13 Dowotkmoie ee tye uy 14 Some Deftitons Ev , iH CHAPTER 2, THEORETICAL BACKGROUND oN i} 21 Introduction. sostieeseecees 2a 22 Denton od Gonpaion 2 ? 2 ‘The Laws of Thermodynamics Bt } 24 Gent Temodyremi tet 2” 20 a ete f 35 Aen ar nai \ operon a etope reeves cececceesoees 26 7 1 26 Hydrodynamics of Rescting Continua » : 216 | 21 Untomly stops Mow One Dison 20000000) 2k ; 3H CaaradenCnnts Dnt - ) The Hugoton . 2a ; Releott vee ssennescenne LE, 2 : } |sce 708100 2 ‘TABLE OF CONTENTS (cont'd) Paragiph fogs CHAPTER 3, ENERGY OF EXPLOSIVES . i i ft t $2 Inlrodution we } 22 rat of Detonation a { 33 Thermochemiatty of High Bien sa t 24 Computation of @ Sais 33 { oe 85 Fragen Velocities 34 26 Aiba en 28 397 Underrater Performance ca cas 38 CUPmmeter 38 . 39° -Maximem Work 2.02. : 36. : Referees 5 1 8 (CHAPTER 4, THERMAL DECOMPOSITION OF EXPLOSIVES . 41 ntrodotion 4a 42 Decontpostion Boeri ss scsessscengeeeseseer 1 43. Decomposition Mechanians «=... a 421 Covent Ligudsand Sole =. “4 : 432 Tonle Slide (Azide). cm co 48. 493 AmmoniomSala 00. 2 IN age +4 Raion Damen te Solids TI aa . References = IIIS ao , (CHAPTER'S, MEASUREMENT OF DETONATION PROPERTIES 2] 1 nbrotietfon oss seeessseeseeee we SL ‘ | 52 Detonation aoe ae 8a | 521 Highapsed Photography 51 522 Photoopticd Systems o.oo icc sccesesessones Bd 523° Bleawial Systems... css s sossssviecseecennes Bet 524 —_D'Autiche Method, : 6s i 53 Detonation Prete... 0... 5s i 531 Premure in Adjacedt Pte TOI se. ! S311 Mane Ware Explosive Systeme IIL se ‘ 5312 Premure Traneets yo ceveccssscssverey cove S10 5313 Particle Velocity Meturescent COLI sas * 532° _Xmy Fath Photopaphy CIID sss ‘ 54 Batt Wave Presse - TEI sas 55 Detonation Tempemture TTD san a | 58 Mecca Conduetivityn “ie Detrnation Zone 522_ oe TABLE OF CONTENTS (Cont'd) Pameoph Pee 57 Baplsial Tots sececeees SMM References 00 searseeseeceesa BO CHAPTER 6. ELEMENTARY THEORY OF THE PLANE DETONATION WAVE 61 Introduetion oo. poe or I 62 The Rankine Hagoniet Pauation sosc ss csene aL 6:3 Properties of the Hugoniot Curve I ee 64 Existence and Uniqueres of Flows fnvelving . Reaction Waves ou 65 The Cpmanougue! Hypothesis Be 619 88 Theory of the Detonation Velocity and of the "Thermodynamic Stat of the Explosion Gas. 624 Referees tooo sos epee 626 ; (CHAPTER 7. APPLICATION OF THEORY lon "TO CONDENSED EXPLOSIVES, i \ f ; ; i } } \ i 5 Btn. a lio i= aes fa 4 \ i \ \ ‘ 72 Determination ofthe Detonation Sate from Velocity Data 78 1-4 Modiietons af the Abel Euston =... 18 1S Appleton of the Chapmandeuguet Condition ta ‘Mixture With Varying Compodiion-....v+eeeveee+ 748 16 Replosves Whom Products Contain Sols Pha... 715 11 TheViril Eguton ot State... IN tae | 18 The Halford Kiiakowshy-Viluon Bqustion of State... 128 i Reference sso. wees BRL (CHAPTER 8. STRUCTURE OF THE PLANE DETONATION WAVE INITE REACTION ZONE 81 Introduction see ooee se BA 82 Conmvation Conditions for Steady Reaction Waves in (One Dimension ose oseeseoe ‘The Steady Delaration Wave "The Stendy Detonation Wane low Behind « Chapin Jouguet Wave... ssc vees cas 88 2 ‘The Detonation Wave With Equlibeium Product Composition Cempoitionsovessecsssesser ne) 87 Fine Strctre of Detonation iy Guus and Liquide ae Welexencet oe eoe Soresso nest ee ‘TABLE OF CONTENTS conta . eer ae ‘ i CHAPTER 9, DETONATION WAVES OF ‘ Peet tarab ata i : aon woes. 8 a $b TRetatat Gang Banos oon Vaody $2 98 Dinan Pow Wiis» Cyne Sjmmetic Sealy scion Zone. : 94 Theories ofthe Charge Diameter Btfct | : 35 The Release Wave Model wos... 5 98 Me sphere Denton ae Toate at Point | Reference, ‘CHAPTER 10. THERMAL EXPLOSION. t 101 Ingodtion a0 ) 102° Desipton of ine Tera Baploon Proce 301 : 163 Mathematical Treatments of Thermal Explosion 107 i 1081 ‘ThelHeat Conduction Equation... 107 4 3032 -Stendpatte Condon 9770 = 0, nd the Concept ot Cate Temperate and Si. 108 _t j 1033 Adiabatic Heating (747~ 0) andthe Conept ot oO! Explosion Tine... 109 Lt | 1084 penne St, Wi Naini } eating seve 100 i 3095 Namen Setbods “120000000 ILI son 104 ‘Thermal Explosion of Hot Spots tot ( 305 Tal Epo ed Sey indie hp 208 Reterenois 10m ‘ (CHAPTER 11. INITIATION OF DETONATION BY SHOCK WAVES M4 —_Underdriven and Overdrven Detonation . ma 12 Thecup Tet TID awa \ 313 Shockpremure Meunstements inthe Gap Tet so...sc0.. TE : - 314 tacts of Shock Waves in Condensed Explother a 5 Shock initiation in Homogeneous 5 ‘nd Noohomogeseout Explonven us j 146 Thermal Bploion Thary Aplied io Shockinitton «13-10 - 1161 Homogeneous Explosives 5 ano 1162 __Beharorof Hot Spot ss IoD aaa ‘ 1-7 Hot Spot Craton by Shock Waves vecccesccccesvesee HLYT 118 Senstity to Shook Initiation 5.2... anemcr rt00 TABLE.OF CONTENTS (Contd) Pargnoh Poe 31-8 Theory of Shock Wate Initiation in Solid Explosives... 31-28 3140 Lowadocity Detonation (LVD) ... ceive 118 Refecaeh se SEISIIIIT ast CHAPTER 12: INITIATION AND GROWTH OF DETONATION ‘FROM IMPACT, FRICTION, AND THERMAL SOURCES. 321 Sonitrity to Impact and Fition « ve aa 122 Design and Analy of Senaltity periments 4 128 Theory of impact Semthity ot 16: 324 Transition of Deflation t Detonation ans Reference CIS aaa (CHAPTER 13. SHOCK WAVES FROM EXPLOSIVE CHARGES. 131 Introduction. 19% Expansion ofthe Explosion reducta 383 BoengyThansport by Shock Wave Propagation 184 Blast Wovesin A fons Explotve Charges. 385 Renuts of Numerical Intepation of the Bye namie aaa 133 335 at ‘Bguatlons for Blat Wav Ait Peetesere 1940 4186 Underwater nd Underground Explosions + 1919 1877 ‘Tho Initia Shock Wave Premio «..- 2 1325 188 An Apmoninne hey oie ePopein +1898 439 Shock Wie Sealing «+ ass 19:10 Exploavely produced Shock Ware in Solid I asas References. CIT aso (CHAPTER 14, COMPUTER PROGRAMS FOR ‘EXPLOSIVE CALCULATIONS 141 Intyodueton ceceeeseese Ma 42 Methods of Hydrodynamic Calculations ==. at 4421 Intoduetion a 1422 Method of Charsctaiatio aut 1623 Method of Artif Viwoty-s. sss. sscssssss 146: 1424 Particle dneell Method un 143 Bquationofsate Computations... un 144 Reaction Mechaniams for Computations sas 145 Summary of Calculations of Wave. Propegtion With Beatie Mechaninit csssssssevsseveneesssecseee 1428 References... DOIININIIIND aaas‘TABLEOF CONTENTS (Conta) Pamrooh Pee APPENDIX A, EVALUATION (OF THE THERMODYNAMIC PROPERTIES AA otodution- Aa ‘42 Thermodynamic Propertis of Pure Condensed Phases... AT ‘AS Thermodynami Properties of « Gar Mixture aa ‘$4 Thermodynamic Properties of Heterogeneous Sysiems-.. A-6 Referencer ener aa APPENDIX B, GENERAL PROCEDURE FOR THE CALCULATION OF EQUILIBRIUM COMPOSITION Bi Introduction. Ba BZ Lhsccrzation ofthe Bauliteium Conditions BL BS Relations an Equation of Sate Explicit in Presrue and Tempernte Ba B4 Relation for an Equation of State Explicit in ‘Volume and Temperature socceeeses BM BS Thelnial Approximation BS. BS Calculation ofthe Bqulibinn Partial Decatves «sc... BS Reference ea Br APPENDIX c. METHOD FOR THE DESK CALCULATION ‘OF EQUILIBRIUM COMPOSITION OF SYSTEMS CONTAINING ‘COMPOUNDS OF CARBON, HYDROGEN, OXYGEN, AND NITROGEN, ©1 Introduction. . penal ©2 Systems With Sli Carbon. tee C3. Rich System Without Solid Carbon, go <2.4e ¢au2 -- C2 C4 Lean Systema Without Sold Cabo go >2 ae +Ay/2s.. C2 APPENDIX D. IMPERFECT GA€ CONTRIBUTIONS TO THE ‘THERMODYNAMIC PROPERTIES FOR SEVERAL EQUATIONS OF STATE Da Introduotion pa D2 The Abel Hauelion of Stata 2... i pa Da ‘The Abel Equation of State ws Mote ty Jones. Da D4 The Abel Eqution of Stale as Modified by Cook pa DS ‘The Vii Equation of Stale of Hinchflder and Rowveare D2 DS The Halford Kisiahowshy Wilson Bquation of State ..... DS.acm pe newer tnt tin phan Pins a be \ 5 t { iv 1 + 5 , ES ee en ae ac 708180 ‘TABLE OF CONTENTS (Contd) Pansroh Pee [APPENDIX E. CALCULATION OF THE DETONATION VELOCITY ‘OF THE THERMODYNAMIC STATE OF THE EXPLOSION [APPENDIX F, CALCULATION OF THE DETONATION VELOCITY FOR IDEAL GASES... -c.secseccsvenonse A INDEX oo eceseeeeseesene Mt aag No. a a 22 23 os te 4“ “a 4 4 410 pers 52 oe 85 LIST OF ILLUSTRATIONS mite Model st Explosive Charge The Gitte of a and fy forte Baplodcn Prods otTNT Region of intone ofa Point P Domain of Dependence ot Aw Bot cee aii Vale Curve Domain of Dependence of Are AB of «The Titi ‘Value Curve and Aro BC of a Timaike o Charsteriic Initial Value Curve Stright Characteristics C,, Paton Path and Partie Path {na Simple Rrefaction Wave... atersecting Straight Charactrace “Cy ‘bee Comprenion Ware son ese-ssceseceyseseveers ‘Onedinendonal Shock Wane Flow ina Steady One-dimeraicna Shock Supporied by « Pion, Showing: « Particle Poth and C, Characteristics ‘Through Point onthe Particle Path = ‘Thernal Decomposition Sigmoid Curve Plot of Loguithm of Rate constant Fw. Reciprocal of Absoute Temperature to Determine Activation Energy from Sope ofthe Line... Representation ofthe Orit yntem of tbe Asie Tou Schematic Showing Boer E to cite an Elston from Valence:Band to Condition Band n iver Asie Showing ‘Technique for Stiiyirg Siver Nucl! trom Decomposed iver Atide ...-.- Schematic for Determining Optical Atworpion Speci « ‘Absorption Coeticients cau Function of Wavelength A At High Absorption, Photon Energy hy Awumed to Comespond to Band Cap Eneray . ‘Showing Exciton Lees. Brerny GapeE, and By Sn Sve Aude ‘Schema for Syn Poteau fC Orbital System of Covalent Azide, HN... laments ofthe Rotating Drum Camere Sytem (Opiical System in AEC Bowen Framing Camere ‘Arrangement of «Kervtfoct Shutter. Block Diagum of Equipment for Measuring Driotation Velocity With lonization Probes. Bigg coco Tae 0 Obtained With Raster Generator DiAutiche Tet Ser» 26. 293 206| \ ‘cr 7000 \ 5 LIST OF ILLUSTRATIONS (Cone Fig No. Tie fee 51 apvete Generator (A, and Shock Wee Bete (B) and _After (©) Hmpings on the Metal Bate. oa | 58 Compemitity of Vass Malere Under Shock Wave > Conditone siz 4 59 Configuration forthe Mearrement of Interface Stes i ‘singe Quarts Pemure Tranedicer -. sas i $10 Confipintion of Mngin-epory Pras Trenance +=. 514 i 511 Form of Polazton Sigal fom Polazaon Gage...» 38 f 12 Nei ele fo Mesing Pern Vay \ snd Sock Vlas se 1 512 Loerintecteromele Sytem sit S14 The Sssheddapagn BAL Pervire Gap for Meaning Fooe-on Aira Prasune 520 S18 Bical Conductivity a4 Function of Tie in the ' ‘Detonation Reaction Zone of Various Explosives oa t 61 Oneddimensional Reaction Weve a2 i 62 —Hugonit Cure for Detnaion and Defagitens sss. 64 3° Nomocatre onthe Hugoiot Cure for Detoatice and | Dentagatons 6s a) €4 ——-Huponiot Cure (H, Raylgh law (By and Tontopes i (Gued carve) for (A) Strong Deletions and Weak Senagations, (8). Chapmandougset Detonation and t Detspaton’ aa) (O)' Wear Detrasoce wed Sesog i Defagatins { 5 Wave ra ad ui in rj a eton { ‘and (B) a Defagration With uy = O.....+.+ or ' 66 Puyol Reuzaie Detonation and Defagmtion Sine. 68 &1 —Rlowina Strong Detonation 16 €5 —Flowin Cupmandouput Detention ent ' ©9 Parte Velaity Behind Detonation Wore Stang , i Detestion, (A) an (8); CharerJogaet Detoratins = - f (B)(0),and (0)... - seoee GAT i 620, Poowin Weak Deaton Wit Coed Bod ast t @21 A Detontion wa Deagation With x Precompreion Shocks 20 { sa Ritalin oon is 4 Waves on t 1A Covolume’ Pundion foe Deonaton Prodi ot t Conese aploden aa : 12 Cowan Fueton for Detonaion Progcts of PRIN oo. 742 a forSeyDenenion1 | | | | | { t Fig No, a2 83 4 8s 1 o 9s 9s 96 on 301 302 103 104 108 108 ao LST OF ILLUSTRATIONS (Conta) Tie niyo Hupsit Cue fr Sty Detonation Waves rereeateese "The voo Neumann Pathologie Wik Detonation Frew abd Patice Ys Bind an Unipaed ‘ChapmanJoupuet Detonation onan Compton and autem Huge Gyn BymmtiFow Throws Detonation Wares Models af the Reaction Zone Employed by Wood snd beech Ne i i a opi Ci oe En nd Corr td (©) Cook Typ inion Repetto of te min Pl fo Un in" War Ctsnns ape Wi he Spied ur Pale Apps Mtn of Roger of Chane Sutuow ft Teena Eile pw Dea ae “Roma Wave They Pare eocy belnd» Spe! Deiat Wats Pein ge 338 cree Pen nd Spann “a {bs Bgminunt To a Go Oa Dane oa Trem Elin i ttn i ind a ain totyp epd i P10 Sng Caerleon Tin) ins Beant ote ype Dapeng 101 nd Constant re Bunnie 108 Tampenii We odo Indion Fer Cased for i Spe of ROX tntay ae loon Tne 3 fr DX in Vos Geetn tay 25% rap ftp yo pe ina, sl ily 25% Tempera Diebn Desig Casing of Spa Fi et Ma Tat ar Ba ed aly lt Uae Temperate Tn Tako Be Seance” a7 10 613 oa on eas 104 105 106 Fst} sou 1038 tox é bFig No. ua na us 4 us 164) 1168) a us no nao nan maz mas at nas as nat 118 LUST OF ILLUSTRATIONS (Cont Te “traumision of Detonation from a. Donor to an Acceptor Charge enero ‘TmeGap Tet Cage oer tnd Dineron for NOL Gap Tet Shook We Pri ae Ho of Zac Gap i te ‘NOL GapTatt Conan of Shock Loin ot 80 Becet Point With Trial Prenuredn Charge « _Ammerent to Meane Shock an Detonation Trav in 4 Nesitmopnons, Slt Pale Use He Woe ‘Tecanique “Rrmngamedt to Meme hock ad Detonation Travelin Homogeneous Liguid Explosive (Nitromethane), «++» Disance ve Time Behavior in Shock Wave Initiation of [Nonhomogentous and Homogeneous Bxploives «<0. Sue Ces Recife! of Roy Sk Ware Induction Time. ‘Shrk Illaon Induction Tins in Nizomthane a Diferent Shock Prewures and at Different Initia Smear Camera Record Showing Btfet of Bubbler in Tnlation of Nizomethane Prmuredance Prefs at Vasous Tis forte Shock Inllation of Nitomethane by a 92. Shoe. ' Promueradius Profiles at Vascus Times for the Drelopment of a Detonation in Shocked Niomethane (G07 Hs, 1090) om «Spe 2 Tempe Ht Spot (1404°K) of 0.292 ~em Radian - Prmurendius Proties at Various ‘hime for the Dmelopment of 4 Detonation in Shocked Nitzomethane (GUT Kor, 1290°K) from a Spherical Temperature Hot Spot (1408°K of 0.06 -em Radi. FramuremdasFrotles at Various Times for the Pale ot £ G028zemradie Temperature Hot Spot (1401°K) to Tsiinte Propagating Detonation in Shocked Nitromethsne (047 War, 1290°%) 5 Succesive Configrations of Shook and Bubble tthe Hot fo he Shook n Helm Hing» Neon Babble. . Nonmaized nition Crain... stot Pate Wb co Minima inning Sock eeure ‘aver 708199 na ua 13 nd uaa uaz nad mad nas nas sag nat saei | | nm ) * | mat 122 | 128 125 1 126 | 121 128 129 320 | aa a i 134 | 198. 186 | 181 LIST OF ILLUSTRATIONS (Cont) ite ‘Buldup of Shock Wane in Sold Explosive to Detonation {ora Surtace Erion (Grain Burning) Law of Hest Release sees ecesr eens oak Premure and Potion of te Wave atx Fusction of ‘Time for the Cae i Fg. 2118 ove eecee Propaption Faure in Blasting Gelatin =. Impace Apparatut Showing Anvibatiking Pin Ase Ukeration of Appar for Delermining the Friction Bendy of Sold Exponve ms Example of « Gentitniy Tet Rem Comping 100 Tals Folloving the Upanddown Method . Cures for Calelting# trom M When Mf <040 ln the ‘Stated Reduction af Impact Senativity Duta... ‘Cavity Striker, Showing Snill Air Bubble Inside Cavity “Explosive Decomposition Daa from the Adiabatic Fume ee : Corton Pct of 80 Percent Explosion Drop Height in the Sensitivity Test w Cede Explosion Temperate for HotSpot of Rade 10). seo. .---- (Charge Atranement Used by Macek to Study Deagration to Detonation Teton Ghanian Diagam (C,) for the Development of & Sampmion, Wee om. Dafegnton in Rity Confined High Explotve =... 2+... Dereopment of Compression Ware from Deflation ax Trond om he rete Dngrn in. Development of Shock Wave About Cylindcel plein ‘Chare Insta st One End... ~ ‘Shemutic Wutration of the Energy Retention Resaing fom th Entropy Incase atthe Shock Pont. Premuredislance Cues for Blast Wave in Ait at Succemive Tsetse ese eveseseseess Particle Velocity distance Gases for Blatt Waves in Aira Sucomive Times. : 5 Presume Curves fr Blast Wave in it so... Huponiot Properiee of the Shock Wave for Ideal Polytopic Air =... Peak Presuredistance Curve for Shock Wares Air Calelated With the Pont Source Model (rode)... Preaurein Atmogphares as « Function of the Lagrange ot Mase Position for the Point Scuroe Solution at Tinet Indinted ees scscescsetessessovesenerersesssont m5 ma 122 123 12s. sat 29 wn 1214 126 aaae 1219 132 196 18 199 139 aa saat sasFig No. 139 1310 aan asa aaa wie 1315 1316 a7 ae sa9 1320 rea aaa ma a ua aaa) 4400) as Aer 70100 LIST OF ILLUSTRATIONS (Cont'd) Tile ‘Spucesime Diagram for Shocks and Contct Suface for ‘TNT Bat i Als (Brode) Pree datance Curves Wares in Ai (Brode) Peak Preautedistance Give for TNT Blast Weve in Ait (@rode). ‘Premume-dtance Curves for the Underwater Shock Wave Produced by «300% TNT Charge Premurtine Cue for the Underwater Shock Ware Produced by 2.500% TNT Charge ‘Bubble Osellations from an Underwater Explosion Premureine Curve for Underwater Presse Waver 80 f ‘om a 2001b TNT Charge. Hugoniot Properties foe Shock Wave in Sea Water Peak Prureditance Carve for the Undermter Elon of TT Cae by Pee an 9 Scone Times for TNT Bat Explosion of TNT at Calculated by Kukwood nd Brnitey g Peak Bxceu Poewire Raw isin in Cage Radi fot {TNT ate Loading Denaly 01.8 gle... Peak Baoom Premure Ratio ve Distance in Charge Radi for Pentlite at a Leading Density of 1.65 gem? (Shear and Weight) Poalive impuloaatance Cure for Peta» ‘Typleal Characteristic ridin the Distaetine le. (Charctarsc Gd for Hartree Computation Scheme Paths Treversed by Thermodynamic and Mechanical Stest ‘Tamugh « Shock Fron; Definition of Ariflal Vazour Stra... Stes Histories Genemted in Tungsten by an Impact With 7 Bpoxy: Quadratic Avicial Vseosty Only With « Cocticient of 40. Stea Hitories Generied in Tungsten by an impact With C1 Bpeay: Linenr Artie Visoaty Only With CoctBciet of 05 (tid fr Depicting Cocrdnats and Time increments - 136 ast 3918 190 ea a2 922 14 x30 3327 1933 3394 1395 M3 ua M4 16 ua 48 ue ~Pose 430 eae Hugonits and Pate for Steady etate Sheek ood Reaction LIST OF ILLUSTRATIONS (Cont) Tile See roles Following impact in «Mele Represented, int Homogeneous Explave ty Simpl Aneasic Modal aN, 46 uans re — ae some 708 180 List OF TABLES. ‘Tbe No, ee Pose 11 ‘TypialBxploive Substances 1 12 Compatitons of Some plore Mixtures. 1 25 Some Basic Thermochemical Data. 39 92 Galrimetric Determination of the Heat and roducte of Detonation ‘30 33, Ident Gus Pre Boeey Punetion (67/87) for Detonation Frode sa uM Mat i ie dia abn 1600°K : saz 35 Caoulted nd Observed C4 Parameters =. aa 38 Correlation Between Q and Oxygen Balance ae 81 Coimpainon of Qc and Q, Based on an Attitrary ‘Decompenition Mechanim 238 38 Compainon of @ and Guiney Constants for Plne-ware Shots sis 49 Comelition of @ and Equivalent Weights for Fie Ai Blast 3:17 310 Underwater Performance of Exploves « Esty 3811 Coneltion of Detonation Energy and Maxima Wort (Baltic Mortar) Fst) 41 -Aetition Energies snd Pre-exponential Fucton for Some Bxplotve Liqudrand Solids... “ “a ‘Term wd Peace Domo of one ele Asides a5 51 Chapman-Jougut Prewores in Vagus Beponver ss... 58 52 Experimental Detonation Temperaturet 5a 7A atmo te Detonation rope cf Composition as 12 The Daina i wis api vet Locus tor Compatition B -..+ 3 113 Detonation Properties of Some Pure Heplesives 740 4 Detonation Propertis of PETN m3 15 "The Adiabatic Exponent for Composition B Along the (Chaprn-Jouguet Locus ma 14 ‘High Temperature Sioond Vici Coeticints of Gaseous Detonation Products... ve mat 14 Detonation Properties of Some Condensed Expl... 738 78 Values ofthe Contant wo -- 739 78 Comparison of Caleulated Detonation Properties -. 120 102 Swlllo Rate Constants for Fistotder Isothermal ‘ecompositin of Explosives. 102‘Table No, 102 Fry 104 108 ma na 3 4 ns née m4 aa aa aa LIST OF TABLES (Cont'd) ‘te ‘Typleal Beharior of « Solid High Bsplosive Compound. Following an Arthenlus Rettion Law +... ++ (real Value for Thermal Explosion rameter and ° Peers ‘Approximate Schitions for Explonion Induction Times for ‘Sent nfnte Pana Explosive « 7 Various Clclated Quantities for Hot Spotain RD... ‘Cited Dameer and Adiabate xplosion Time for RDX.... ees ‘hock Senaivity of Sold Rocket Propellant the NOT Gap Teese. seeeeaee Calculated Shock nliation Induction Time in Homogeneous Explosives. Btfectof Donor Charge Diameter on Shock Senatvity ‘Experimental Cardap Test Rawal... Raila of Lowaelonity Detonation Stablty Studia With NGRGDN..- rs. - LWD Gap Test for 1,2DP! fet of Confinement ‘Geometry and Sonic Velocity... ‘Corelation of Senitivty Tea With Reaction Rates... Into of Explosion of PET inthe Praereot ‘Kinetic Propertin of Explove Materials rom Adiabatic Saltheating Experiments «+5. Hotepot Bsploson Temperatures Caulated on Basis of Detain Table 122 seve ecoo 108 109 i012 1038 1019 1019 naa aaa 23 a8 19 180 1190 0 raa2 reasce 78100 PREFACE ‘The Engineering Design Handbooks of the US Arany Materiel Command are a coordinated serier_of handbook: containing baie information and ‘andamental data uel sh the dain and development of Army materiel nd ayes nthe lst sever dcader-cersiny since World War Tima get del of ‘work, both experimental and cheoreta, hasbeen performed on explosives hd thew efleclr "There didnot exit n-eny language 2 wtstctry, ‘Compreienavecompistion peseting a unified, wi-ecnaatent, theoretically Competent treatment of thie aera. Also, «lege umber of interesting Conittulions ftom ‘Governmentaspporad: and Government liborataren, which have now been declifed and should provide vlable Infortion, Vrs comparatively nacowble to the average scientist and enginer. "This Handbook etlempls to correct the Stuation, Proened is unified tmestment of te iporant ope Ierature in whic i included not only ‘ticler fh profeional joumaly but algo the avalable military reports of Simportance Orignal contaibutlons alo have been mace to the theoretical portions, Much eumrent research on explosion phenomens involve numerical {oitions to compler mathematical equations of fuid dynamic, chemical Lineley, thermodynamic and: est tanapr.. For tia reason 1 description ‘of some ofthe novel computational techriques (computer code) thet have tren developed for thee purpose ix tcluded. While te Handbook isnot a Compre eatie on explotes, it dows disuse at length topic aess that reconsidered to be of atest value in an expostion ofthe princilen ff explosive behavior of Sigld and wold explosives, and thus proves 2 feadly rowble colecton of important teoretical and) experimental tenis on explodes and expose effects, "The Handbook dow not corer the synthesis of explosive mbstice, compilation of properties "of explodes, or the” manufacture of ‘aplosver thes opie ae the mje of exiting handbooks, ‘The Engineering Design Handbooks fll into two base categorie, those approved for tlate and al, and those elsied for security reasons, The ‘Aimy Natenel Command policy is to velese thee Engineering Design Hand. ‘Soaks to other DOD ties and thel contractors and otter Government eences in accordsce with cv-zent Army Regulation 701, dated 9 Xptember 1966, {willbe note; thatthe majority oftheee Handbooks can bereblained from the Natiotal Technical Infeusition Service (NTIS). Procedures for seqirng these Handbooks follow:‘ae 70-10 PREFACE (Cont'd) ‘Activities within AMC, DOD agence, and Government agencies other ‘than DOD thving need for the Hagdbooks should dct their requet on 4 official form to: Commanding Otficoe Letterkenny Army Depot ASIN: AMXLEATD ‘Chambersburg, Fennsyivania 17201 ‘Contactors and univenitier must forward thls requests to National Techical Information Service (Requests for clamiied dooumena mst be sat, with enpropriate “Need to Know” jstiieaion to Leiekenny Arty Depot) Comment and suggestions on tis Handbook ate welcome snd shouldbe saddened to U8 Army Materiel Command ATTN: ANCRD-TV Wabingto:,D C 20018 (DA Forms 2028 (Recomended Changew to Publications) which fare avallable through noreal publications supply channels thay be used for comente/ iggestions,) wt141 INTRODUCTORY REMARKS Explosives have been known and ued for 4 ery long time, Blase powderma mixture of potassium or sodium mitts, sulfur, and carbon Dlack—has been employed aban explosive since cient Umer, Mirogycern,elscorseed In 1616 by Sombrero, end the invention of ritogyemin-based dynamite by Nobel in 1667 fan be conadered asthe sar of the rao hgh ‘explosive echnology. This ra which extends to ‘crrent times as betn the developmen ofa ast ‘umber of miliary and commetcal explosives {hd explosive apliestions "The development ofa fundamental theory of detonation algo ad it beginning in the ater part of the 10h century, staring with the Invetigtons by. Mallard’ and L* Chatler (881) and of Derthelot and Viele (1882) on (Gucous expledons. They. found that she fxplodon proces consited of propesing trae of chemea eaction and tinged {ype of seaction waves. ‘The ft type et relatively dow. moving flame having near ' , i { \ \ 4 i : ? \ { ‘velocities on the order of 1 to 10 cm/sec, and grag Societe re mt } SSS eth ane mo te } Seca Go ht emis { Shier sugges a three aogy } Be ade sat cpanel Wirt ais itm cca enters mt ean kN ioe i sr ee Sk we ae ec ead al" Beas | i a a kta eat ee, ad tet ses SN Sat m,n {0 Seee 2 mee oes stacy ea as ee Sere eee seeming? Since nel ta ted et Ses Se Pett eee } Sa caro See fas { Se ec rman tnd ie } Ses dnc y Canaan ; sae ey rsa ee ~ CHAPTER 1 INTRODUCTION teadysale detonation This theory employe an Ideaized one-dimensional rpodel in wiih It is siumed thatthe explosion energy Instantaneouly relewed in a dicontinuou, hock front ‘sefose whi the consemation fonditiont of Rankine igoiot appl. ‘The ‘elocty of the detonation wave was sumed to be the minimum veloctty compatible with the Lydredynamic conservation equations. ‘The Chapman-Jouguet (CJ) theory thus defced a nique Weadyeite detonation velo -wbich could ‘be compared with experimentally (bsored eloitie, and dae clelations faucous detonations were shown t0 be ih ‘cellent ageemont with experiment. nthe period 19401843, Zeldovch (USSR), von Neumann (USA), and Déering (Germany), each working lndependeey, sefined the CU theory” and -exiended it to. the case where ‘chemical reasion occu in finite sone tend the front ofthe detonation wave Tis work wal stimulated by the events of World War I, which re pwe grat Impetus to the devopment of Fea of the modern highspeed electronic and photogeaphie techniques for Hudying deals of ‘xplesion phenomens "At the present me thee exits a substantia corpus of theory and experimental ata that ean ‘be Sid to provide a good deseo of many sapects of explosion processes. The theory 3, Fhowevee incomplete in many respecte inthe it eas inthe rain with Mdealzedconfiguntion ‘ot met wih in peactice snd doesnot treat ome ofthe events upon wih the performance ff an explosive depends. I wo se the esting thoory a a point Of departur, there ace many aces which can be frilly ‘explored tye ‘heortcl and expariment! investigations ‘Tn this handbook an auempe bs been made to oseibe the principles of explosive bear a ‘they arly to condensed explosives. ebay been he principal cim <> presnt a comprebensine freatment of thove topics that are necessary fr fh appreciation of the lersture reporting the fewute of irre resent. ‘The author bare Geveloped moat of the important telaons of thermodynamics ond hydrodynamics upon ‘which the thesrtea tontnent of explodion : “i | | sc 708800 Phenomena i bated. ‘The casi theory Geveloped sigorouly and in dela, since this ‘theory isthe ass both for an understanding of ‘actual explosion phenomena and for he theoreti investigations that are cunently Ia Drogess The trement of topie for which Aheory is incomplete necacarly "ore ‘qualitative and rele heavy on ducusons of experimental data and siaple physical models ‘The. techniques employed in_obianing the experimental data ue thesfore Gacuned in ome deta. Much coment serch on exploton Phenomena involves muedcal wolutions to Complex mathematic) aquatione of uid ‘dynamics, chemieal neti, thermodynamic, Inydrodynamicy and beat trnapore, For this eaon some of the nove computations techniques (computer code) which have been developed for thee purposes bave been ‘eerie. Te has not 27 Sie aim of the authors to provide colaprehenve tretee on exlonves, ‘ut rather to ducus a! length topic art which ae thought to be of pentest value fn an ‘xpottion of the principles of behavior of iq sted woidexploaes. 12 DESCRIPTION OF EXPLOSIVE PROCESSES. Explosives are substances ox mixture of fubetancer which are capable of undergoing ‘rothermlc chemical tection at extremely fast Intes to produce gueous endfor slid reaction ‘roducte at high presure and temperature. In {he cae of »t7pleal “CHINO” explosive such at TINT, the molecule—whih contains carbon, hyetogen, nitrogen, and oxyeru (ee Table 1-1) undergoes a decomposition action flowed by reduclionosiation reactions which eventually Imad. to low moleeular ‘weight "detonstion Products auch at CO, CO, HO, Nz and voli easton (cf. Chapter 8) The chemical reactions ‘ecu in microseconds with an energy eens of 5°10 alg, Por cart TNT this can result In a Setonation eave with resie, temperate, and socty ot ~ 200,000 utm,™_3000°K and ™ "7000 ‘njsc, espectely.” The large. snergy ‘ete and fant veloly ofthe detonation wave epee temendous power level of energy fonvenion, 5 X10 W pee sq om of Getonation font, This vale ean be compared with te total United States etic generating apuclly of 3 20" W. Its the high power evel an igh zeaction presure generated which fre ‘the to. the primary aplication of xplosies, namely, ta compact souree of fvergy for Blasting. Other appiatons (eg, ‘welding) flea tothe song shock wave thats ‘Groce wih the detonation font ‘Since the performance of an explotve depends stongy on its energy relene. iy ‘detonation, "considenble theoretical and fexperimenta effort bar been. cased ot 10 bredict and “to memute the energy of etonation. The” thermodynamic theory ‘developed in Chapter 2 and the dictions in (Chapter 3 rltedrety to tia bjt. ‘Observation ofa detonation wave propeing song long eylindieal charge of expoave wil ‘how that the wave moves a contant veloc, In the more energetic miltary explorer thir ‘locity may be as high as 8000 mee, Tae ‘otonation velocky is reatvly cay to mesire find for’ many. years war vtually the only ‘experimental das avaable, However, withthe SMvent sf high speed. electronic tevin ‘equiprene, sonk camera photopphy, Cash Zora, and mangas preture gages, having ime secolions of 10" se, ha bon poube to ‘meatie delonation preted as high a 400,000 stm, and patce veloccan at the detonation front. fet, Chapter 8). Unfortunatly, experimontal “tetiniques for reliable ‘meamuremcat af Zatonation tempeatire ave ota yl besa developed, ‘The constancy of the speed of detonation ean bbe “readily oxplained "in. terme of Chapmansouguet (C3) theory “and the Zaidovichven Nevroann-Déeting (2ND) model, ‘which wo deolojed in deta In Chapters 68.18 {his approseh, the detonation wave may ‘be considered as 4 tong shock wave supported by nergy relase ina. small zone of chemical feacton just behind the font of the shock, Le the detonation font, The mrt instantaneous fcomprenion and heating of the explonve it pases trough the detonation front tng the Supporting chemical reactions. ‘The table detonation velocity a dexeibed by clase Co theory represents an upper lilo deal detonation veloc, and stil refers toa Planar devonation ware Such waves ao indeed {ound to be approached in cylindcl charges oflarge dlaaeer. In practie, bower, it found that in-small dametor elidel charges the Getonalion front is curved, and i weocky ‘depends upon the degree of charge confineme’* tnd charge diameter. Aso alerved that for ‘ach explodve Der aerial valve of charge Gdameter q telow which ¢ eadyatate ‘etonation wil not propagie. For example dy 1s about 1 em for ext TNT, about 10 em for explanation of these “noniden” etonation ‘henomens relates to the effects of charge fxpanalon and intra energy lower on he ate (of chemical reaction in the detonation reaction one. “Nonidel”” detonation behavior “ie dacamed in et in Chapies 3 and 1 Tf we take a slid explosive sich a cart THT and tet a match to if wil probably bum (Genagrat) with a linea velarty of =1 ems However, i we strongly shock: the explosive i vwildlonate at 7 X10" om/ee tea io be bveved that if bumiag explosive is coofined fe maleta Thi bring up. very practical ‘questions sch a what are the condone which aoe the ination of detonation in an losing, and. why do diferent explosives, oF fren the ‘ame explodve at tfrent alk ensities, “react diteently to inating ‘imuliwe fy shock, impact, ctor, par, hee, ter The heed 4 deign relable etonation Iniation. deve and. to prevent. acidetal Inations ent ent impetus to studies devoted to charactriting the ease of inition oe senaivity of explosive rates, “There ie now substantial eridence that all detonation initition processes we esentlly ‘heal in igh, By Uh meant ha niin ‘tral simul such a shock, Impact, and space ‘ue heating of the explosive and the cretion of theraal\ expotion-sometines in amall Tocalzed regione of the explosive charg, Le, hot spots "The thermal explosion, i ft la of suticient intent, wil propagate u etageation Ando shock ware which rentualy lads the formation e's Setonation wave, The factors hich doterine whether oe not the stil ie fbifeen? to cause thenal explosion and Whether or not the thermal explosion i of tulfcentIntensty to gow to detonation re sc 708-190 very complex, inteving, chemical Kinetie, hermedyeamia, mast and heat traypor, and hydrodynamic fow. A delaled dacuaion of thermal explosion and’ it application te 1 designs te ae, tt Snr 1 = 2 designates the apeces CO, ete," compotion of the pu phase of a nixtte of ‘huny contents abe dese by he moe mumbore m= Qo hte {(mmolesgram) in tho number of moles of the Lh content fa uit weight (egy one gam) of tnt We sll ame tht any condensed Phase inthe micure in poem, Dee Ercaing cosaderaon of ali or gud huang and we dente by it andy! the amber of mole of ul td sd specie in HE weight ofthe mice The compton of {he mic i th ecibed by the numbers mjeand nd, 2 0) The phe ie Shposer teste’ onthe number of te iguanies n tad tat may be none. Ie'Sistors of pti inte mot of thee ‘titties wil be sr, 1 Thy tea ey ‘tem ihomopeneoun coating ots gape iy. "We devgate by © he number of ditfeent temic ements contained inthe diferent Species comprising the mistre and employ a Index, Aft 1,2, oops an element inde ‘Ths for exami it of element iC tay he index k= 1 designates the cement C, theindoe k= 2 deg he eiement "The grow compotion of the ays ean be ese by the uanien gh (R= 1, 2s ‘when gis the mime f ematrie nighia a the #0 slement contained fount weght of the mixure, Ifthe pos compestion of theance 708100 system of inter i desi by some othr set (Of parameters, the quantiles q) can always be obtained by simple cofsideraton of Soichiometry, and we asume that tis as been done, For extple, the TNT formule refered to In, 21s amesited wilh the vet of usb, hich can be represented by the vector g” = Gus, 81, 67, 8180 Th a ysem conning ty constituent, iis posible to select net of conatitunts which are ffclent for the complete deception of the (Gow composition. Tas i the mixture consisted Gr the edected consitonta only, the amount ‘of ach eament prewnt in the hypotheti ‘tom would be Ue same a toe inthe ayer of interent‘The coeatinent thor auflent to escie te sytem arecalled the components of ‘he ayatem. One posible st of components for the reaction produsla of INT is given in Eq. 24a. The number of components a usualy, but ‘not necewaily, equal to the amber of flementa. Por the development here In which the expleion product a well tthe explode tue expreued ar » sum of the components, he ‘example, if the ln of components tC, CO, ee, {he inde j= 1 digates the component C, te Index J= 2 designates the component CO, et. "The molecular formula ofthe £20 cowttunt or chemea species ofthe misture of explosion products canbe fomally represented by YP axD ox ox? @2) vere 2° isthe symbol of the fh element tnd, ithe mbseript (which may be 2x0) to {is efibol fn the frum of the Fh specie, or every specie he amy hy (A= 1 Bron) datineeavector 2 (Maye igs oS) (29) that canbe eal the formu vector oe th imbalance, As shown by Brinkley® it is a ‘ceaary condition forthe aection of «proper ‘et of components that the formula vector of the selected constituents be linewly Independent, which implies hat the determinant Penldoee not ani, We denote by a, (molesgrin) the numberof role ot the f2h‘component in unit weight of the hypotinetical system consisting of components ony. The gua tes ¢ U = 1,3, ) ae cal the slchiomet ie costente ofthe tram for partsla choles ‘of componen ‘For proper set of components we require at the raiciometie constant g, be greater than 2zzo for al 1 The soichiowetie comtants Incate’ the “quantity of each component ‘without reget phase; hence, they are mame of Ue mole member: anata? eo) Sts this hypothetical system is to have the same great composition whe yim of Interest then the quantity ofeach element must ‘be the same in each yates Hence Aaggrd then ane @8 ‘The 9, provide a specification of the gos competition ofthe sytem that ean dtemative to hat provided bythe gy "A cholee of components is generally not vulgue, Itt i arbtearly amumed that the ‘Ghia elrente in their wandard ates (64, Gy, o) a embers of the ape (een ‘Gough the concentrations of the elementary species may be to low as tobe negligible), the Clements constute’ w proper choice” of ‘conpenenia ‘The elements as atoms (iy in ‘Gatocited forma) sayy conse a proper st ‘of components even Gough they maybe petnt In negighle concentaions. Then @) = 9 However use a set of componente other an {he eluents is advantages if te hypothe syitzm of components & a good spproxination {o the sytem of inter, This wil be te ca if 8 ie poaible to atect ae components de predominant species ofthe mixture and if the fincentntions of the speces tare not Selected are anal enough to be negected a a rexgonabe approximation, it the nypotneson rytem of componente is an adequste representation for the mixture fealting, fom the decomposition of an ‘explosive, the equation forthe decompestion action ean be welten, om stochiometiea Seen epee nad eye tsp oats 2 a ong oho" Beapeetentmmeetcetes po dteore mice. loan nectarines eee petite sleet ‘decomposition equation of the form of Eq. 28 Some cendeee te Soham creme, Sov Sere cranes Seale ras oe ere See reas fe eeeae secant sharpener neat beste ereeuanenas fe ree fb Sees man rcemeeteTeteeaats cnet Seren, Seis cess cole ciara ses Ae ree ee Zane penta e Se are Beste ancien paste atten oreeaas ron pastor eens i ee oral as serie crate Foon feiss eee nan ate Snare ee eae aang See ee ree ata sone arin tee er nes =o ere} where, ‘componat, es) yea) = fonmula vector of the jth tthe. diroeiated elements are taken to the component = To ec of qr br er commande Sbee recton ‘arte reeoentel foal by saree com in he fomaon of ach of we Contifuents Ow niskie tea he Sonpone Tea gra che of company he retcons tte fm of Ea. 3. can swap be writen by open, singe contr lt {ex balancing chemialegiatone Toe tonne Aicanon of th parr intended nt to ‘Seay te meming of the const ace its poate fo feels « compte gran tat il contact able (mea) ae ‘Seti fy tom the cote “he conver of mu by te estos of ge Ten eprom y the matone, wham a ries, sd My (enon) am te Faso wh Sti a one Sra fak compocens mpectecy Tre SSoerten sf non efron 1 whol Saas da oats A= Say) On mbt Bae 27% ito Ba, 29 and feguating the “confficiets of Mj, there are ‘obtained Ba, +n) 10) U= 3,2, 0) Bgs 240.ae the solchiomene conditions “According to the phase rule, the numberof condensed phases is at most © + 1 (end it ‘number of condensed phases can court in feulram with x gua phase only for w uniquely ‘ecified set of slolehiometsic constania at & liquely specited temperature nd pres). ‘Wesimplty Bas. 210 by making the assumption that any condensed phase Ie « pre component wwhowe state of aggregation (solide liquid) is Known, More geweral tnreatments of heterogeneous systems present’ no special, itticulty but reult “in a. considerable famplifation of We notation reguired {or & sang oymcr 708100 rer dicanion, The stems of interest in {Bie handbook are all compatible with thie resition With thieasumption, Eqs. 2-10 ex te writen Samy ean here ni the number of moles of ondensed (told oF guid) component Jin ualt weight of the mixture ‘ttn equilibium compsition of amixtureis 6: be determined, the conatluenls to. be conderod must be chosen 0 prior. The election will usualy “imply the neglect of Certain pecan whowe concentaione st feulibrium can be expected to be negligibly ful. Tp general, the corectness ofthe choice fam ‘only by confimed posterior by Ghiculation demonstrating that the ‘concentationt of the neglected species a in fect negigble. In some spplctions, addition species may be wbitanly erchided from Celdendion even thoigh their equilbeum oncentntions muy be sipificant, provided etc considerators imply that the ate of their formation is too. aall fo be sigoieant undet the condone of tax application We tay ssrate the rtaton ofthis ection by conadering the deecmpetion products of ‘TNT. We astume ¢ prior that the products Consist of w mixture Of alld carbon with a gat hse compried of C, CD, Hy, Ny, O,, H,0, ‘H, In thin list we ave arbi neglected & numberof poulble distosaton products; they fon be included i dmited. Becaure of he Swrgen desc in the THT molecule, we expect (he mea abundant species to be C, C0, gy Nar ‘nie slot thew pods sa composed. Th Gouficlene @, of he formula vectors and of Ba. 27 ae ected in Fig. 21. The fit four rovs of dhe wray (atic) ofthe f corespond {othe Wenilter raullag fom Ue chaice of compensa. The emaning rows represent the ‘Shami reactions of Eq. 27 200-C =0o, 4H #00-C=H0 wy =H ty means of which tore constituents that sre not components ae formed fom these that ae For TNT, C,1,0,%,, ™ 4, = TMs a = 6M of = SIM a, = ay where M = 228.18 ja the molecule welgst of {INT The olution of Bas. 23 1 ay 7 Us a, = 61M: a, = 12M: a, = 9/281 23 THE LAWS OF THERMODYNAMICS ‘Thermodynamics i an exact mathematica science, based upon seal number of basi presses or postulates from which all the resale ff the scence are deduced by logical proce. ‘Applicaton of the sence to physical systems always Lavlves -lltional hypotheses separate foom the since Hel. Tea rcemry to ssue {he relevance of the mathematica mode! to the physcal system to the one towne comet of {quits employed by the science to physically tenable poperir of the system. Tt a0 every, except in al eases, to appeal ether {o experiment or to other theory to evaluate the ‘rasouefunetions required by the eppiaton of Uhormodynemies Jn thei dependence upon the Independent variables of the piysica system ‘A thermodynamic system (cle spam) cont that interacts with the sunoundingy by frshanging het and work through ls boundary, Sh bolsted este i one that dow not intact ‘th the sutoundingy, The state of mayor ie Getermined by the values of ia various properties, the nate and neceaay numberof Minh ae to be delemined, A este. Composed of « finite number of homogeneous part calle phases, For some aplication, Inay be necewary tn consier the Gite number ‘Of neahomogeneout regions forming the boundaries “between pais of homogencost Biases; for mowt cae, the elent of ich egons is small and they can be negected in ‘ccoparson to the homogentous repens. Some properten of the homogeneous pace are rearded a fundamental) Le, temperature, Interna energy, presure, entropy, and volume ‘Properties such ay intaral energy, volume and ‘entropy ar called exteave becuse thelr valies fora gen phate are proportional to the mass of the ple, Te vale ofan extensive propery of mente sytem is tho sum of the value of et, fof the constituent phases, ‘The mole elu of eonsve property ia thel fora stably defied (pam-meleclarwelght or mole of materia The {pecifievalueot an exteravepropety i thst forELEMENTS 8 sZzg SIN3RLUSNOD sre s s ‘SIN3ALUSNOD Ho ‘The Coefficients ay and fy forthe Explosion Products of TNT Figure 21,‘ance 7100 unit weight (e4, one gam of aera. We wil (enarlly employ capi letter to designate an (xteuave property for woght § of materi fwhere may” be a sully defined (Pammolecular weight, and the lowercase later Cesgntes the ae ofthe extenive property {or ut weight. A property is called intensive it fir value fort gen pha i independent ofthe nae ofthe phase, Te empertite and fissure fe such intensive properin 'A thermodynamic proces ina to have taken place if «change i beat fo have taken place In ay macroneople property of the stem. AD infinitesimal proces proces In which there in only an infinitesimal change in any actocopie property of the system, A natura Droces a an nfintsinal proves that coca fpontancounly in eal sytem) an unnatural Drocea is one that cannot eecur ppontaneculy Snr tems, Reverable procewes are citer tural or wnat processes which can occu fn either direton between two. wales of seule, "The fint law of thermodynamics for an Solute system can be sated a fellows: There felt fmcton ofthe ate ofa uniform phase called the energy which le conered for ony Drocem overall the phases porticpating Ia the Frc "Fr tintin ces he Bt Zanes ean where 5° i the enemy of the Kth pase, Note that Know rafen to the phase (coli, Tigui, oF gat), not to the element a in the preceding peragaph. Because energy li an Extenive propery, ihe enemy of the whole totems dtined by ze pet ea) ‘We shall ner limit consideration to tho ws in ‘which all of the work done on a phase ‘Produced by the pressure exerted on the phase, We ruppose that the phar Is in pressure quirium with ix suroundings in the sense {Bat I the peaure exerted by the phase on is sumoundings isp, the presste exried by the turroundings i p'* dp oe P~ dp. Under these circumstances the extemal work gerformed on the th phase i revere, equals p™ do, wa ae a bg Mav a) where 8g") ig tho heat absorbed by the en ‘hase, i the pressure of the Hh phase, and 4V" fe the different creme in volume of the phase daring the process producing the change de iB, "The cond law of thermodynamics for an Snclatd eye can be sated at follows: There texte fnetion ofthe ste of uniform phase lle the entropy Which To cnveroed foray Fevenile procem and which Inreses [or any Ureertle proces over all of the phases Dartipating tn the process. For an fies bros yas! > 0 atop here $e the entropy of the Apa, The exiy sign soles toa reversible process and fhe inequality sign #0 an imevenible one Because enzopy if an extensite property, the entropy ofthe wile system ceil BY ses" (218) ‘The statement of the ycond lay completed ty the farther sumption that re a partcuae hs prtpating in a reverse proces wm , 5a? » (221) as ean where 77 it te temperature of the uniform ek pe and 53 the Neat abgorbed by he pawe from is tacoundings In the reversible prowess producing. the change Sin 5"), Then Bq. 2-14 can be witen as = ras" - pMav (248) fox reversible proces ‘Note that tne rommation of Bas. 212 and 2-15 inover all ofthe phaser performing Work oF fcchanging beat. during the proce, and the total system devcribed by these equation is an isolated system for which the total volume iconstant and thor the boundary of wish no best dows, “a textbooks on thermodynamic, is shown hat “a general (tevense oF never) Infistesinal change in the energy 2” of & has canbe wan, a) = as — pave” x9 + wpa where Mi the total na ofthe sytem (not the (Pammoltcular weight at in he. previous Pengaoh) u(") ecaled the chemical potenti ff the 2h phase of the (0h. contituent ‘quition 219 can be shown 10 be compatible swith the first and aecond. lame of thermodynamics If ndependent vasbles other than the snltopy and volime are to be employed for 2 Darius ryan, is conveient to define new ‘itenive varus: enthalpy, Helmbolt fie ‘nergy, and. Gibbe fre energy. The new sale ‘asablee te defined interme of quanies Ueady’ introduced; they "40. not" provide ional information concering the ate, The Charctertc. function for the independent ‘ables entzopy, preeure, andthe mole Tere i called the enthlpy, denoted by Hf, td defined fora phase by w= EM phy) (220) For the independent varishles~iempertu volume, and the mole numbere—the Charclaae fincion called the Paimbelis fave energy, denoted by 5 and defined fora pha ky eB gh) (ea) For the independent varabler—temperture, presure, and. the "mole numberte ‘haractenstic Aneton i eaed the lbbe Se nergy, denoted by 0, and defined for phase yy GM =H = gm (2.08) For any infinitesimal proces of the whole rylam the extensive properties satisfy the ‘uations cr 708100 as = as! yan» pan” a sav" ar = gar! | (243) ae= a8 , a0 = pac” hen the deiitions of Boe. 220, 2-21, and 222 we diferentnted and combined with Be. 219, we oblan| a a opted aon sae av «pain } (224) dat = sets ag sa For 4 particular phase, the chemict) potential ca be defined by ty One ofthe relation he Fl “alGe) “),T- I the aysem cons of singe pure phe, ep. 19 nd 2:24 con be wan ae = Tas ~ Pav an. As + Vip ar =~ sir piv 2) do =~ sar + Vip ‘whey ts unnacemry to relan the upemcsiot Mba of tho phe. These exprewiong, for ay Infiietinal proce involving onl esi pure hae, aay the Gt aad becond: Ie a bpewed by Ba 238 ‘The variations of Bq 2.28, with Hop. 219 sed 2.24 re biry, except tht the aati Unpo must sataty the loka onatons, Bau 2-10, which we write i the ‘om, Erna = 0 ean ‘When the asurplion in ade tata proces, cars at fad compolon, thw conection: ¢ ee ee,‘ee 708100 see automalicaly satisfied since anf? = 0 229 forall and by definition. “The equilibrium conditions are the conditions under wich a process in an inoated sytammar described by Eau. 223 and 2-24, and subject 0 ‘be stleiometts consists of Eq. 227—i a revenble proce, ey sales Eqs, 212 and 248. The analyas for the cave of fsed Somposition is given in standard hermodynamict texttooks, 4, "tat of Guggenheim? The snails, when te fokhlometse conditions ate exprewed in the form of Bq, 227, has been publiced by Baie Both under constant composition constant snd under he constant exprewed by Eq. 227, the mechanied) end thenal equilibrium condition are obtained in he form Map Men where p and T are the unifonn.prewure:end femperstre, respectively, ofthe whole rem. For the gener. stoichiometric conditions cexpresed by Bg, 227, the chemical equilibrium ‘condone be obtained in the form 29) w= RBH, ea) wher the 2, sre parameter that can be ‘Siminatd between Ege 2-27 and 230. Tn the derivation of Eay. 2:99 and 2.30 tht Jha bean oulined, 2 proces occuring at ‘constant toll volume "and. constant total ‘entropy in an lated sytem wa considered ‘The mals can be extended to cases where to system. Of interest exchanges eat with ts Surroundings or perfonne work "on. it suncundings by concdting of en elated ysam onsaing of the sytem of interest suoundod by an addition phise sod separated fom iby membrane impermeable to the exchange of raalier but through whlch heat can) be transfered ot upon which work canbe performed, ot both, W the added phe forumed to beso large tha the exchange of heat, ‘sulin wnelgbechange ins prose, in the proces oecrting in the system of inferest may be at constant temperatare, or consant Bressre or bol I xn thes be shows Dat Bas. 2.29 and 2.30 ate the condiions that proceat bbe retenible when. the proce occur at constant entropy and pure, at consiant lemperstare md volume, or) at condant lempeature and. prewure’ of the system of Ilene Bqs. 2-29 and 230 ate. thus the conditions for any infinitesimal process to be a fevesble procar and they are thus the general ‘udion =: equim ‘When Bas, 2-28 and 229 are said, the system ein rrchanial and thermal ula, ‘ut is contained to conta compoaion ee stale ofpartl equilibrium toes may provide a {ood approximution to the slate ofa teansent ‘jatem If relation tne, for equllbration of fempetore and proware we dort and relazaion” tines "fo!" equiltation of Composition we long eimpared ‘0 the time Shametrsing the tangent ayaare of the fyetem, When Ej 228 and 220 are sted, Bay. 219, 225, and 2-26 can be wetter dé = Tas ~ pav aH = Tas + Vip sy) oP =~ ser'~ pav dG =~ ser + vep gs 291 ae identical with Ege. 2.26 for pure singe phate, We conclude thatthe equations for an infinitesimal proce na misturemhich ‘matnsine thermal and mechanical equilibrium (hunng the process and eo te consiated (0 Conant compoutionnare identical wih those {or singe pare phase, When Bos. 2-29 and 230 are satistied, the system ts In state of completa equim 1 ‘may provide «good approximation tothe tae of a tanslent system If rolxalon Umee for ‘ulation. of temperature, prewure, and composition ae a short compared tothe time harctersing the tanent™nalure of the ‘json, When Eqs, 220 and 290 are said, Eq, 219 and the third of Bgs, 228 can be combined to ive a5 = Tas pV + RONEN YE on” In viow of Bq, 2-27, this exprasion reduces'to ii” ae Tis pv 2.80) Simlany, Bags. 229 and 224 recall in the expreaion dH = Tas + Vip ap =~ sat'- pay} (298) dG =~ ser + Vp ay, 2.92 and 2.98 ate identi with Bg 2:8 for'a pure ingle phase. We conclude tat the ‘qations for en” infiitesinalprocea it @ ‘mleture that matntsna equllriam dura the ‘rocee are identioa! with thowe fora ingle pure Phe ‘ning Bat 229 and the extenze naire of the enthalpy snd free energy functions we ca also write Hoey PRES ean, G-H-1s {or « mixtre, These expresicns have the same {orm oth definitions gven by Bay. 220,221, snd 2-22 for asingle phe. "The energy and enhalpy ae undefined to the extent of an arbzary adive constant. The fettopy. undefined to the extest of ‘Stlora arbtary alive constant, The fee ‘neni ae tbs undetined tthe exient of a8 Sdalve constant and an ada eat function of temperature. In practice, this lick of ‘Sefwition ecemions no aifily since one it SSways concerned eth the enegy oF entony ‘tlrence between two sates and oe fiferences ae completely defined. The ck of fetniton can be removed By defining foreach conaitunt of a mike slandard tate ‘whlch energy ‘and entropy” are achiral Aeciged the aie seo. Tes not necemny that the standard late be phytialy acceubie, provided a proces: can be defied that wil produce the state of interest from the sandard Fale md for which the change in energy and ‘entropy ean be calculated, "Now suppor thatthe entropy and volume are sno functions of te Independent variables pres, temperature, andthe mole numbers, fy that the fetions represented by, ‘ater 708-180 #2, Bayon) 2 WB, Te moon) se known, The the sake of dfinitnes, we fmploy “the specific enkopy and specific Walume. If (1) the system is a sage pure pose, 1 (@) the sytem i a mixture comsenned fo coustant compotion, of if (2) the composition fof the aymem sie the eqiibrm and ‘Molchiometic conditions atall values of p end "7, we may tegurd the enizopy and volime at Impletly prscribed functions of p and T oly, nH, 0) =o, 7) andard state hasbeen define, the thi of (38) i ag. 233 end the Information summarised by gu 235 sufice to eauata the Gibbs fee fenerty at a function of peewure’ and temperature. Therefor, the ction roe) ray be roped as known, where g 4 the ipecitic “Cibbe tre energy. The other ‘hernodynanie properties ae Sin also known In parted, the specify energy cn be regarded a knowa function of prewure and temperature te exprmed by 4, T= a, 7) + TH, 1) ~ pp.7) (286) ‘Simi, it may be uppowed hat the entropy and. premue are known as funcions of the independent variables volume, temperature, and em number my, Sy Tam) Pe PU Ti myyot,) Under thee eecumstances, wo may regard the atopy and prejure as inplicly presrbed functions of vand Ponty, 1) en b= 2) 1a ganda state Has been defined, the wcond ‘ot ap. 239 and the information susmaeized by Hage 257 sutiee to detomine the specific Heboliz ee energy asa funetion of volume and temperatize f= M00)aM 705300 ‘The ofher thamodynamie proper. are then tho Inown. tm particular, the specific enerey fem be rgarded'a knowa fonction of volume Sl temperature, expres by fy D- Ty — (238) Biter ofthe xpresions v=, Te msn) 39) B= Pl Tmo) represent a tation between peste, vlure, ful temperate tat i called an equation of ‘ate. Ether of the expresions FAB, Tenysoon) len FH Toyo) cn be evaluated if an equation of state and fecian thermal deta, to be specifi Itt, are ows. The infomation rummarized by Eas gs ts sometimes riled the calorie equation of state, atnough these data cannot usually be ‘xpresed in walytia form. “A fila ducuation rene ifthe pac (4p) sud "(gu). arecomidered a Independent ‘lable. The energy Is snot naturally, fom & purely thermodynamic standpoint, considered & ‘alae of the later pale However, except ina ‘pprosimation to be noted Tater, equation of ‘fate and thermal dna ae aways presented in {he forms summasized by Bas. 288 nd 240 40 that te energy, repuded a function of entropy tnd volume, determin parsmetealy by Ba. 238 orby bys 296 and 257, ‘We conse thatthe thermodynamic state of ‘system isuniquly determined by the values of fo independent properties ofthe rystem (state ‘varaies) ifthe lavs of Shemmodynamicy an fquation of slate, and the thermal date Hummarized by "one of “Bgs. 240 are Simultmeously sated and it the system, fonds of single pure phase, a. mixture fonstained {0 ‘constant competion, or a mixture whose compedtion satstos the ‘Solchamete and equlrium vonditions at all ‘ales of the Independent state variable. The Sate of a stom is uniquely spelt’ Ih this tray from purely themmodynamie considerations Under no oer erumstanees, 24 GENERAL THERMODYNAMIC IDENTITIES To delamine the thermodynamic properties (such at energy, presue,eathay, temper, specie hea, es) of am ata aya, ie eesary to. define or to delrmine Ils emportion. It In also necessary to ow the equation of tate of Vie gaseous mixture and the ‘junlon of si of enh have prevent. Then {Be thermodynamic properties re determined by the general cations to bo summaizd inthis paragraph. ‘These restons are desrbed by ara Jevietives of thermodynamic quantiten ‘To detemine’ the properties. toemstves, the ecivatves. must be. integated long some thermodynamic path, Beamples of uch integrated exprasions are presented in Appendix A ‘The gener thermodynamic rations axe erved fora heterogeneous mixture. int the ‘aril derivatives of volume ‘with rpecs to fempentare and prewar, Te derived ad then the Gervaves Of prenre wis ropect 20 volume and. temperature are" derived Then fpecitis heat, and derivatives of entopy, ‘ergy, enthalpy, and chemical potential ro onaided, Finely the adabete exponent and ‘he sound speeds re derived. ‘The equation of sate of x beterqentces mixture is contricled fom the po“? tltions for each of the content pass, making ase of the fact that the volume ofa mixtae i he ‘im of the volumes of fs eacttuent phase. We trl lev denote the specif volume. of = Tat, Vj the molar volume’ of the f0h fendensed component, and the volume ofthe fps phase for unit weight of mixture, For a Fomoqeneots ryrem contting of «ua phase only, 7. Tn gener, we consider any ince we have rected our discusion to bnfctunesIn which v9 condensed phase cores tg pure component” ‘The eqiation of rate of « yure condensed plas isan expen ging Wir yw vere Bay, (42) ‘The dependence ofthe molar volume ofa purecondensed phase on pressure and temperature is Tualy’ determined for ech subtanes by fexpetinnial measurements and tne data have been represented bya. varity of empital equations Without such data, tho molar vlume oft pre condensed component maybe egatded-as an approsimatina conan, and st tempentura and proures fr removed fom frdiary values tuted as en adjustable parameter "he equation of wate of «gas phate may be an cexprion giving FHP, Tino) 49) Later we consider the case where presur i a ‘ineion ofr, T, and the ws. The paral molar ‘olume ofthe (th meeous constituent defined ” fc i) ean fn get Use tonanon of the form Uf, mim, in lextbooks on thermodynamic, ie ‘own that ed easy ‘enon, Ba 2-41 cane wren orm py eat vies te eqeion of ate of he gpa TOR TEapcte nd peau nepal iicive "ie lems pet temperate and prowufe and at constant ‘compention are where the subscript m1 means that he ‘Etirenstion i fo be performed at constant composition. qui paral derivatives of the volume’ with rerpect to temperature and Dpresure are mated othe derivates at constant composition by ean Oe) Gh), ne, - of whore the oqulbrium nature ofthe deities Indicated by omiting the subset. The dkiatvs of te mole number wil rapt Io fenpemtare and preure ae fo be determi from the “varlaion of the equiriom composition with tempersture and presure. ‘Thee explicit eraluaion is escebed in ‘Appendix B “Alteratively, the equation of state ofa gus fase may be an expieon ging Bm ple, Tomson) 49) 1 the system consis only of «gs phate, 10 {hat 't the nant of tha egal, paral derivatives of prewure with rept {0 Temperature and mixture volume. is stalghtforward. Tels convenient to define i mB) om (1 not a patil molar quantity. From the ‘einary rues of difrentaton, we obtain the ‘elton, (: @). + 2np, eS) The devvatives of the mole murbors with respec to temperate nd gat volume ar {0 be Setormined from the vation of the ‘equlibrum composition for changes tn these ‘lable, Tf the mixture heterogeneous, the ‘aprosions for the partial derivatives of the resurewith respect to temperature ant Fintute volumes of an awkward form because fof the mixed character ofthe eguations of stats, ‘To craunte thom, wo fist emaluale the auntie esy ancr 78-10 @[email protected]@).> | (OL G), ag, 252 a ablaned by diferetition of Bq. 241. ‘Then the ‘xed compouion partial etvaves of the: preaure. with respect to enperture and. miime. volume en be obtained rom identi, (282) (280) #.-G.-@.(0. SWentiies of Bas. 284, yt for the cuilteium derivatives by the amination of the hvedpt, "A weondary thermodyname property is the beat capacity. Ifa system ie heated from temperature To 7 dP, the hat absorbed by unit weight of to wystem evidently proportion toa iq = at wher cis the heat capacity pat unit weight. 1 the change taking place Inthe heating procs ave reverse, wo may employ Eqs. 26, 217, tnd the soon ot Bas 2-28 to wrte Bee Bbq ' = Te = cd wher iste spectc entropy. If te volume is Tad consant dusing the heaing proces, the an quantity ¢ i alld the spect heat capacity a fonrant volume and denoted by ey I ihe Dresser Deld constant durog thé eal proces, th constant cial te serif beat ‘teonsantpresure and denoted by 6 (255) It in dition to presare of volume the composition is asumed to remala Ted during ‘he eating process, the hat capcitis are cll ‘the heat ctpociiee for coatant composition, or ‘more shortly, the "frozen" hea eapaces. They fa bedenoted by 6, otc, gs Were ‘The exprewions for spec meny ¢ and specie enapy (fom Bas. 220) can be swan de = cd pdb dh = cd + dp valid ether for 2 change between equlibsium tater of for & change at constant composition. Te fellows that alternate definitions for the beat ‘capaci ae gen bythe expreions ‘To eraluue the fhowtn est capacity at content volume fo a elerogencous system, me Introduce the abeeriation oe a @. ss) and employ the identityEapresions for the quantiles ¢,,, and (efee)p ze given 8 Appendis Ry and txpreis for the derivatives of the mixture ‘lume are ven by Bs 2-52 "To calculate the equim heat capacity at constant yolume fora heterogeneous yim, we ploy the quantity ep, @) where we ave Introduce th abbreviation and where B; the molar energy of the $¢h ‘condeneed colsponent. The quantity, is not ‘alee qantly, An expression ‘or Bi {Gren in Appendix A. Then c, can be obaied from the identity of Bq, 298, written for the ‘eullteam derivatives by dhe cimination of the heer "An expression connecting. the froten and ‘quite hevt capacities at constant presse ‘an be ween in the form (280) eon) where He the partial molar enthalpy ofthe ith ‘pieour conatient we) om sand where isthe mola enthalpy of he Ht Condensed component. Bxpresions for he, tod fae gen in Append A We ill have oceaton to employ the feed compasiion purial. desvatnes of several fBermedynamic functions with respect to temperature and prewure or with respect to ‘empeatare and veume. They ean all ely be ‘blaned from the definione of the functons snd the thermody namics ls by appietion of ‘he rules for partial differentiation. For yurpocet of reference, we Tat cetain of thee reatlons ‘without derivation. ‘The derivatives of entopy ‘wth respect to premite and volume at constant temperate ae G.. ‘The deivatives of energy and enthalpy with respect to volume and prewar, eapecively, ab Constant temperature are @.- 8.» a Wire” 1 aon, 280 By 264 and 265 complement Bas. 286 and 251. The patil. derivative of the chemical pote of the Fh gaeous constuest can be Gi. (288) Similar eatons spp to the chemical poténtia ‘ofa pure condensed phase, f oF 5 I eanDetivations of dheye relations can be found in ‘hernodyeamis textbook, ‘A retion between the fced composition heat capacity at eonwtant prewure and. thet at ‘ongant volume canbe obtained in either ofthe ‘equivalent forms | the fiat of which ie convenient for the Independent varabat snd T, andthe cond of whichis convenient for ‘the ndependent i ‘ries p ant T. Tt can be shown that an fxpretion of the same form comects the ‘aula heat copactes . (269) (a 70 siete ecu date of pee or ‘olume ae cmployed in" ealuting the "eAthand eof te equator. “Toe no of the heat cpuely 1 conmant peau tht a conan tole on oe Utne freer the Bowen tet capaci ot | forthe equltrim heat capacities, We dei | te gualle 70) : 17 Galen Using Bas. 268 and 268, we obtain the follwing Useful relations: ze). EtG. lan 2618), + G16) ‘The adibatic exponent is defined by 2 iu) em ‘This exponent is se to deserbe the adiabatic expansion of gua. For detonation products bata value of approximately 2, and for perect pees, BY we of the thermodyname Meni Ge. P “7, 2@)--~Q)@), o IE Ege 2:78 and 2.74 ee combined with Bae 2:71, we oblain the ofl expretont 65 @, G7, “10-20, “30 le (a8) rene ind o. (2) 2 w-Q am nn were 6 = Uo isthe deny of the maeture. A Fixed compotion ge froze sound velocity &, can betimay defined by‘ ‘ { a. @ supe em Ege 275 can be combined with the definition of the sound. veloty to oblain seh fxpreaons relating this quantity. to the ‘erivaiee of the oa ‘thereto Phywically, the frozen sound vaoclty comeponds tothe yeloclty of propagation of found. waves in Unt attained igh ‘Roqueney and the equllbriam sound velocity comreyponds to. the propagation velocity of found waver in ‘limit alianed at low frequency. “A differential coetticient which is ‘complementary to the adiabatic exponent ard whichis wel in nalysw where volume and nopy are ken as independest variables can be dotted foran equbrium system by -2(2) co) ’ 70) com) fnd_for_ system comimnned to fixed ‘compaition by ‘These quantities are related to derivatives ofthe tquaton of tate by eon) It ie vometimen wef to regard the energy as # function of preaure aad volume, with the pata derivatives ae) oe (hoe wich define the suefticent iy fora gt roped to Sed compotion. and” the ‘Soefilent 2 for'an equim ‘vem. The eneponiing cates of the energy Mth oper tothe peur re @) 2, )-2 eso Man | Beh, ‘The coetcints Nf, dnd ae not independent, ‘bu are related hy the expression fe) ow ‘An analogous relation ‘exsti between the comeaponding coeticents for a system of fced ‘companion Tntegated explosion for the thermodynamic properties of gu mixture, of condensed Put, and of x composite heterogeneous rate. fe dived in Appendix A. These expreaiont (Ste the property of intarat asthe sm of two ferme: the fit i the value foray eal watem fu the second if the contribution aang from the sonidenl nate of De ack eystem, Terme fof the second type involved integals of the ‘uation of slate. In Appendix D, we it the ga Imperfection contibutons tothe wri ‘thermodynamic popert as eahuted. for several equations of sate that have been employed to describe propertion of the ‘explosion product of expleives. Tes been noted thatthe equim misture is oten employed to reprevent the composition of real mixtures of explosion products, The ‘composition of this minture is determined by Se thhlonsse eons, Bae B10 e087 || | | ‘cr 708180 the chemieat equlibriam conditions, Eqs. 2.30. Because gg. 210 are linear in’ te. mole numbers, while Bay 2-00 are linear in the Togastime ot the Imole number, an iterative ‘roordure must be employed fo determine the ‘eullelm mixture. A genera method to solve tBese algebraic equations is formulated. in “Appendit B This method can be erployed as ie tals fora compute progam of very broad splieaton, but i not well adapted for hand falclaiont. In Appendic C, theres prosented'a flnplifled method of computation for systems Containing compounds of carbon, hydiogen, foxy, sod citiogen in which, withthe Sema nature of the aysim specie 1 powuble to achieve x pari epartion of the Yarables and thus to simplify markedly the ‘omputatonal proces, 25 APPROXIMAT:ONS FOR THE THERMODYNAMIC. POPERTIES ON AN ISENTROPE. 1 poate to pefonn an exect ealcustion of al of te properties of the system, provided that the equations of sate exit forthe various pases comprising te system, This calculation, however, ivolier lage number of succeive ‘umerical steps, and the dependence of = property such arth energy onthe independent Slate variables such atengopy aid volume, Le ‘the fnetion efi blaned imply and not szalytealy. For some theoretical inveatgations, {ere it & need “for approximate. analytical ‘xpreaone of sch factions. or an ideal a of constant compoutin, the sdabaic exponent defined by Bg, 274 neu fo the mio of te heat capacity af conrant retro to that at constant rhume, k= 7. The {her ropertes nan idel paar frequently rpreimitad with sufficient ccumey by the SStumption Liat is constant. Such gue ik called ‘an ideal. polyiropic gus. ‘The ‘hermodynamic properties of such gues ean be fxd in atitely simple form and the ‘pproximation hasbeen extnsvly employe in the development of the. hydrodynamics of comprenible Mus such a alr for which at Moderate temperstres and provures the plyttopc assumption is «good approximation. "For the products of condensed explosives ‘na been" experimentally found that the adiabatic exponent. 7 toa good fpproximation, independent of th density aed ‘function of entropy only fora considerable ange of preaure Iesceme proper to davgnate st {\nonides!polytopie gas any gt for wish xis Contant onan aontope. the adabaic exponent js a function of entropy only, Bg. 272 ean be integrated slong path of condantentopy wit the result part =a" a8) where p "2/0 i the density and A = A() is function of enizopy en. Bq. 2-85 can ho be cexpreted in he form mie!) = pieh) = ple’) (288) were p’& pu!) and =) Brom Bq 2:22, (eto), =p Using Ba. 2-86 and iteratin longa'pah of eonsant entropy, we obtain fayette 2S ‘where B = Bf) ea funtion of entropy ely. Bg, 287 car also be exprewed in the form 1 eres iq- pe) 289 yore) 8) where 2! = ef). The enthalpy he + po is ren by ne(*) won a) on (pu = pi’) Hed rast wher W' = hips’, By using Bq. 26, the sound tloaty canbe inttoduced into Eat. 287 and 2.90 with the ret 9 apo xe = Ye = B) = (= yh = B) (20) 26 HYDRODYNAMICS OF REACTING CONTINUA ‘The fundamental ditferentid equations of smotion for rusting fide deivod in is perngrph, For one-dimendons! problnas they ‘ge simpliied tothe usa ‘Bullen and Lagrangian equations. In pr. 27 the ethod of rymer 708-10, charctttcs is appli to the one imexslonal "The tretment of ahock waves at lei en i pr. 28. Tn the mecrowopie deciption of « physical tyslam, the information oncering he wate {pe insant of time may be considered adequate fone can oblan fornia resonable o Xe chemical spctions ate revomble, the totropy centaied in an lament of 5d hanger io accor with Eq. 2103 onsegeence of the entropy inerese Suing 90 Ineverbe proce "heady flow i etineé a one in which al ot te pil dete uh pect Yo trea ero"A flow it eld siblop snl, ot ‘peconi a's point an w= LT ee than, ‘gil to, or gesier than the veloc of sand ¢ that pln nthe pariulse coordinate eer, bei we Si 2.109 are to be sled abc to iit snd ound conden and to &spectestion of the ate of te fd, 1, aowtege tthe fineton 1 eB nl Ital ofthe proces occuring are renee 80 thatthe energy trang equton canbe replaced by the enttony ianportequlien pened by Pi, 2108, then the sate ofthe fem sls Sty spelled the Cancion P= pl.)mcr 708100 le known, Under thi ctoumstancey gr 2108 an alto be expressed in the form 2(B)rov-t=0 @ ay 2.Qj0-0 — } oun a. a hie ces deine of ny the peas Talpae vc "Bge 2109, and thir altemative forms are calied the Eulerian font of hydrodynamics. When supplementad—at Drovoualy meativaed by ita and boundary onditions and by m equation of at, they can in'prneple be sohed to dotemine pp, and regarded as funtices of poston ad tine. The Inia conditions east of «knowledge of thee ‘uantiie as finctone of podiion a ome tne Sthich i taken at the tal instant. Boundary Conditont are ef two. types, kinematical (Gelocy and diplcement conditions) and ‘hyaieal(prewure) A Kinemalial condition is the requirement ea! the components of velocity rota to at interface be oqual 7 bol sides of {he interac. A pica condinn Ut must be fale by an rvs id in contact with fied boundary ir that the prenure shall be forma to the boundary. In te case of two Trwield uid presenting face of separation the phyticalcondilon tobe atid ie hat the Dresue shall be continuous atthe boundary in using trom one wide tothe other. The wurice parting two fide or the sume Ald at (Giferent denier called contact wrtace ‘The equations of hydrodynamics comprise « sytem of paral differential equations ofthe fet order that are quusinen, ie the paral derivatives appear ines, Formal aolatios of thene equations eas be obialned ely In special "Ar a example, the Eulegan equations of Inydrodynamir for nondusipave audt = 0) ‘ow canbe welten for motion a ona dmession ibctoe ar () (8) 20 gq a }(2-113) a, 208 B5G)-° where a ie the partite velocity inthe Z-direction, ‘The "Eulerian equations for ‘onecimensional adil flow with sphecal ‘simucley oan be writen So Bee #208) «0 a lad where u is now the partie velocity in the “Bretion ofthe all coordinate. ‘There ie anolber mode of expremion of the fundamental equations called the Kagangan form. The label coordiaten of a point my consist of ia pedtion coordinate or Bulan ‘Soordinata a te inal inant of time, Ths a Doral derivative with respect to time at ‘onaant luca of the label coordinates as he “ame meaning Whe operator dat in Buledan coordinates, and (2334) a8 ane wheres the poston vector of «point at tine E'The Lapangan representation i especialy Sef for" protens in which intety-e and oundares must be preserved andin which high Brecon in the conservalion of ass and fmomentim ie deized. Lagangan ie general fepaior to” Eulerian for vonedinentena Problems ‘but not neceaaily fortwo" Ot Tree dimension! protinns, ’As an example ofthe Lagrange representation, we may consider the eae of plane ow inane Smenson and let the label cooedinae of 8 particle x, to be the value of lt poston (Gslorian “coordinate + ct f= 0. The paicle ‘locity a given by x= @ei00,, (en8) “Th for taken by the equation of continu in Lageanglan coordinates ir mest easly doduced for the patticlar ill crcumstances of the ‘id. Suppee Lat the Mud ie italy uniferm ‘wth constant density p,. The conseration of ‘hasan be exprewed By = filte an»where x,t isthe Bulevian coordinates time ot the pint whose Bulan coordinate at =O sas x, snd 30.) i the Bulan coordinate of {he pSln tal was on x plane throug the oiin at f= 0, Differentiating this expreasion with repect to #, at constant f, we oblain the Lagangan, efuation of continuity for plane ‘No of eal uiform fd Sn the form ‘The Lagangan equation of motion for he same ‘id in plane flow can be btaized from the second of Bas, 23 by the use of Bas, 2138 snd 2117, We obi 3) ER) + For ondisipatve flow, the entopy transport ‘egalion hatte forme Gil,-° ‘The Lagangan form enviage the pouty of taining n deciption ofthe properties of the’ fiom, iniading the Bulan coordinates, at onctiont ofthe time and the Ibe coordina. ean) ens) 27 UNIFORMLY ISENTROPIC FLOW IN (ONE DIMENSION formal. solution i pomible. ‘The flow Considered tote in one drctonegy the {rdeclion—which mee thatthe properties of the flow ae functions of the s-coordinate ely tnd independent of the y- and zscoorinaen in ‘ectangulis coordinate system. Whenever there isa portion of the xt plone in which all the ‘alti ison the same aenteope te, when the material is ‘uniformly isentropic. or omentopioit Sr posible 10 taneorm the fdimental equations ef par, 26 to another form that ede to Riemann. For nondiipaie flow as described by the nto teanapor: eqallon In the form of Ea 1210 the prossure and the sound vlelty vary within th flow a funtion of the density only. tin “han convenient to Introduce the quantity ct 70800 o=feme (itn, =e ste te tn pb fant Se tee tase are Enter tease a leraeasle sore eee sealer een Seed ete! ess ieee Eo) -)-e Bi) -sQQ-0 SG)» eee ae eee (ono) eam 7 er Ae Reg} -o | which is die to Riemann, The fom of Ege 2-122 "suggosta the -dfinition of three chanclertie drectons-tbeled Cy, C., and (C.nby the definitions sure 223) a gif an [A charectoritie curve In the plane i eine ‘cme tat ie tangent at every point to ‘harnteitie dieton, Ths, Bas 2-123 ae the ‘equations for the charsteiis curves. The chatacters Care evidenly the parce }‘ance T0100 pitht a the 1 plane. Wh thee defiitions ‘Bg. 2-122 can be Interpreted a tating that en ‘hamctrite cates Cy Fex+usconmmnt (240) on characte curves. F=o-u=conmant (2428) hile on te particle pate C,, the entopy is onstant. The entropy “anspott equation state ‘at ifthe entropy i intly constant, it wil remain constant for flow without ducontinuites lovarante If they are known at given PO, thenit and ore known there, Lt, on Gene un Go rom thee, the dens an be obtaned from 2g, 7-120 ad the pressure fom the equation of state For matedale with s constant aie ‘exponent, devribed in pa. 0 = Belle ~ 1) ‘An expecially simple cue cecum for "3, since (2328) Qs mackie aia wens oo war (aan) ee Cae Since 7 constant song sues Cy md Fi feria ong ines bn 227 can be ‘that the charastertc curve of each ind aro ‘eight lie for = 3.'Tis cae i of paca! Interet.beeause the explosion prodicts for condensed explosives have an adlabtic ‘exponent thar neat the value 3) and, ‘onaequenly, flows for wh k= prent the ‘alate feature of tha lows ofeach gue. Tn genera, the characteristic carves have the following useful properties (1) Theres acure of ach type rough erry point on the ple (2) If curves of «given type having different values of the inarlantwsoelated with thst Spe Intenect at a point, te flow cannot remain fontinaous because” diferent values of the ‘pendent vatables woald ‘be obtained If ene charters of the other were used in ‘compulation. Thus, ther wil be dicontinulty Ins pote. at that point. (3). 1 in gven reon, Fhay the same vale along sajacent C_ cures, the Cy curves are Sieaigh Unes in Bat mpi. Por Fis constant Mong. C, cure which wil ero the Ccstver find 7 i ao conaact slong the C, cores, oth u and o, therfore w and, and therefore the ope of the Cy cues must be constant (4) Simbins, if F har the ame value ong adjacent, ‘haves in given regon, the C cures are seit ins i ha eon (8) A weak dscootinity (nota shock), Le a dacontinuty ina decvative of x ftncion Without a change in the function itll is ‘ropepted int the flow from a boundary along ‘chaneteratie curve It both the density andthe partie velocity se gown along 4 line in the 4 plane, then 7 fd ¥ and the two chancleiatic dectons can ‘be casalted foreach point along te ine, Such ‘ine may be the saz, ip Which we the Information on he ine desceibes the ntl tate ‘of the Mui. Information may alto be giver arto fone ex mote properite of the fow along fiona path in he xt plane. Por example, uh ofa platon ney be precribed along which the velocity uk hnown, Sime, the ath of shock wave may be gen along whieh, we bal seo, the denaty and pace elect tre known, Tei necesay to conser bef the niunt of ill and boundary information that fui, fom which the propagalon Squitiont—Bqs. "2-124, 2126, and 2af-uniguely delerine the fw, point {allowing + gen cure la the ef lane moves superonieally with rapet to the local flow, ae lesiarul>e then the cue called spacelies if such a point ‘mover sulwonzally wit repost fo the lca ow ie ldeidt = ul ce hen it 6 ead mel, and if uch w point QO© > er 70-100 ‘morse sonically with respect to the local flow, a leat - ul= 6 then the curve is charset. In gener the ‘characteristic curves are not perpendicular io the fdrection of flow. Therein, therfore, downzeam direction on the charsctriatic faves of such type. Ifa etal alu curve it fpacelit, Hees outide te eon between the (Arections ofthe two characteristic curves;iitie timelike, i He inde the region between We ‘dzecons of the characte curve, TC an {nial ave curve colneder with nchamctriati, ‘point moring along the curve moves with Fepect to the load Bow with the wlosly of finde geidtl =e ‘Tee azine spt. The path of & pion ‘moving sibeonelly “ith sapoct tothe Local ‘ow i timalt, TE the values of the dependent variables u and © (or Fad are changed a «particular point, {his change can only affect the properties ofthe Tow inva repion of Lefuence of Bat pols, ‘which iy the angula: region ‘between the Character though the point. The region cf Infuens- of polt P is teetabed i Fg. 22. Now, consider the ace AB of «space in ™ ‘| alus-cure, a8 shown in Fig, 23, 1 vient {hat point inthe x plane yng ouside ofthe region encloved by the Cy charasteritie through ‘Bethe Cy haractarintic through 2 and the ae 4B we wraffecied by the values of the “dependent triable on the are AB. The ron ‘hos eneloned it called the domain of dependence of the spceive we AB since this region contains all of the flow determined by {he ven fia vases. on AB, Including the end poles, then the How iv unique and eontinuous fm the domain of ependance, including i ‘boundaries Ifthe are AB on «tlle curve, ‘second iiemectig curve-which may be eee Soother fimelike “cure or a. chvacerlie (tenis required, we abown In Fig. 24, to bain a downstream domain of dependence. It a be shown that only one dependent variable ‘must be specified on ech such fiwike oF ‘haraclaic curve (both being known a > {ntemeetion) to obtains unique low in the domain of independence Th earla flows, the Ineariant «ia constant over a cerain opin. The C, chancieatic ‘ures are then slg ines, at as alent been ‘mentioned. Flows. of tha lype. are ced Drogreive nla waver. Asan example of is type of How, consider the cue of an ininite EGON OF Figwe 22, Region of Inftuence of «Point Ppcr 706190 tube closed at one end by a piston iniilly st characte incre in moving backward into rest, At the intial instant of time, the material the flow and the C_chanctersties are curved. If Inthe cylinder is at ret with w= = 0 (tbe: th piston paths pecied, an analytic solution lower sit of Intogation of Eq, 2120 ls here of the flow equate easly constucted, Now taken to be p,, the denity ofthe undisturbed suppose thatthe acceleration of the piston malrial). Thi, on the spacelike x-axis, 7= f= cess and its (backward) velocity betomee 0. Therefore, bot i ‘ofchemetertccurver conan, The charscarutien of both typer fignaing oo the sas are aight lines. The originating on the part of the piston pal are CCaenareleates through polnte on the -ari+ then stmight ines, The ow in thes pene that cover the whole 2 plane since the tube is consis of thre regions: tuppoied tab infisiely Tong, Therefore, £2 =" /3) The inital undalubed region of tiform Oven the waxy, F= 0, s= 0, and 7 = 2 danaty and zero pattie velocity between the everywhere, andthe Cy chaaceritcs are sais and theC, character labeled Ain Fig fteight line everywhere. Suppove at shown 25. Fig. 25, that the platon begin to more the (2) The simple wme generated by the negative -dietion atthe ial invant of time accelerating pton in he region batween hs Cy ‘hus inating a eartaction wave moving Gown characteris labeled A nd 8. ‘the tube in the positive divection. The particle (3) The fina tate i the gion to the left of ‘eocty onthe piston thitequal othepiston the Cy charscerutie labeled 2 of uniform ‘eloeiy and-ris known on this path. Since the dent’ and particle velocity necommodaed to (Cy characteris are sightlines,theic ope the paton vloelty constant. Since 7 & chonging from one C, Te wil be noticed that the front, of, the ‘harictetie 20 to another, the slopes of tie Cy rarefaction wave propagles withthe velcly of — Figure 29, Domatn of Dependence of Are AB of e Spcelte Iii! Value Cree | t | j 1‘und inthe unditutbed medium while the rear (Of the wave propagates with the velocity of Sound inthe final medium of reduced dest lus the (negative) parte velocity inthe fa ‘medium, “Therefore, the rarefaction ware brondens agit pases down the tube, and no rong dacontnulien cons, I the piston a been btantancouly scclerated 10 le final ‘loalty al of the Cy characteristic in Uh wave Tegion would have emerged from the point at ‘which the piston motion bogan. Sich x wave it ‘Alled wcenteedvinple wave ‘Now, & cinta to the flow jt diraued, suppore thatthe dietion ofthe aton iin the Dontive sediection, at shown in ig. 26 [tating progrenive compression wave, The Felling flow remains simple wave Wit T= 0 everywhere and, consequenlly, wilh Cy ‘characteristics Get are straight line In this eae, however, the C, characteristics originating on the pit path do nat diverge but converte, and ‘Ac? 708190 they must in consaquenceinteest. has boen ote thatthe flow eanpot remain continuous fo characterises of the same type overtake tach ote, for different values of she low ‘araler ‘obtain on ease of the intenecting charles. The duconnuty that appar 4 propeuive compremion wave a called e shock tueve and, in any ach compreson wre, shock ‘wares form inthe body” of the Mui. The Doundary between a region where characteris of the sae type intect and one where they fd not man envelope of these characteisticn, Intemecting characteristics of the sume type ing. phytcaly imyomible, the shock wave bogie atthe fit pout of Ut envelope, the Pilon is Ineantanerasly sccserated to tome {ina faite velocity. the envelope begins 08 the ston path It can be conehded that compreuion wave) of ‘lle empl cannot propaga wires! the {ermation of shock waver, Each Of the Oo * Figure 24, Domain of Dependence of Are AB of a Tnalke Intl Value Curse and Are BC of @ Tielke or Charteritic Init Value Carve 28Oo oO ay wonionfany ating © ung ariang bio png worm“) somanoRIIND IBIAS. “oe AT ace 706300I | | | { | | | ! { | { i nce 708400 haracteitic curve pasting trough a potnt ‘omerponds io + sound wave, Te one 8 forwardimoviog ave andthe oir {0 Stckwerd moving wave. The Intersection of two Gy, characte corresponds physically to the ofertaking of one Zorvard:moving wound wave by a ater one with higher velocity. When later found waves overtake atic one, Sere ist ‘Mowpening of ware profes nth continuities fof the dependent quantities velocity, presi, tnd density are formed, That auch fincontnuter should form in the case of omprenion was supported by an sceleraing Dikton i apparent inthe fact thatthe sound Felocity ik grater in the compremed, ‘labatcay heated rodim resulting fom the ‘ton mation than in te undisturbed medium. "The one-dimensional unsteady flow equations ‘ha have been dacused in this paragaph ae an Smullaneous Tint order para differential uations for which two el characteristic icections can be defined and which, for that fenton, are sid to form hypetoll stem. TC fhe equations are Lear, 2 in the example of ‘his paragraph they ze aid c be reduce, The equations for tro-dimendona)saady, notion, uniformly Isotope ow form ‘ich a eddie hyperbole ays. The theory ‘ot hyperbole system of equations i eated in (ealty Courant and Feeds 28 CONSERVATION CONDITIONS Av A DISCONTINUITY. THE HUGONIOT EQUATION: A shock wave cont of «very thin region in viich te properties of Ue undisturbed medium tery rapidly become thooe of the docked roedium. ‘The ructure of this region i determined by th vconty of the need and IP affected by the iroventie proces of Seat fonduetion along the very steep fempertire PATH UNFORM STATE ‘Ragurs26. Intorsecting Straight Chemeterites Cy During ‘Compresion Weve982 708180 tpadiont exiting inthe tanition region. Inthe ti ‘Apart from the dconinity, the flow can be Gemeribed by the atferen. equations fr fonlnaous flow described ip par. 26, A more ‘complete Gacumian of shock waves given by Flee MecQuoen, and Wakh"* We considera tock wave propagating in one ddmension in tho dizvion of norening valu of the cooedinate x, and we dnote is weocity ‘vith rape tothe undisturbed material by U. Exploying the notation exemplified in Fig. 27, ‘we fix the ceign of the coordi in the Toving shock wie and denote the veloaty of {Undsbed material and whocked material wth ‘apect 10 thir origin and in the dzection of incre + by Wy and w,, eapectvly. 1, fivd uy ate the coteaponding velocities relative {oa fed coordinate system, mea emo w 0 (2128) ‘The undisturbed medion is at pressure 2,» nay on, aid bas aptiic energy and he Shocked fader i at pressure 7, density 2, aa as apc ene, fir amolit of mass «9,88 brought up tora unit an of the” moving lscontinuty from the eight and an acount of tase 9,10, de emoved from writ area fo ne Tete: itn & made very amall so that layers on eller aide of the discontiulty are infinitesimal, the mates brought up on the ght ‘must equal thet removed fo Pal = Ms (2229) even if Ue not a constant. Silay, the change fh momeatum of thin alice of mater of 805 Pair per sit wen must be ‘equal 10 the ‘fant force stig on unit aea, that pub aterm 190) ven JEU Se oot a constant, Pinal, the work done on the matter in the thin sce by the {ores acting on 1 must be equal to the intense ‘enemy of the matter into io, so that a tule wa = py, = nyuy(2490 ‘even if U x ot constant Fo the iervenible proves: ste shock discontinuity, the second Taw of Warmodynamies requir: tha 4s (24s) By rearangoment, Bg. 2129 and 2130 may be ‘weitten i the form Ae, = Am (2139) 2, = B= Potty ~ 04) Ege. 9-189 are called the mechanial ‘conservation conditions When they are wed to Figure 27, Onedimenonal Shook Wave Nodpues 700190 ‘simply Ba, 2181, we obtain =H, 2-5) (eI94) Eq, 2494 was obtained by Rankine and by ‘Mugonot, and tis eal he Rankine Hugoniot uation Tt contains temmedypunic quantities ‘only. Wiis thermal ut and an equation of tate Of he materia, the quanta e, e(P,0) and 4 elpyt,) ate doteined, ahd there ‘F134 dbs a cure in the pt pane for gen ‘alues of By and oy, which isthe Lous ofall tats (py, 2) which satay the conservation condi £6 «given initial undistued sate. ‘The cute is called the Hugniot curve and its said to be centered on the pain (2, 0) ‘Shock wates ee stable, Le they. do'not break vp into vert shocks nor beeome & gradually hing "wave, if the laentroper ety the oat te ‘nen this condition i atsted, the Hugoniot curve rprevenis states which canbe reached by {shock pros from the inital tate (P.,, {ind took wave of rartaction do not exit” Te the tata of he full fern ot ob ede of the shock wave, th shock velocity and wate fon the other ade of the shock wave we Completely determined by gs. 2389 and 2194 itone addsonal quantty’ gen. The ‘sldtiona quantity ‘Tay be elther w stale ‘sible, the ahock ave veoclty of the pectile ‘locity, except tht ifthe parle velocity it (Gren as the adaitinal quantity, iba necessary fo smelly which iste downstream ade of te shock wave ‘Additional properties of the shack wave can te deduced drecty from Bau. 2138. Since p, > yy letllows that wo, > i, sy tae the HOW ik ‘kceleated In pani Urbugh the oc front then fllows tat p, > py, from the fst of ‘the mechanical condition It can also be ownage, by Couantand Pedra the flow velocity relative to. shock wave is fupenonie ahead of to wave and subvonic Behind it Therefore, Cy charcteritie hough {a yoit helnd «ahock wave overuke the wave nd the tock overtakes C, character head OF K Mig. 28 Wustmtes ‘the Dow in steady Plane stock wave mipported bys pion ‘ropagning into unflorm flat et. For many appiations of the shock wave conservation equations, tre undisturbed mediuch ‘Wat rst in »tationaty coordinate sytem, Por this eam, tbe mechwiea!cowervaion ‘eondiion an be writin the fom = 0-4) (2185) RR AMe In this case, the pastel velocity of the shocked ateral i bento be dreied tomar We shock font. ‘The conservation equations of hk patagaph provide relations between the dependent faiales on the two see ofthe tock Slacontnulty, In he eplns where the Sow ie continuous, it & desebed bythe dtferetial ‘uations ot pz. 26, The complete flow i ths eemined by solos of De fferentil futons that “are subject to ‘conditions ‘ecified on the shock path which 10 be ‘earded ar hed lial ale cavence rn x 2)per 7090 REFERENCES. 4, Willard ib, The Selec Paper of J Wild” Gidba, Vol. 1, Thermodynamics, Dover Publlestion, Inc, New Yotk, New York. 1961 ELA Guggenheim, Thermodynamics, An Advanced Treatment for Chem and Physciaty, Itercience Publahers, New York, 1057, R. Count and K, 0. Preis, Sperone Flow and Shock Waves, Intneience Publuher, Inc, New York, 1048. XD. Richimeyer and K. W. Morton, Difference Methods for ‘Intol Value Problems, 2nd Talton, Intenclence Publier, New York, 1987, . SR Baines, dr, "Note on the CCondons of Ege ibrium fer Systems of Mazy Congitueta, J. Chee. Phys 14, 165564, 688 (2948). 5. R. Brakes, 4, “Calculations of the autem Componion of Systeme of Many Content”, J. Chen, Phys 16, 07130 (1047). wo. a SR. Brlikey, Jt, “Computational isthods in Combarion Calculations", High Speed Aerodynamicy and et Propulsion~Couibuttion Procemer, Princeton Univ. ‘Pron, Princeton, New ders, 1986, VoL I, pp. 6497 1. 4. M. Rihardaon and'S. R. Brinkley, J, "Mechanics of Rescting Conus", High Speed Aerodynamics and’ det PropulstesCombuation “Procenes, Panceton Univ. Prax, Pesceton, New dewey, 1966, Vol Il 9p. 208.18. Witlem Bs te Mathematica" Pryic," Van Noatrws, 4, Wied bbe, Vector Any, Dover Pubilations, Ine, New York, New York, 1960, M. HL Rice, RG. McCuem, and J. M Wath, “Comprasion of Sold by stieng Shock Weve", Solid Slate Petr, Vl. 6, F. Belt and D, Tunbul, 24, Acsdenke Prom, New York, 1958,| mcr ro8-100 CHAPTER 3 ENERGY CF EXPLOSIVES 34 INTRODUCTION Explosives are subtanots that rapidly berate the" chemical ebergy at eat to form gucous ‘nd. slid decomposition products af high premure and tempenture, The hot and ery ‘dene detonation produc produce shock water in the surounding medium and upon expansion impart Kinetic ‘enerry to the suounding ‘etiam, The eergyreeued in the detonation proce andthe energy svallbe after some epee of expusion respective measure the Sblity of the explove to generte shocks and to impart motion to the environment. Consequently the energy of an explosive is 2 ‘measure of Its performance. Morover the beat telewe in the ‘detonation Jean” inpertant quantity, as will be shown, inthe hemorhyérodynamic Chapman douuet. (CJ) theory of detonation (we Chapter 6 for a ducusion of te 0 Ue), 32. HEAT OF DETONATION. In priniple, @, the eat sleued ina etonatlo, ie obtained for some standard sate by Hes la according 2. OnE a carn - Emaar, 2) where na the number of moles the th species Ot detonation products whose standard hest of formation is (Ai), and my is the number of mole of unteacied explode ofthe species ‘wow standard heat of formatin is (427 ),.1¢ the Lewis and Randall convention ix e, the [ght hand aide of Bg. $1 wuld te negative for sn exothermie stacton However, itis ‘latory to have @ postive for excthernie feuctione Thus Qn = Aivreoyen, where veer isthe right and side of Bey 8-1. Ta race‘ sume out thatthe compoutions of fhe detomtion products inthe CY tate, or at dierent degeet of expansion, we unkown. Since chenieal equlria ean be influenced by the lotal prewure of the stem, the product ‘componition and consequently @ can change as ihe prodica expand. and. the fata pressure decreases. Expansion also reals in cooing and comequent product composition change, Below Some "temperature, cham rection tates ‘become #0 alow ‘hat rther temperature and presure decrease (expansion) prodsces virally ho further change in composition, ia, the ‘composition is “fezen”, Thue any caloric ‘measurement of the hast of detonation Aig, may not be the Q forthe C¥stata, butte heat ff reaction for some expanded “frozen” fullbrium componton, ‘Mewumné ests of eaction will vary depending on. bow the calorimeter mewaremsate wie de, Le, hhow much the products are allowed to erpand ‘before the compoation is ese. Thi i probly the main reason why many confleting Yalues of Ally have been reported. Further Confusion arse ftom the fat thet smetimor Cllorimetse hsts of detonation are“comeeted™ oe the baa of vaporization of water (one of the ‘major detonation products in secondary fxploives). Ina eaorimeter measurement water fs in te ligud ate, but under detonation condtions It in the gueout ta, Tous 10 ‘biain @ trom calorimeter meseureents a heat ‘of vaporization conection should be made, but ‘nfortunataly it not almays powile to female ow much water wae pruent ender ‘Setonaton conditions even though the amount fof water formed during the reaction in the Calorimeter har been detained. 33 THERMOCHEMISTRY OF HIGH EXPLOSIVES ‘Thermochemical data snd empisial formulas {or sever explosives, explodre mixture, and Ingdients of explocive mixturs we. git in ‘Table 8-1, togeder with dat for ther mat decompottion products, These are important ‘quntites om which theretisal properties ‘explsives canbe edeulte, Thre ino oblous oration. bebwemn Al or” AM and. the “atablity” of “sentivity” of an explosive. For example, NG and FETN which are own to be "Sensive™ have large negetive AF, these compounds are thermally stable wit respect to thle comattuent snes, On th other hand TINT ‘which ule “tenitive” it most themeneatal with respect to lit elements 34 |‘ce 704180 MX and RDX which are certainly less Seanaive™ than PETN oc NG are thermally fuwable with respect to thelr eloment, Similarly" Ai's donot comlaie with Sensitivity, eg, ttyl is much more “sndtine” than “aftsomethane but (OMe )iox > (Bifgaqsr. Morena it does not becca follow ‘hat & positive Az rests in a lage Bay 86, (Bias (Alacer By’ far tho best avaiable dlerminations of AH, snd profuct compoation ave thow of metas", His rete are gen in Table 3:2. Note the exellent theneal snd marl ilnce btaingd. Certain usefl generalization can be Gea fom these deta, namely: “L Confinement incees Ally and ‘changes produc! composition in oxygen-nepive txplosten but not in oxyger-baanced explosives (see par 8.4 and Tabi 8), 2. In confined oxygen-ne cexploives, at lan packing deity, an fppresiale amount of slid eatbon jr fond Sn the product even though suflent oxen is sealable to form CO, ein HK. 3. ‘The Muerine of Taorinecontaning explosives appears ae HF in the detonation products “Condder the data of Onell (Table 3:2) for unconfined explorve, If the products for lunconined shot expand very sapaly so that the pemute becomes mc lee than Pe, at Ty, the lemperatore at which equilibria a foten, then these products should approach peetct gas Behavior aj, If we know the equilris Involved and thr idea egulliom constanis as A function of tomperatre, we ean compute Tye able 33 gee the fre energy ineton G°/R forthe impertant detonation products of CHNO® fexpindves. Prom dese data AG" /(RT)ean be obtained for aitferent empertires for the rections of interet and. del equim fenwtants computed acording fk = - agen) @2) where (Or standard tate Gibbs fee enersy Re gueconstant ete sanime tht the waters eation ce te he eps of iia nee at the eager clon the chapter Wal Be ‘ined CAND waplotee 33 ©O:+H,=CO+HmO te contig equim, To it te ea ae Fe ytehcOny se ge rane eo nD heat oes carbon ot Sipe Se a Coane ne =a x, Poo = “ es) Puyo ~£ (0-C-X) ra, EL ouiso-0+n tee Tsu unter of molt uit 5 apes 2 EAE, uttn ‘The idea equim conan fr reaction (8) © Pewee _ (C-¥) (0-C-X) *FeoaPng ~ XUUCHYC-O5%) ENT 7% Ky y For FREN with X= 2.96 comerpending to Ty, = 1600°K: eterna emai ae yn “aioe cca ‘This equilibrium mixinre matches almost exactly the compodtion found by Omelint for SSneonfined PETW (see Tele 3-2). In Table 34 we show that for Tye = 2600°K dhe computed {eal par moxttes for HMX, TNT, at well a ETN, age clomly withthe realé of Orel {or unvonfined cares. ‘Or teuctlons which must be considered at ‘igh premures (confined chars) ae 200 = C0, + Cte) 00 + Hy = HO + C8) (0)[At low total presure (unconfined charges) the ata in, Table $3 give, ~ 9X 10" and Ky 4 Xo forthe equbbrn (0) and (2) at Ty, = 1600". ‘Thur the nepot of reatlons (0) and (oat low preaure is entry” justi According to Le Chatelr's Principle, esctions (Gy and (e) wil lft to the right at hi Desi, and we should expect more COs, Hg0 find Cl) for confined. charges than | for Uinoonine charg At high prearee, the ial ‘26 laws are no longer sppicable and simple Somputations of equim compositions are to longer pourbe widiout the appropiate PVT ‘uation of wate forthe products, Ome has tmade computations foe CJ enteope omposilons st 1600°K and st 1800"IC using ‘the Becker Kisiakowaky-Wion "(BKW) and eanarédones Devonstize (LID) equations of fate for the products Agreement between ‘bearved and computed produet compositions ix ‘gle good. Ths suggest thet, for eontined Charger i betwoon' 1500" end 1800°K in Sgrtment with Ty, = 1600°K for unconfined charges, "AS high promures and temperatures of the ‘ordee of 1600" to 2000°K the actions Ny +38 = 28H, (@) fy) + 2 =cH,—(e) ‘acono lier nagible the equiitxium mitre (Getore condaering rections (2) and (e)) fontaine appreciable H, Bqulliba (a) through (6) account forall the observed products (Table 532) withthe exception of very minor amounts ‘ofHCN. 34 COMPUTATION OF @ Examination of computation for unccnfined cjarger (perfect gu) as Well ss the mo ‘dsborate calculations for”confined charges BRW, LiD, etc) clealy show that when an ‘exploave contains suficent oxygen to conver, AI ts yrogen to steam and ts carbon 10 CO, (oxypentalnced), the water gx equllbriam completely dotemnines the composition of the products, Thc aqulibeam is rater Insensitive fo. the total pressure at equlllriam, (Condemation of thes thoretial computations fa found in Oral data for confined and confined PEIN (Table 32) which how ‘ementilly th same pout compeulion a high nc 78-300 pressure and at ambient presure. Convery, in fxygen deficient explosives eulibeia() through (6) play an important ole and at ‘expected, the product compositions for an Cxygen-ngatveexploive are very diferent for ‘confined ahd unconfined charges (Table 33). "We now return Io the question of @ the best pleted In s detonation and its rationdhip to ‘i which is determined calorinetily. @ fannot be meared rely. It can be computed It ¢ PVT equation of sate is known {x the dense detcnatien products. Since tere is no general agreement about the proper form of ‘PVE equation of sate for delonatca product, the bet we ean dois lo compare Qs computed With afferent equation of sata This i done in “Table 2-6 using tree rather diferent equations of slats. Somewhat unexpecedly turn out that @ by the heat of vaporization of wate. However thee is tome prewure drop tnd, consequently, the equa of wich eactons ar () an e) efter tothe ih in the Cd state than in the alorimetie. Restiont (@) and (e) (au well ag (2) and (0) the less Important reaction) ae exotiermi, and thet ipentr degree of completion in the Cd state {nda to compensate forte elect of he hea ot vaporization of wale. ‘Some free conclusions may be drawn from hada in Table 35. As already stated, at 8‘Abie 70810 {xed denity for agen expasve,@ dows not change ‘with the equation of sate but the computed CJ temperature do. change. The computed CW presures (which axe generally in esonable agement with experinent) do not change appreciably with those equations of Male but do, chunge strongly with nial Sensty. Now for a gen equation of sas, ‘hinge in inital density produces nich gresier ‘change ia the computed preware than in the computed temperature. Tels computed ore ‘change is confined by experiment. Note the computed Q for « particular explosive inl ewes decreuet as the ‘computed presure ‘ecreaes but that It Tally independent of the computed temperate. Thia same tend sppeared in the date of Table 82 where tho {ipece-out temperate for all the explosives ‘wero about 1600°K. but “the -cqulteam Pewurer and product "compeatons aed Gepending on wheter the explosive was ‘confined or unconfined, Thus it appear Ua product competion (which delemnines Q) i fore stongy influenced by the fal prestre than by the final temperature of the system, “The relative nondependence of on OF temperature may be nionalize a fllows. For corygentalanced of oxypensich explosives, the water ga equim (reaction) the ‘mary reaction which detomines the product Composition. Thic equibium changes rather lowly with lempenture and furthemmore small ‘ching in squllriim composition produce ‘ary Htle change in Q because reaction (2) is not themmoneutal, ie, (Alco, = (Aico + (Aluyo. For onygen'poor fexplodves the explanation is not at apparent Reactions (b) and. (¢) are senstve to ‘temperature, and they re not thermo-neued Tt ‘may be that equilib (b) and () lie far tothe "ight (ws witen) over wide ranges of detonation tenperte and prestur, "Two. further generations can be made about the Testy in Tele 9-6. It we aang ‘explosives acording to thelr oxygen balance in ‘order of ictessing unbalance, as we have done in able 3-6, then become apparent that the Megat Qv are obtained with anced exposes td Dua the Q' area. fay slowly for ‘moderately oxygen-poor explosives, and more rapidly for oxygeneh explouve, The reer at be warned tha there areexcepdons thie Evy smeraization (e.g, Eaplosie D and Hyérarine ‘ite in Tate 9.5), ‘A more fruitful approach to «prion estimates of Qs shown in Tle 9-7 eis cleas that Q's bse on the best avallable computations agree lowly with Qxr computed sce on the bats fof initial explosive composition and thermochemistry with the arbitrary (Q) “All the intlly avaable hydrogen forms seem. (2). Any oxygen remaining forms°0,, (8) Any caton remaining eppeat oll (0) All henitrogn goo Ny. ‘Thus quite ccurte estima of Q appear ‘pout if the initial explosive composition and ‘Bi of this compodtion ae own, 35 FRAGMENT VELOCITIES One of the moet wie functions of a secondary explode ais ably to produce and ‘coset Bepmentsfomed fom Its imisediate ‘vironment. Tt weer likly thatthe effiency fot an expouve in accelerating agments should be teltot to the enargy contsined in the explosive. The discussion. which follows wil ‘Sow tat this expectation i fulled ‘The socalled Gumey.fonnila? are_very suzceafil in determining teninal fagnent ‘eloiden. These formules ae derived ot the ‘aa of tee Andamental seston, namely: (2) The chemical eneray of the explosive 1s conrad into kines energy of fragments tnd detonation product. (@) The velocity dstibution of the Getonation prodics vas linemy fom 2x0 to ‘he velocity of the fragment (8) Tor density of the products is uniform or a lee independent of postion, Ley, Pot) but p Apts For cased cylindeealexplsve charges these sssumptions ead to re v8 eae oo{ { , O whore ‘Y= terminal tagm.* veloity (no ai a). VB = depen Gate consant (ving the dimendont ot © = weit of eapenie he “eipitoteaing or the caw of pane wave delonaion seesetings Mat pla, the Gumey fora 7 a vaca — n ‘Gumey constants computed from expeinents: ita obtained from sve soures ae compared ‘vith Q in Table 38. On the average (with @ ‘Uaioe from Ba 3-4, wing experimental A) ad = 0.85, however, tere may bes {fend Yor tisratio to deere as py decrees. ‘The rents for TNT ae contadetory. The oly ‘alah information for ntrometiane (NM) ‘aakes i appear a an Inefficient plate ving cxplosve, Nevereles, the data fn Tatle 33 Clearly. show that in one-dimensional ‘etonations the chemical energy of explosver is very elclenly souvered Into Kinet’ energy (ound 90% ccatusion) of fragments and explosion products. 36 AIRBLAST ‘The stfclncy of an explosive In producing sicblat is usually ves Jn toms of equivalent ‘weight Le, the weght of TNT (ot sine othe: andatd explosive) to give the same air-biat ‘verpresure asthe te explosive where both ‘measurements are mde ta fixed distance ‘Hom the charges (see Chapter 19) For ‘measumments made faraway from the explosive ‘arg, Landau and Lishit? hate shown hal {he Ommpresiie i proportional to. the inital cnergy of the explo, ie, to.mQ where mis {he mas of explosive; consequently, ‘oquirlent welt = mm = @iQr (38) cahere the superscript © rofers to the standard explo. ‘xpetimental equivalent weighs are compared to computed Q/@ry-x and to experimental AH,/(Gi err is Table 39. Ageement ‘tween mayer/m and @/Qpyr it een to be ite good. if (Aitav n> may xm except ‘Amc? 70-180 for Comp. B and Pentolite which contala large roparions of TNT. This not suprising since {tis @ and not Afi which shoud eorrelt with equivalent weight. Using the approximation of 1g, 85 bring the AH, vals Into much beer agreement with the equvaint wight ration, ‘roep! in the case of alminined explosives fr wich the “eomected” Ady rato stl realet {han the equvalent weight to, ‘Thin suggest ‘hat ie unconfined alumni explosive charge ‘the auminum dose ‘not contiiute al iis chemled) energy presumably because the ‘Suminum reactions are slower tan the ote ‘etonationvestons. 37 UNDERWATER PERFORMANCE Pace? has suggest that a cision of the underwater performance of a explo gen bythe sum of the shock wave enemy (ata fixed distance which is large compared. to the texploste dimensions) andthe oxclating bubble nergy. To 1 fit approximation both shock nergy and babble vary dieely wid explosive ‘weit and the sum should be approximstly gua fo the chemial exergy of be explaivet Consequently, Eq, 8 i also wplianie to Undervater explosions ifthe m's af the ume of tquivdent weghs Tor shock ve and bubble merges, The data b Table 310 Siow excellent Agreement “between equivalent weights and Garr except fortwo explosives (ENETR 1nd PETN)” which have only aight oxygen Geficiencer Ar dicuwed: in ‘par 8:3" the competion and, conseguestly, Qfor thee two explosives donot change with connerett: For the ether explosive in Table 310, and pariclaly for TNT, composition could be feed by confinement Inthe direction of fmabir Qa caliente nduced. Te is onceable that the computed Q's for the tye negative explosives are ocestinstes of the actual @'s for the sondtions of the ‘experiment, snd consequently Grew /Qrarr & Grween/Gry should be larger tan shown in ‘Table 0. [Note that aluminum geatly adds to the underwater “porfo.iance of aluminized ‘explosives, Presumably thts du to the longer ‘confinement period of the sumoundlng walet ‘which allows the alminam reactions to go 12 Completion before too mich expansion occu,acs 78160 38 Cd PARAMETERS In per 8-4 we indiate that calculated Q's for dense explosives re insensitive to the form of [PVD equation of sate used inthe computation, ‘This meane tht Qf avalabe experimentally 1 poor extrion for choosing the bet equation ft sate, On the other and quite good ectiates ‘ot Q appear posible bwed on Qy oF Aig ‘Thee “cotmaes can then be used to get spprosimate vauer of Ty the equllbrism temperature of a constant volume explosion, Pog the Chupaum-Jouguet pret, and D the steudy detonation velocity. Appeenimate wales {ory can be obtained from @ he n 69) aa where GAS heat retested in an explosion computed on initia! explosive ‘compesition and thermochemistry nd arbiter ascgument of produc hewn in par 34 ‘urbe of mole of ga ut equiibriam (Sesiled. from abitary reactions ‘din obtaining Qe specific heats of products averaged ‘ve the iamperture range Ty ~ Ty ‘The Ty blaine trom Bq, 39 should repent an upper limit to Tey, since all the chemial ‘energy is asamed to go into thermal energy of ‘Ge products and no allowance is made for foeny of repulaon which tury must be present inthe highly compreued C¥ sate. I the Getonation products obey the polytopic gx: lays Le., PV" cosetant, then Dm» 294(u1) (61 Por upyie-3) BAD Agreement between experinenal vives of D fd Peg, and toe computed using Bae. 3-10 and 8-11 ts only moderacaly god. Using Qy-(ot ©) and “in2.5" the average deviation of computed and experimental D's (detonation ‘locity la 8% (45 to-19% maximum deviation) {or 18 amos voidiew explsives Por hese same ceaploiver the average deviation of computed and experimental Poy it OR(+18 to -11% ‘maximum deviation). For ten other explosives for which experimental dita‘ also arable ‘the deviation i rester than that yen, Seven of these ten explves comin NM or TNM oF Doth Por other values of ky agement i even "A better approach for etimating Poy is 10 we experimental D vaies which are often ariable ‘where experimental Po, sta are ot. A Convenient equation to ue Calon on 28 exe (ome of se sce swt trode Sn) a Eid cet eprint Dd Foy get fees of 25h main eg 4 S0"Faw nso whch pe Creu titre gee NT Sd sland Sm Bolan ex 30 MAXIMUM WORK In an adiabatic proces, sctonting tothe fit lay, the maim work Wy oy thal a element ‘of txploave can do on iaslmoundings AE (oot ‘thatthe tom dlabtie refers to:no heat ‘bin ot low by the element from orto the fSmounding), For a consant volume explosion, fxpledon products (lomed in an exothermic action) tamed 10 be a plytuople ga and ‘egectng the Pr term forthe vlid unreacted explosive, AE = 5, B, * D(A) peste 2 set em a) HO + Fer a polytzopie ga ty may be related too sccording to ts where the subscript refers tosome intermediate Sate ubove wich the poly topic coetBicient i tnd below ‘which ihe cotficent y= Gpleo, Pow. = Pj/2 ls the constant volume Splosion pur, and the wubecnpt 0 rees = Pol and Pal = 20?nce 70:00 to the standard explosive. For typical dues of fe parmeler involved. and an whitey turignment of (2/F)/2~ 20° It can be own tat By Tag, 50% ‘Consequently for constant volume (x expledin | Wmue Qe, (O14) 2g, 8:18 i ao applicable to a C4 detonation xcept that 6 for a Cd detonation i diferent thom fora condant vom explosian, For 8 Co detonation fof = Float + OP Poot anda bear a= P50} im With the same smumplins at before ‘<0.03 and we Wn @ (916) Because the presumes ee feat nd onmguenty Be ches equa ould be ‘Stent @ doer not necemaly egal QT ‘ata Tabe 38 mgt fat Q>@,, beau PDP. Theta” reno. compllaty unambiguous rmewurmamt of te maximum work done Sr cplodve; however, Se Bala Mocat Probably conn cot to being rl of the marimam work, tn ths fet » tancard rein of eplouve fred ins sapended ‘mortar wit a tightly fiting ste projectile and the angle of recoll of the morar a memred. Real ae generally exprewed in tems of « Mandard explosive, g, TNT. In Table 3-11 we omprre mearited Bale Mortar rate with Qrvbere both quantities re then wlative to ‘INT: Iti obvious that conelation x poor. I the Comparison in made with Aff, rather than Q, ‘ormation ie mich bite andit becomes better yet if one arbitaly aig (A, )puy = 1.00 Seals rather tan the meanred (AH)rj = 1,08 keal/g for Uighy confined chase. As trendy dace the heat velene of TT, but ot of other explosives rach as PETN, ieetrondy fnfumeed by confinement The explouve Toads fn the Balle Mortar are genery at fry low acking denaties so that detonation products fn expand alighly before the project starts fo move. During the period of weelention of fd not @ a baler mean of the “maxima ‘work measured by. the Balls Mortar. In ‘Thble 3:2 we wow Wat AH for TNT vain ‘Hom 0.88 to 1.09 kcalig depending on the degre of ‘confinement. Conequenty, the tibtimty choice of (AH )nyrr * 1.00 Reale ot uamescoable a this case, Tn the Ballsc Morar, ot in achat and ‘magment propution, shiminized explosives do not perform aswell expected roa Delt ‘Beoreteal @ values- ee ee en _ i : ‘cr 0 i 2 ce ett | : ; REFERENCES i Hl | 1, BL: Ome, J, Phys. Chem, 72, 2590 3. D. Price, Chem. Rev. $9, 821 (1959) t i (tobi) end Onelan et de Rew. o€ Se 4. RLM Cole) Uhdenoater-Bsploina, : {int 27,907 (1900) Fioceton Usk. Pea Picton, 8-3 ‘ ! 2 LD, Landes and BM, Uitte, Mud 1048 4 “Mechanics 6, 972-377, 392-396 (1958). 5. W. Gumey, BRL Report 405, 1943, ' } ! 2 1 z i : i i ‘ i | { “ | ! | . i i Os 1 « Mo ‘ >| } e i oS | 3 ?TABLE 31, SOME BASIC THERMOCHEMICAL DATA‘TABLES3. IDEAL GAS FREE ENEROY FUNCTIONS (C/T FOR DETONATION PRODUCTSsce 708100 TABLED4 WATER GAS EQUILIBRIUM FOR IDEAL GAS PRODUCTS "ATT ATH AND 1000 Product compotion, Eeplosive rmolesinole ETN Hux. ‘wr. | CO, 880 146 ‘00s ot co 1.60 284 538 | 0 380 284 00s 07s 4 080 14s 248 Ny 850 400 1.80 i ly) None None 1109 i NH, 18x10 1x10 A sx10+ cH, Nove None on2 Qrkeae Lat 124 ost 098 : ‘ad on computed compotion M0ee mRa TABLES, CORRELATION BETEEN @AND OXYGEN BALANCE Explosive 0.8 myo.2 TH x neers Pete 2y Sema) 3m Explosive D par nydrasine nitrate 1.90 1.00 aaa e weatls 149 1.0 Lae a8 aaa Le 0.85 aa aaa. 0.90 nverage valce shom in Table 9-5 “onpten batence = ~ ‘Formale volt oxygen —Belence’® 0.00 Cae atone 48/20 a8; tc 70510 Vy t~ TAMLES7, COMPANION OF Quy AND, BASED ON AN ARBITRARY ! DecownoetTion ueSianae .f } \ Explorive Po, is | wee | { ven oe han nego ke | mm esas nee ads mx cwiatote ae ha \ a owes Leo. nae a ota Least { mmm cymsho, Laka i ™ cao, has gee | Ps } wr ephah%e nest hae \ reste Aer cymstye kta kas ania cating Leap ona aplontve Dcglghey Le or .08 PB 906, ay aala.siMaey MO LT 3 com.t-3 cy alah agOs gy 7 uA La core. ¢ Sieg bk Le * room arbitrary decomosition fonygen t0 4,0 and CO, with excess carbon appearing as C(s). 0.03% Prom Table 3-5, and WOLAnd ASL compitat ons ectansam easigning all availablea ' i sce 708-180 i | aay \° ! | | \ — i | * | | | i e O} i a | | = | | os \ | “ 1 i = | i | vi ! i | ' { | i Al | | | | xTABLE3®, CORRELATION OF @ AND EQUIVALENT WEIGHTS FOR FREE AIR BLAST os Soo . Tt 90/5 moK/wex 126 ae 1a pore 139 t 7 “ Las cay ma iar > $0/80 Pentolite 1.6 - 6 aa 1a - p = * run trom 3. Pete dnnaly NY, dendeny of Sesascus 18,915 (1968), : GO) Avsinad sighedy emcitor than the 1.2 £8 1448 Keal/e comptes Oy 19D oF BY 5 SING festearde toe. o 4, = F'n aK, © catouation ging the BEY equation tt 00 U3 GHIA + 0.7H0, «DADO + 1/9 64) 17a, a we| i | ‘TABLE910, UNDERWATER PERFORMANCE OF EXPLOKIVES nox 95/3 oxox 75/25 cyctotot Comp. 8 50/50 Pentoiite eter Explosive D Munintzet 70/30 narB/ A, 0/3/25 wox/¥ax/AL * netstive to mr, this is the equivalent weight for shock iy + buble enorsy. asta: ©) Nou computation of @ (©) Qy2 2642 heals tor 6g (assuming @ = tity (0) age 2:2 keat/g. tor 1/3 0.48A1,05 +0.531,0 + 0.47%, #CCs) +My Beutvaent esant® ae 1a Ln 2.08 0.91 nay 1aq aaa aan 2.09% aan ova m0 masr® © mat Data taken f20m Ref. 3 Naa + AL = 9A1,05¢ BH,0 + CO,HSCIN egy Dgt 0098 at tafe‘TABLE341. CORRELATION OF DETONATION ENERGY ANO MAXIMUM WORK. ee Rag ay = BHD, saves wat (BALLISTIC MORTAR) 8 ree @ fea ste a nal”) raat?) aa)It | CHAPTER 4 THERMAL DECOMPOSITION OF EXPLOSIVES ‘41 INTRODUCTION Beplosve liguds and sls can be ecompoeed by heat and ight at relatively tmoderite tempers, During decomposition, Considerble heat ltemted ince these feactons are exothermic. When ihe rate of Secompesiion in. 'the condensed phase is Steely high, then an explenon may ral ‘dee to sethettng be, the het generated duro Secompeation exceeds heat os to the ambient by conduction and other means. This phe of ftconpoation (elthertig) is analyzed. ‘Copter 10, Ibis clear that dead information fon the stability of liquide and slide is needed fortwo. rewone Fin, 10 delernine the endilons under which ihe unstable materials ‘may be handled with some degee of safety Second, to determine the. conditions under ‘which "explosion wil result since many fxplosions ae preceded by a phase of mpl ‘Secomposiion ‘The ft step in ssesting the stay of « liguld or solids to consider the thermochemical properties Detailed Information is needed op fates of decomposition, activation energies, snd beats of decompesiton. Some information on ‘hve properties is becoming avaiable but there Is consderble crepancy in the values quoted by aiferent worker, There ie ao Isck of relishle values for” many. of the. thermal properties such as sect. henl, thermal ‘ipansion, thermal conductly, and other simi properties. tthe conditions under which explouon evelope ae to be contzlled, then its vital fo Undemtand the mechnisn ot the ‘decompenition, This has been recognize inthe Tat ten to fifteen year, and there are active centan of research throughout. the world oncentating on this problem Lguld exposes te ually charscteriaed by covalent bonds and ‘hore i onaierable background of search for telsted mater 1 make it poste to propow ‘easonable decompostion mechanisms. At the fame time, the development of moder fquipment makes posible the analysis and fdentificetion of intermediates in’ smal Concentrations and. of short Me Mase fpoctrometer, eeetzonapin resonance and nuclear magnetic resonance equipment, RONO thus indiatng the way i which lteates may be efor and aso how sites canbe produced (uring decompotion ofthe nitate esters. “The alkoxy! radicals can undergo a vanely of reactions and rarangements, an Inthe case of fhe simpler alkoxyl adeals these have been Aesrbed in deta ina review by Gray and Willa "there may” be usocation with radious, hydrogen abstraction, rearangements (omerztion, decompostion ofthe raleal to Simpler radiels ands” Wydes or Jotones, ‘spropetiontion, and decompastion by 7radical stack, It ie evident that Wl thene euctions ean lead to complex products and {hove are found in the decomposition products or the decompostion ofa nitte ester soch se n-propl nate the following et of equations ‘maybe written aa sequence of rections duting ‘Scompeaton 1-0,B-ON0, += CyH0+ NOs 2-480 Cally: + NO, C410" NO snd some C,H,NO, CHO > city: + CH,0 Gti: + NO, + et 2-080 + NO-+-CyH,0NO , Schemes wach as this have been proposed for ‘any nists and related eaters. Wht i needed I the activation energy for enc sep; some of thew are now known futyaccurstly. Syeteme uch a geal nae, aktogycein, sed’ PEIN will behave ithe seve way but, Since there are mote sate goups Th ach molecule, there iil in working out te rede order f the eps to the final product, {Than gycol dnitate would be ated to decompose ideal in the mannee NO, OCH, CH,0NO, *2NO, + OCH,CH,O ‘ 20H,0 cx fr more complex dnitates nce NO, Ga #1eHAEO +8 HO, + on (c14,47180, or PRIN, nittoycern, and related stems, ie 708190 cate compound-ich sora Sore compe Sangeet od Sten ae fad umlonoy, tnd helo th Seay mda ae led by te aon Sead ihe compotion of itopyeein Sienia'a he pease ae sowed SSO ov bad aa none Sout tom gov pececeieh NN IB Gor iM nt Het deed ‘ion ot cocsed aces ae nd. “ie ncaa sles tuo deconporel Wy clei sed etn se at Sn ay hon ton, Pan ew he ‘mos ote ered ate RONO, " RONO? + RO + No, cited tate which may revert to the ground slate or uocite to ge free mal “Andreev ha made an extensive study of the ecompoation ‘of nite ater, and) of the fffect of products and wdaitives on the reaction ‘ata He llowed the éscompotion of PETN 4 vaiety of piysca slates te slid, molten, ole “and pucour ates, ‘The tle of Secompostion greatest 1h the gueous sate td leat ne ota, "The no compounds have also been studied Ingome deta A revlew of the decomplion of nittomethane ty Makowky and Lenj™ records the information sealable upto 1958. The vapor Phase decomposition at different terperatres And premurer har been followed by ate and ‘ow methods. The reaction hat been shown lo bit order anda are nuraber of te products ot decomposition identified. These include NO, 0; Hp, CO, CH,, 00, and taces af C,H, fH, ahd NO,. Mote conieated product at timed at high presume, e., HON, CH, CN, HOHO, ec. The ovenll acivation energy fot decomposition is inthe tegon of 6053 ‘caljmole, Mos investpton favor bond fsion 1 the inal step inthe eecompeition. (HNO, + cH + NO, Numerous other steps have been propoted to acount forthe promt of decomposition, and fom ofthese are vento inca the fype of reactions envisagednue 700190 (Ci: + CH,NO, + CH, + -CH,NO, -CH,NO, + NO, + C0 + NO + NO, CH,0 + NO, + CO +NO + HO 2 cH: + 07, 5 Rescions ofthe pe City: + NO + CH,NO ~ CH, "NOH > HN i +H,0 | see ala probable reactions. ‘On the other hand at high peur, in the o rmgion 1240 stm, Makonery™ and Guenvwald ‘onder the rections (CH.NO, + CHNO + 0 0 + CHANO, + CHO + 1INO,, ets may alo take pace, ‘The photolysis of fRiromehane has been studied recently by | Nihelion* who postulates bond fiona the | india step inthe decomposition. "The decomposition ot the higher nitro aBaierseas nltoetiane, Lead 2 ‘nkzopropant—hat ao een studied though In Ita deta. For nittoethane, salves of tho atiation energy ranging between 41nd 48 hcal/pole seem lo be the most rable, Ther Is ‘conaideble debate conceming the fi step in ‘he decompouiion, The ON bond strength is ‘timated at eal wd tho atation enecgy forasured some 10 Kea! smaller than thie for nlzoethane. Pouible schemes stating with CaH,NO, > CyHly + NOs ‘athe fest stop have been evolved but the ‘Bamative reaction CaHyNO, > Cyl, + HNO, a rong candidte, For this rewon the Seuiledscheret for the two ral eebanime Sel not be ven; the dette may be found in the erature "For Dalirepropane, a careful study by saith and Calvert gies the following expres for ‘he decomposition ae constant ke La1 X 10" exp [-89.5/087)), 867(48) “ ‘This bated on propylene formation ina state ‘system. Many ofthe arguments put formard for ethane aso apply to. the nitropropane tystem. Ago, there is direement at #0 the {ist step ofthe decomposition but the weight is perhap favor ofa sap ofthe Kind (CH CHINO, CH, + Cli,=CHCH, + HNO, Here, intzumolocular elimination of propyene smd nitrous acid takes place va acyl mtivaled ‘Complex, Tis i followed ty mses of dca ‘eaetons. Some of? ae proposed are HNO, > OH + NO OH + CH,CHNO, CH, +H,0 + CHyeNO,CH, +0 +" CH1,CHNO, CH (CH,CNO,CH, ~ CH,COCH, + NO CH,CHNO,CH, + CHi,CHNO + CHO + CHyCHECH, + NOy (cH,CHNO ~ cH,cNOH CH,CNOH + NO -> CH,CN + HNO, “The higher aliphatic ltzocompounds have not wen studied io sufficient detail for likely ‘ochanieme tobe proposed. The alo tr fF tome of the aromatic compounds wuch a pire mia 4422 ome sou (azo) rom the practical point of ew, lad nie is the, most intereting of he aides. On the ‘qallative se constdeble information exists Gh tater of, decomposition, explosion lemperntres snd he like. Tt has only been ralled fn tecent year, howevet, that one need {op frthor into” thir problem of tht Cheomposiion of the azides, Figures were falable tno. cal underianding of the tnechanism of de-ompostion; thi stl ue to °R wart bas bown me onthe simple ies in the slid sate which are represented at MN,O- | | | | and on the rated compounde~the falminates (HO and eyanamides CN —since thee form 4 ueletrone serie, Consier a slid ike EN, Itisknown that ts compote of ons Ky and’ Ny, nd” hat it ie elanely stable ‘compound The aide on gainer syminetcal soup NiswAnLithy~ with sateen valence ‘decttons\ and the orblalaysem canbe represeniod imply asin Fig. 3 where the bonds, lone pal, and the bonds “ae indicated: ‘The orbs which ae of intel from the pont of vlew of electron talons fhe the dloelzed 2) and 3, nonbonding ‘ottitals since electron’ will be! excited from hve celia to higher ceils, "The azide font aso electronic with the (60, moltcule and ll the vale for the vibiation trequencier-symmetial stretching, faymmeteal atething, apd bending™ae nove from infrared nd Raman sects. Frm, theme, fore constants may be acute, if one comiders a simple sties of the monovalent arides“KN,,TINy, ABN, GaN Hg, (N,) .~an orpnie hide ao), He 1s fond Ut te tay vals in the order KN,> TINy> AGN,> CuN CH Ma)a Sool sides, The stably decrenes along the veties K {o'Cu atthe falation potental increases, oF nce 0180 ‘more accurately as(T~ Byincreases. ere Bis the ‘eeteon affinity of Ue aid (N,) zal ait in the order of 2.8 ev, although higher values than this have been quoted. The problem io explain why the saity vais in this ways fearonable explanation ean be given if we the band theory of sli Tn the case of KN, [4.92 «1, B28 er; therefore (IE) is smali. For greatest stability, ‘the sold should be competed of fons K™ and Nj. The. sricture Ww tragonal and all ‘ntlalaitrogen dsances are the same. It hat Dropestes typical of lle wollds such a2 KBE, the rebactive Index is low (ofthe order 15), tnd the optical absorption edge occurs inthe ‘cwum ullrvoje part of the spectrum. The thver alts “ABN, “and ABB, however, ae Unsable solide ind realy decompose on Iating oF dung ixadation with ght of stable wave eagth or oltng latin, Bans oxo sina 2agBr > 2Ag + Bry where Q represents the heat of decomposition. 5 -F,,Panbonding orbit ‘one pair N\ fam, bending ete N+ ne eae ponding orbit 7,29 bending. orbital ‘Figure 43, Representation ofthe Orbital System of the Aside Ton‘Te bromides are sentioned since thece In {aot a close semblance between the behavior of the ardes andthe comesponding bromides. The fone mdi of Ag? and of KY ae 1.26A and USGA, respctivly, which ae not to diferent (On the other handy the structure of AWN foxtomomie, and there are directed bonds: In ‘he sold, there are four long versnitogen 32.798 and four short bonds of 256A, ‘The solid hata peril layer tpe structure. The Physical properties depend markedly on crystal fection The tetctve index ie igh ard it ppresinataly 20-for ligt of ong wave length, And the optical abaorpion alge ie now muck {hither into the vibe part of the apeetrum. Al ‘hee properties indicate a depute from an Soni type of lattice in he sve sal. ‘The decomposition of silver azide by het is exothermic to he extent Q-148.Keal/mole rom the ren chemin equation iti clear that hile the lai seompored manly of ions, the ‘Products ae neuttal so at an electron transter mechani must operate at some sine of the Secomponion. Before the mechan. of the ‘scompoalin can bo eablised, it necenary to detrmine the electron energy levels in te telid~in other words the energy vequed > ‘ct un lston fom the valence tan to the conduction band where, a in Fig. 44, we fsume the valence bande formed by’ the ‘overlay ofertas ofthe snide Jone while the conduction tand ib formed by the oredap of ‘rbtar of the metal Mone ‘On the experimental side the over activation “meray for be decompoition of iver aide hat tren determine from presure-tie curves, and ‘below 100°C the values 44 teal/male or 9 er molecule. Some information i sao svalable on the cllape of the late in psig from aver taide to mealie aver. Tie w oblained from flectron ditmction wading of cry aw tdcompose under the action of an electron beam i the difimction carer. Orentnd vera formed with labice parameters alightly greater Conduction band (overlap of orbitals from M° ions) Valence band {overlap of orbitals trom N3 lone) gure 44, Schematic Showing Brergy E to Exclte an Electro. from Velence Bond to Conduction Band in Siser Acidei \ | ~) mcr 708100 han for normal sive, adit copeluded that @ Aifusion of slver kes place to lstice sos Imade vacant by the removal of azide fons N ring” decomposition This wil give ono tlverniciel with large siversiver spacing. Finally, there ea cole to naval slvr. The slver hat is formed during decomposition is ‘ery mobile and appears on the surface mainly 1 diocele nile which gow in size unt Bey ‘over te whole ofthe strface, The nile may belles than 10A in diameter (the limit of resolution of the dectron micromope used to dolermine ther ss) to yrater tan 2000, ‘These nuclei play an important part in the ecompostion, and fr the reson a knowledge fof thew size and detibaton i needed. The fechnigue ued is simple. Crystal of slvr ido fe hested or iadated. with light giving Surface fim of sve, which consists ofthe large Sod small nate ae itrated In Fig. 5(A). A ‘arbor fm i evaporated on tothe nucle (Pig. 1154), and undecomposed sver aide dsolved ‘vay ia dlute ammonia solution. The carbon ‘Mm floats ofthe Tiquid surface and i picked Up on am econ microscope pd which ben studied inthe normal way. It it powitie that siver fom intoraly slong dislocations in ‘the crylal in the manner found by Mithll and arated in Fig. 45(C). No evidence for this type of inhavor has 8 Ye been found for tho ‘ides, Bvon with costal of slver cyanamide Which resemble ler azide but which ae more ale, the ser i mainly atthe surfce. This has been "verified frequently in. electon ‘microscope studies. The situation, Tar as Gdslocations “and. thir iftncs “on te ‘compotion ofthe aides concered is that ‘poubilly exists that they do play 2 ast in the deconpontion tut ect proof & not at Dresont aralale. An etching technique might pethape give better rte. "Tae rain ‘Secompotion seam to lake place at the surface Reference was made elt tows ofthe bind theory of ellds in coraeetion wih the ‘explanation ofthe sai of azies nd it was Stated that iti neesay to determine electron nergy levels he sold. The simplest way to Aetermine energy prs is rom the optical and Ietrcalpropertis of the sll. The opti! sorption spetn are determined in the normal way, and one can represent he light path as Fig 46, 7, the incident lta of Ih snd [the lane ints, then in the ie cae the absorption coatichat einem? is gen by tho expresion Fl,e"*, where ¢ is the Ahienes of the cnslal in! em. Absorption ‘onticint are determined ae fctone othe vravelengh of light and for value of «inthe ‘eglon of high absorption coresponding ' 10" tor 10® em i aimed that photon enengee ie commapond to th band pap a shown in Fig. 47. Hew one is concemed with diet femngtions from the valence band. tothe ‘conduction band for values of the wave vector 0: On a simple ideal this would correspond to the energy requzes for the following proctss but this concept should not be pushed too fr: Mom toe side on aude radial electron in Inlatice (postive hole) conduction band Measorements ofthe absorption spectra at ow temperatures, patcaaly at lquid ‘bellum temperatuee, revel the, presnor of exited ates. Thos ae xeln Ieee ani below the conduction band (Fig. 48). They form a Inydrogerlkewties and tee frequeey even by anexprsion of to form Hat Hy Rn a where is the frequency corresponding tothe Gacton “ef quantum number m7. 8 the frequency of the sere limi, and Ris an cxcton Rydberg constant. In the case of the ‘Shall metal aides, Deb ha eld the n= 1,2 fod 2 Tins and has found that at lige elim Temperatures the band gap for KN, b 8.6 oy onesponsding f0 light of wavelength 14804 fn fhe vacuum wizesole, and the m= 2 exciton line octet T896A or 6.6 ev. hase gope ate ‘tte age xclton lvls have azo been identified in rik ad AB, Howes e no find sorption ge isn te vicinity of 500 A ce force tide Te values for the pe tue: E) 3.6 er opti; 2, = 06 ev opteal (eso Fl. £9), Thao ae muth smaller than for Polassum wide can aio. be eatinalad from dlctic conductivity measurements thigh teperstres bat the interpretation ‘of the result not slays casy since both ionic and clectonis Conductivity have to be conddered an 9‘Figure 48, Showing Technique or Studying Siver Nucl! from Decompose Silver Azide en ee‘ice 708189 la suzadg wondionay trond Puimuune sof arouokeg op ahsic 70: St canton bood | \ ! \ «|i Esty atkeo 1 1 i \ 1) lence bond w » ure 4:7, Abworpion Coefclents aes Function of Wavelength). At igh Abwortion, Photon ergy hv Aasumed to Corrspond to Bond Gap Ener) E Fe Sam Low temperature ‘spectra of = (omar Figure 48, Showing Briton Levels asc 706-80 CONDUCTION. BAND : } i | E706 ev i optical ; | nel exciton level | i i i E,=35ev opticd i silver azide ( valence band ‘Faure 49, ery Gat B, ond By i Ser asie a3 }sce 708100 bbe estimated trom photoconduetivity experimenta. Hore itis asumed thet one fmearer the thermal “energy requzed 10 Aigociate optically formed excitons in the Nirman? ME ny ee) aston ea 1% at Af et acts ‘when they are irmdlated with light near to the Dilute cept ate ie se ee eee Se Se ee ates Pe tered Bom oy tab alta ea wes Alpine oft see Spada trang toa oe Sechn Serat So ae Soros apne hats SoReal seen tide gaan Pee Ma dotnet andi Hse mot Seer “an Stas © Seca ti apn pee Se ee inal Set et weer safer te breed oe Saat anes kien nee, Tacs Eee Theo "tbat ot padcocpe ae gees gt ters aa ary tral ea ie Site ie Sat rea tae Pandoonts ful edWethed Somey pe ittmina aa mee) an where, le a thermal eneny, Z, the Comesponding. optic emery, the high frequency dilectic contant, and K the state cf low frequency dielectric condant Ky. ‘timated from values forthe rfmetie Index n tnd for value of n coresponding to wavelengtis ‘wel away trom the aborption ede Ky =n" Subattuting the sppropvate taluer for ever side, one oblains for Ey avalueof 188 e- TAS 4 the thermal energy tequted to excite an decton fiom the valence band to. the Conduction band. ‘This agrees remariably well with the sctation “energy for thermal Gecompesiton of 19 ‘ev (below 190°C) determined trom preuretine cures It i isggetad in fact that Fy in Fig. 9 for aver tide i connected with thermal decompoition ind Ey withthe aclitation energy for Bhotocemical decompo. Tt i, therefore, Pelle to propose a genenlizedschere fo the femal and photacheniea decompestion of {he hewry metal azides. This is own in Tee reg TE must be emphasized that the cheme very general. The deed mechanism much more Eompiex since the prvence of point deft, ‘didocation, impart, metal parle: and the {ke ve been ipired. To a gener stse, however, te probably cone and resemble tatine the mechanism of devompenion of ver bromide nthe photographie proce ‘An altempt can also be made to explain how the sabilty dcrewes slog the ade series, "T Ag, Ca, Along this ele By is found to decrease quite appreciably tis dane that the ate of decomposition at a grentempersire an be higher, The station wth KN, tea ile ‘more complicate. The tnd eps szevery lege {id the exciton level n= Lt wll below te Conduction band. With KN, Jacobs” and ‘ompkintasume that during detompostion for ‘same by lh, excllons ae formed. Soece may te tapped, at vacant fatice ae, for ‘example where Xion re mising. The eckon from Be exciton is then lot to form an F center, The poiive hole (Ny) finally can give ‘ltopen gu Such a mechahiem ie pause Becase jut an the cae of the alkal halides, color conten ofthe Fceter type realy form fn the alka sides and could play «pat inthe decomposition. "At soon atthe Joniation potential becomes too lamers 1 810 ev-the sold Tonge ‘ompowed of ions but a coralent ype of ld is formed. Examples are merurout side gs (Ny) hydrate ach HN, and he orp atid, "There are now directed onds toons end ‘tthe ade group Slower ie doanee Rett snow mic ager SSan'yhy tor exe sag ere, Gi) bond eng and bot ngs we!i ! Il 9 TABLE42 THERMAL AND PHOTOCHEMICAL DECONPOSITION OF SOME ‘eral Deconpnion otek! Dronpoton sete aio Feat enton (NE =N +e + waNit G) Nebr N, +e Teealbe Se poste toe ana Sm “et Senn endo oune mya @ pe Ture ‘realtion: of two positive holes at thermal res oc tincen ‘inci ; * berry | (0) AeA sort setae BMS ee Sdn Pant mdau'ind teteen = Sstefmining oon So iow ae ss ane HI ! senalve Battery vorating wed type electrometer Figure 10, Schematic for Studying Photoconductty of CrtNasly. ci, 56° 1 we consider hydrazole aca the simglet of thee covalent sade the obit system maybe ‘tena shown in Fig 411 ‘There now exit Afeences In_physeal propertie to the ionic azide in vibration frequencies, since all are now infrared activo, snd inthe dacomposition behavior to heat snd Tight "The ila step the decomposition probably bond fusion, e.g, of the longert NN bond, ent, a, tn 6 HN, + HN+N, ‘The subsequent steps in the decomposition depend on the salty of MIN it M i metal stom, or onthe activity ofthe fre radical fit of he type HN. For example, ammonium side can be fomed from hydnzole tid. The Getaled mechanism is, however, the sublet of Inher vielent argument and controversy atthe rest tne, 40 Unt al the slepe wil not be (Gren ore Tn the cave ofthe crane andes the Fadical RN can undergo. rearangement barticclary ifs of the comploe variety and is Served, for example, from tpbeny] methyl and Similar goups R Unally the covalent aide are ‘more alae than he foie aside, although the Matament ist be quale to! some extent Since” ome of the coralent aides are tacredingy unstable, eg, BeNy, IN, NON, td the lke, Solid HN, i als aid t8 be very Uraable at there ie noreliabe information on ‘ha point ‘A number of other systems ae being studied In the same way asthe azides, The Ist would Include" the acetyl, fulminta,styphnats, and picrtes. At the present Ue impo to predict sccuntely the propertin of these slid, Polassium fulminate, for example sone ‘ofthe met unstable materi in this is and the eaten forte not lear. It holdin fact be 8 Feusenaby sable solid from whut oe kxows of Ue simcture end other proper "The solide preriouly dacuced are all of the simple type. fn te ewe of andes and acetyl “8 formed from transition meals wich a nickel and cobalt, de staation is alile more compliatad, Here one’ dels with coordinion complexes, ligne theory, the study of the effects of ‘ervironment of anions on the energies of the ‘orbitals of the eation, has proved valuable in ‘ucuning the optial and magnetic propertice and he sabiy of thew ali 433, AMMONIUM SALTS ‘The decomposition ofboth amsmodlum nltate ‘and ammonium perchlorate har been studied ‘extensively. These are widely wed ox explosive mater. The decomposition can, however, be ulte complex since the physical stale of the selid my change and it a poulble to have ‘ublimision and melting, Ammonis nitrate in {he slid tate can undergp large number of hate changer” overt. risively smal femperatre range. This har led 9 wef Jnfomation on rotation of the nitrate fon std

te ammonium fons in the sli, Bes. 210°-260°C ammonisnairate gs. if nitrous oxide and water, but above 300°C ‘explosion “can take pla. "Some mitogen it ‘produced and impurities, for example Cr, can fave a profound fect on the decompouton ‘The overall decomposition can be represented cs NH,NO, + N,0 +2 1,0 Brwumhaw has dicused the decompotition of ammonium perchlorate, The slid exist in two modifications, rthotiomlie below 240°C fand ‘cubic above 240°C. The product of Secomposition are oxygen, nitogea, chlorine, Chlorine dixide, “nitrous "oxide, mitogen tetroxide, hydrochiovis and pechlors acd and ‘water. An unusual phenomenon i observed uring thermal decompoation of wings crytale ‘below 300°C. An amorphous aolid is left asa residue and, strangely enoug, this is. lso Srmonlum perchlorate. A sll observation Ihr alt boon made for sodium aide ty Serco. "The decomprition af ammonium petehlorte, like ammonia nae, depends very markedly fon the surface ares of th eli. Inthe case of ‘ammonium nitrate, considerable effort hat gone Into the preparation of solid of low desl (ca 0.6) and bighsutace ares, This material i Sald to be very senalive to shock but there iecr Toi Swi ‘eme¥ suxeneg Jo wareks reso "Irsome diagreement on tht, The effect of mst Oxide clays on the decomposition of ‘tmmonium perchlonte can be gute marked Manganese dloride nickel oxide, chromic oxide, ‘apie ore, and tine olde eve all ben ted for example, te adtion of sins oxide ean have ‘profound’ effect. In this cam, the rate and texto of decompodion can be increaed, and {the explosion leperabure canbe lowered by tome 200°C. Many of thse effcts have been Interpreted in terme of dectonle procases ‘which our ding decompeaition; second’, Gelaled Vnowledge of the catalyst, putea by Its semiconductor propertien, is needed. Caabon har ano been added to ammonium per- ‘corte and ean iatsence the Kinetic of the ‘ecomposition “The emmonium alt ae foie tli and jst se for the asin, eectron tanafer can occur ‘uring dacomposion. On a moleciar wae ont Ina vine the Nig and ClOg fone in tho {alla andthe formation of Nil, end C1Oy ‘adlcale (under the setion of miitie stimu) nd. the mibaequent” rations Another Poaibilty, Nowever, ie the diociation of NH, C10," scording to the equation NH ClO, ++ NH + HCI0, ‘This i refered to ae proton tnufer and the reaction wil be dominited by the subsequent ‘decomposition and reaction of CIO,. Which ff these two mechanisns wil operate wil Gepend, on” temperature, and. Galwey and scobe™ ‘have sigpsied tat below 280°C the ‘Secton tater mechanain ie the important fon. Here oly 0. percent of the solid compen and, as mentioned, the residue it sil NH, C10, in an amorphous form, The fetetiog energy for ‘ecompention ie 32 Nealmoie “At higher tempertures, 350° 400°C, the proton tater mechani wil be the more important and the setvation energy {er decompoaion 198.5 kel/mol. The proton leuafer ies pltce on the arte of the slid {ellowed by Bie oxidation cf the ammonia ex, ‘ome of the stepe in the decompostion ot perchloric aid which have ben proposed are 2HCIO, “+ HO + ClO; 2,04 ~ 201, + 704 (och «cn ANH, + 50, ++ 61,0 + 4NO ‘The ote! decomposition may be represented 5 NH C10, + 4HA,0 + 2NO +0, + Oly Similar schemes have also been proposed for front nits, One favored by Rusian ‘workers HNO, * NE + BNO, ‘ NO, + 140 +0, 1H, + NO, = Ni + HNO, Nil. + NO, NO, : 80 +140 NO + Ny + NIQNO * #0 ‘a many schemes ofthis King thera no problem in writing down =e fee rade ‘avionn ‘Thr an ificliy i Yo deernine eter thac i fat Jo ake pace aod the Treas iwivedin the roca. 4 RADIATION DAMAGE IN EXPLOSION SOLIDS Bgplodve sods ave been sbacted to a varlelyof Toning radiations and nuclear Darts, "There ate, cetton beams, acand {Peavy april, Hee, neutrons, proton faion Sageents and éabllew others nol lated there, These would clude mesons and thove Datticles discovered. in" rocent. yeam Decomposition canbe induced in slide by these parison and, by taking novoxplosve solids at fodels, ome inight Into the suaton damage {hat i produced ean be obtained. For the lighter farter the damage ceoed is Hudled by a fariely of tichniquer Opical and eectecal Property, win resonance echniqies, chemical methods to identity aw spectes, radioactive teshniquer — all ae studded to determine changer within the crystal woh at inti, ‘wcunlea, fee radicals, color center, and Tputy” formation. Wheo ne damage. is cnsive as with fion frgments, igh Tesoltion ection miescxopy coupled with Mote! finge techniques can show tacks and location Loop inthe eget OO a asoo ce 00 For lone solide the main damage i cased by fonization, and electron proceae, simiar to ‘those diacised eater, opente. in addition, ermal tects, meol, nd decomposition ofthe anion ty oookt depending on he nature ofthe {diation: Covlent olde ge in general ore Stable, Post defecta can be crated, and sin fd ‘diocations Introduced into the latice, Localized decompoaition hat sso been found ‘ion fragments can cause an appreible Sncteae in narface aren ofthe slid All ofthese ‘actors can infnce the rate of t= mubeequent decomposition. Although the mala of ecompeiion may be enhanced, the effects ‘observed up to the preset have not been very spectacular, Inno cae has en explnion relied With the poalbie exception of electron ombardment and here heating hasbeen shown, tobe rmeponibe for the explosion. This i Dpethape a fortunate reel ine exponve slide tke aledy muttciendy dangerous to handle, without the added concem of excenive sentation by fonzing dation,REFERENCES. Boot: 1. FR Bowden and A. D. Yotte, aut ‘eictionin Solids, Butterworth, 1988, 2 JH. De Boer, Ed, Reastlty of Solid, Bee, 1961. 3. ©. B Colbum, Ba, Developments in InoyganicBlrogen. Chemistry, Paci, 1065. Chapter on Inorganic Andes uy A, D.Yotte, 4, WE Gamer, Ba, Chemistry ofthe Solid State, Btterworths, 1955. Contains a number of excellent "chapters on Secompeiion of explosives. ‘5, “Radiation Damage in Slide", Course 18, 41962, Proeedingsof the. Intemational Sehoot of Pugvics, "Braco. Fermi", ‘Bead Pres 6, PLR, Bowden and A.D. Yotle, Endeavour 21,126 (1962). See ako’ A.D. Yote, Proc. Reval. In, Chem, 1961, p74 on properiee of senave compels 1. BL Bras, F. Gay and A. D. Yotte (Chem. Rev 88,515 (1950) for review on sides, Also P. Gray, Quart Rev. Chem. See, London, 17, 441 (1863). 8. B.Geay and" A. Willams, Cher, Rev. 59, 239° (1089) on the thermochemty and activity sf akoxyl cals 9. A. Mace., Chem. Rov. 62, 41 (2962), sity of explosives, 10, A Makowsky and L. Lenf, Chem. Re. 58, 627 (2.956), onnitromettane, ‘The following references are ven to at more va soure of raerence than to show pelorty ‘re oer nventignions. a a a u 15. 16. n ». ‘Trudy. Smith and J.C, Calvert, 3. Phys, Chem. 63, 1308 "(1958), "them ecompesition of 2itropropane. ALJ. G. Nicholion, Natare 190, 148 (et, Photaiyan of nizomethane ‘A, K. Galway and FW. M. Jacobs, hem: ‘Soe, p 837, (1959); p. 5081, (1960). “High temperature thermal ‘dicompostion of ammonium perchlorate, F.Solymoal nd L. Reva, Zeit fur Avorg. Chem. 32%, 66 (1963). Thermal Akcomposton of ammonium perchlorate In the presence of snc ex. RD. Smith, Tras. Faraday Soc. 84,1840 (1957). Thermal decomposition of KUN. Brom, and A.C. MeLaren, Proc. Rey. Soe. (London) 266A, 329 (1962). Mechaniom of thermal trsformations i sold amaonium stat, ‘Attracts of Ruan work onstrate etae athe otk of Ke K. Andres and ‘coworker see Chem, Abst, 60,2728 (984), Some recent work on sadaton damage of fxploies, See TB. Panag, 2. Pht ‘Chen 6, 16 (1962). Lend stypbnate, Je Jack, Tet, Farday Soe. 89, 847 (2968). “Thermal decompeation of Idiated led side,‘Mc 708-100 CHAPTER 5 MEASUREMENT OF DETONATION PROPERTIES 51 INTRODUCTION In Chapters 2 and 6, relationships among the

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