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XXXV1.-The Action of Nitric Acid on U n s a t z i r a t e d

Uydrocarbons. The Action of Nit& Acid o n
Acetylene.

By KENNEDY
JOSEPH ORTONand PHYLLIS
PREVITE VIOLETMCKTE.

THE action of nitric acid, in contrast to nitrogen peroxide, on

unsaturated (non-arocmatic) hydrocarbons has not yet been thor- -
oughly examined. Such references as are found in the literature
indiaate t h a t complete oxidation to oxalic acid or carbon dioxide
usually occurs. Baschieri ( A t t i R. Accad. Lincei, 1901, [v], 9,
i, 391) and Testoni and Mascarelli (ibid., 1902, [v], 10, i, 442;
Gazzetta, 1903, 33, ii, 319), on examining the action of fuming
nitrio acid on acetylene, obtained, however, a mixture of complex
substances, the, constitution and even the composition of which were
not with certainty elucidated. J. Schmidt (Ber., 1901, 34, 619),
who prepared from stilbene and nitrogen dioxide a dinitrostilbene,
suggested t h a t this behaviour foreshadows the manner of reaction
with acetylene.
We have examined the interaction of nitric acid and acetylene
under varying conditions of concentration, of temperature, and in
the presence of metallic salts, in the first instance to ascertain
whether tetranitromethane or substances such as nitrof orm, which
could be easily converted into tetranitromethane by nitration, were
produced. This quest has been highly successful, and thus a source
of tetranitromethanel, which has a certain usefulness as a high
explosive, from inexpensive materials has been obtained.
Acetylene is absorbed with very great ease by absolute nitric
acid, or by mixtures of nitric acid and sulphuric acid. With dilu-
tion of the nitric acid, the rate of interaction, and hence the readi-
ness of the absorption, decreases. Rise of temperature and the
presence of the catalyst (mercury salt) cause an increase in the
rate of the interaction and readiness of absorption. In these com-
parative statements of the readiness of absorption, i t is to be
understood that the method of bringing the gas and the liquid into
contact is unchanged. Obviously intimate intermingling of a gas
and a liquid will promote absorption and interaction, and may lead
to as ready an absorption by a dilute acid a t low temperature as
is wibh less efficient mixing only found at more favourable tempera-
tures and concentrations of the acid.
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The reaction is accompanied by a small development of heat. On

the scale of our experiments, the temperature was kept thereby a t
5-8O above the laboratory kmperature.
The products of the interaction of acetylene and nitric acid are
various; and the nature and the proportion of these products is
largely determined by the concentration of the acid, by the
temperature, and by the presence of a catalyst o r of sulphuric acid.
The Italian investigators (Zoc. cit.) isolated from the interaction
of acetylene and nitric acid (D 1.52; the proportions are not stated)
a t low temperatures small quantities of different solid products,
some neutral and some acid, which were frequently explosive.
Nitroform was also1 found among the products.
Omitting the products of reduction of nitric acid, the reaction
yields nitrof orm and certain substances, which can be converted
into tet~ranitromethane,carbon dioxide {and a trace of carbon mon-
oxide), and other substances-among them sometimes oxalic acid
(“ O.S.” in the tables)-which cannot be converted into tetranitro-
methane; the latter may predominate in certain circumstances, such
as high or low concentration of the nitric acid or low temperature.
Of the antecedents of tetranitromethane, nitroform usually amounts
to about 75-85 per cent., and the others to about 15 per cent. Of
the metals which we have tried as catalysts, only mercury causes a
marked increase of the proportion of nitroform, etc., and a t the
same time reduces to a very small proportion the by-products which
do nolt yield tetranitromethane. I n fact, the reaction is simplified,
and the acetylene is quantitatively represented by nitrof orm, etc.,
and carbon dioxide. Table I summarises the results of experi-
ments, which illustrate the1 elff ect of concentration of acid, tempera-
ture, presence of mercury nitratel, or of sulphuric acid.
U-nder (‘ t.n.m.” i n the table is the! quantity of tetranitromethane
(as a percentage of t h e acetylene reacting) which can be obtained
from the product by a treatment described later. This quantity is a
convenient measure of the extent to’ which nitroform and the other
anhoedents are produced undelr given conditions. If 2 moles of
tetranitromethane were formed from one of acetylene, ‘‘ .t.n.m.”
would amount to 1508 per cent. in a quantitative yield, or if 1 mole
of acetylene yields one of tetranitromethane, which is far more
probable, 754 per cent.
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TABLEI.
A . Varying Concentration of Nitric Acid. Temperature, 1 5 O .
C2H2absorbed
by 100 grams of -‘t.n.m.” ag per-
Experi- Percentage of nitric acid. centage of C,H,
ment. nitric acid. Litres. absorbed.
1............... 100.0 1.610 75.6
2. .............. 97.5 1.516 163.0
3............... 95-0 1.296 238-0
4............... 90.0 1.097 160.0
5............... 85.0 0.546 158.0
6. .............. 70.0 1.043 37.4

23. Sulphuric 9cid present. Temperature, 1 5 O .

C2H, ab- C o g evolved
sorbed per per g r t.n.m.”

100 grams 100 grams as percent-

of nitric of nitric C02/C2H2 age of “ O.S.”as
Experi- H2S01/ acid. acid. by vol- C2H2ab- a percent-
ment. HN03. Litres. Litres. ume. sorbed. age.
7......... 0-11/1 1.336 0.295 0.25/1 148.5 77.9
8......... 0-5 /l 1.41 0-137 0*09/1 0.0 95.6
9......... 0.5 /1 1.615 1.092 0*67/1 129.0 57.8
10 ......... 2-6 /1 1,774 0.17 0.1 /1 0.0 95.9

I n Experiment 9, 0.33 per cent. of mercuric nitrate was present.

I n Experiments 6 and 10 the temperature was 30°.

C . Mercuric Nitrate present, 0.66 per cent. Temperature, 15’.

C,H2 ab- CO, evolved
sorbed by per
100 grams 100 grams “ t.n.m.”
Percentage of nitric of nitric C02/C,H2 as percent- “ O.S.” as
Experi- of nitric acid. acid. by vol- age of apercent-
ment. acid. Litres. Litres. ume. (3,332- age.
11......... 90 1.490 2.27 1-5%/1 204 9-82

D. Temperature Varied.
T”.
12... 95 1.20 0.54 0.39411 104 61-0
13... 15 95 1.296 1-04 0.8 /1 238 44.0
14... 30 95 1.49 1-565 1.05,/1 33 1 25-4

E. Mercwric Nitrate, 0.3-0-66 per cent. Telmperature, 30°.

15......... 95 1.571 2.22 1-41/1 523 0.0
16......... 100 .3456 4.87 1-4 /1 410 2.4
17......... 70 0.581 1.1 1-91/1 47 1.9

It will be seen that both a high concentration (in the absence

of mercury salt) and a low concentration of nitric acid are unfavour-
able to the formation of nitroform and the other antecedents of
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tetranitromethane. The optimum concentration is about 95-97

per cent. Obvioasly in the interaction of nitric acid and acetylene
the acid becomes diluted, and the yield will only be a maximuni
when a small quantity of acetylene is absorbed by this acid (Expt.
15). 'To obtain the maximum quantity of nitroform (and tetra-
nit'romet'hane) in one operation the absorption of 3.5-3.7 litres of

FIG. 1.
65

70

76

80

85

90

95

100
0 1 2
Moles carbon dioxide or nz'trofoma.
Carbon diox'de: no mercury present ......
............ - _ - - -
~

Carbon dioxide : mercury present

Nitroform: no mercury present ............
- . - .- . -
Nit rof orm : mercury present ..................
................................

acetylene, by 100 grams of "100 per cent." nitrio acid, t o which

0.33 gram of mercury nitrate has been added, is best (Expt. 16).
The yield of nitroform is then about 14-2 grams, and of teitranitro-
methane, 16.7 grams (or 410 per cent,). A t the lower concentra-
tions (70 per ceat.) of nitrio acid, oxidation to carbon dioxide
increases; the ratio CO, : C,H, (by volume, molar) approaches,
and i n Expt. 17, under the influence of mercury nitrate, flearly
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reaches 2 : 1. The dependence of the products of the reaction on

the concentration of the nitric acid is well shown in Fig. 1. This
indicates first the volume of carbon dioxide for one volume of
acetylene, plotted against the concentration of nitric acid, (a)when
no mercury salt has been added, ( 6 ) when mercury salt is present,
and secondly the moles of nitroform for one mole of acetylene under
similar different conditions; about’ 1 litre of acetylene has reacted
with 100 grams of nitric acid.

Effect of the Presence of Various illetallic Salts.

The effect of the presence of small quantities of salts of platinum,
silver, uranium, copper, and mercury on the reaction between nitric
acid and acetylene has been examined. The metals were added as
nitrates, except platinum, which was i n the form of chloroplatinic
acid. The quantitiies used were molar equivalents of the amount
of the mercury nitrate required to form a 0.33 per cent. solution.
I n 95 per cent,. nitric acid solution was complete, or nearly com-
plete, except with platinum, when a heavy, yellow precipitate
appeared and remained throughout. With copper a precipitate
appeared during the reaction. Table I1 summarisw the results.
The nitric acid was diluted to 95 per cent., and the temperature
was 30°.
TABLE
11.
C2H2 co2
absorbed evolved
by 100 Per Percent- Percent- Percent-
grams 100grems “ t.n.m.” age of C age of C age of C
of nitric of nitric as a per- in C,K, in C,H, in C,H,
Experi- acid. acid. centage becoming becoming becoining
ment. Metal. Litres. Litres. of C,H,. “ t.n.m.” CO,. “ O.S.”

18 ...... Pt 2.68 2.25 203 13.5 41.8 44.7

19 ...... Ag 2-73 2-20 221 14-7 49.3 36.0
20 ...... Ur 2.60 3-32 222 14.9 63.6 21.5
21 ...... cu 2.65 2.64 37 1 24-2 51-5 24.3
22 ...... Hg
23 ...... None
3.02
2-81
4.38
2.72
453
341
29.18
22.6
‘70.81
49.0
0.0
28.4

Mercury stands alone in having a markedly favourable efffect 011

the rate of interaction, and hence on the readiness of absorption.
Again, mercury is the only metal of those examined which exerts
a beneficial influence on the production of nitroform and hence
tetranitromethane. All the metals, save copper, favour oxidation
of the acetylene, a t the expense of the production of nitroform,
etc.; uranium is peculiarly active in this respect. The experiment
in which mercury is present stands out in that other substances ”
are absent. Platinum has the opposite effect, and causes an increase
in the proportion of by-products.
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The proportion of mercury is important; the most faxourable

proportion lies below 1 per cent. Table I11 summaries the resulb
of experiments made with the object of ascertaining exactly the
best proportion, which is obviously 0.3-0.4 per cent.

TABLE111.
Temperature, 30°.
C2HZab- COa
-
Per sorbed evolved Percent- Percent- Percent-
cent- by 100 per 100 (( we. age age.
age grams grams t.n.m.” of C in of C in of C in
EX. of. Hg(NOl)gofacid.nitric of nitric as aper- C,H, be- C,H2be- C,H,.be-
pen- nitric as per- acid. centage coming coming coming
ment. acid. centage. Litres. Litres. of CzH2. “t.n.m.” COz. “ O.S.”
24...... 95.0 0.66 3-06 4.39 383 25.4 71.5 3-1
25...... 95.0 0.33 3-02 4.38 453 29.2 70.8 0.0
26 ...... 95.0 0.33 1-55 1.62 552 37.1 62.7 0.2
27 ...... 97.5 0.28 3.16 4.34 429 28.5 68.2 3.3
28...... 95.0 0.165 3.03 3-83 431 28-6 63.1 8.2
29...... 95.0 0.0 2.81 2.72 341 22.6 49.0 28.4

The mercury salt appears to have more than one effect on the
interaction of acetylene and nitric acid, and at different concentra-
tions as well as a t different temperatures one or other of these
effects may be the more marked.
The most characteristic effect is the elimination of products other
than the precursors of tetranitromethane or carbon dioxide. These
products have been grouped together under “ other substances,”
but two important groups can be distinguished. I n the first place,
when the nitric acid is highly concentrated, substances are produced
in considerable quantity which do not on further treatment-
“ nitration ”-yield tetranitromethane. These are probably the sub-
stances isolated by Mascarelli and his co-workers. Thus we find t h a t
with 100 per cent. nitric acid a t 1 4 O “ O.S.” may represent 86 per
cent. of the acetylene absorbed, but in the presence of a mercury
salt a t 30° “ 0 . S . ” is reduced to zero. The large increase in the
yield of tetranitromethane from less than 100 per cent. in the first
experiment to 460 per cent. in t8he8 secolnd sholws t h a t the effect of
a mercury salt is to cause the1 substitution of precursors of tetra-
nitromethane for these other substances.
In less concentrated nitric acid, about 95 per cent., mother effect
becomes apparent. Now in the absence, of mercury an important
by-product is oxalic acid [Ca(@02),,H20gave CaCO,= 69.15. Calc.,
CaCO,= 68.50 per cent.], which can be readily isolated from or =ti-
mated i n the product. When 1.5 litres of acetylene are absorbed by
100 grams of nitric acid (95 per cent. a t 30°), as much as 25 per
cent. of the acetylene appears as oxalic acid. I f a mercury salt is
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present, however, only a very small quantity of oxalio acid is

found, and there is a correspondingly large increase in the carbon
dioxide. Direct experiment shows t h a t a mercury salt does not
cause the oxidation of oxalic acid by nitric acid, and it seems prob-
able, therefore, that now, i n the presence of mercury salt, some
intermediary other than oxalic acid is directly oxidised to carbon
dioxide.
The presence of a mercury salt also modifies the reaction of
acetylene with a mixture of nitric acid and sulphuric acid. A com-
parison of experiments 8 and 9 (table I) demonstrate8 this effect.
It will be seen that the precursors of tetranitromethane are only
produced in the presence of a mercury salt, and, further, t h a t con-
currently there is more oxidation of the acetylene.
The mercury salt is without effect on the conversion of primary
products of the interaction of acetylene and nitric acid into tetra-
nitromethane, for addition after the absorption of the acetylene
does not affect the yield of tetranitromethane in the subsequent
treatment. ‘I’he mercury salt then determines only the course of
the primary interaction.
Formation of Nitroforin and other Precursors of Tetranitro-
methane.-In order to account for the formation of tetranitro-
methane in the interaction of diacetylorthonitric acid, aoetyl nitsate
or nitric acid and acetic anhydride, Pictet and Genequand (Ber.,
1903, 36, 2225) suggested that nitroform, which they isolated, or
even trinitroacetic acid, preceds tetranitromethane. The formation
of tetranitromethane by the nitration of nitrof orm had earlier been
demonstrated by Schischkov (ilnnalen, 1861, 119, 248), who used a
mixture of nitric and sulphuric acids.
Nitroforni, as its characteristic ammonium salt, can easily be
isolated from the product. The estimation in the complex acid
mixture is not so simple; but after removal of the “nitrous acid ’I

by ammonium nitrate the nitroform can be distilled in a current of

steam or extracted with ether, and then titrated in the distillate or
extract with alkali hydroxide, or, better, with permanganate.
The quantity of nitroform thus determined does not represent
more than 85-87 per cent. of tbe tetraniti-omethane which can be
obtained from the product, and is in some circumstances less. No
want of accuracy which can be detected in the method of estima-
tion of the nitroform will account for this discrepancy between the
quantities of nitroform and tetranitromethane.
Clear evidence t h a t the product contains substances other than
nitroform which yield tetranitromethane when heated with sul-
phuric acid is adduced by the following experiment. The product
was obtained by passing acetylene into 95 per cent. nitric acid at
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30°, 0.33 per cent. of mercuric nitrate being present. The nitro-
form found in a portion of the fresh product was equivalent t o
15.6 grams of tetranitromethane, whereas the product yielded
20 grams. An equal portion of the product was heated at 8 5 O for
two hours before treatment with sulphuric acid. The yield of
tetranitromethane in this portion was now 16.6 grams, and the
nitroform therein was equivalent to 15.3 grams.
The yield of tetranitromethano also falls off, rapidly at first, if
the product is kept for some time at the ordinary temperature,
whereas the decomposition of nitroform in the product, which is also
observed, is very much slower.
0bviously substances which can yield tetranitromethane have
been destroyed by heating or keeping the product. It is clear that
they have not been converted into nitroform, for the quantity of
nitroform is approximately unchanged and, it is to be noted, after
the heating, is nearly equivalent to the tetranitromethane.
The formation of nitroform from acetylene and nitric acid can
be represented as the result of a simple addition:
CH:CH + ZHNO, +(NO,)&H*CH(OH), --+
(NO,),CH*CHO +(NO,),CH*CO,H either +
(NO,),CE€~+ CO, o r possibly (NO,),CH-CO,H + HNO, --+
(N02)3C*C0,H-+ (NO,),CH + (20,.
(The addition of nitrogen peroxide is not considered.)
Dinitromethane very readily reacts with nitrous acid (Duden,
Ber., 1893, 26, 3003), yielding the isonitrowcompound, which
under the conditions would probably be oxidised t o nitroform,
thus :
(NO,),CH, +- HNO, --+ (NO,),C:NOH -3 (NO&CH.
The isonitroso-compound does not appear usually t o be present in
the product, f o r in normal experiments there is no marked indica-
tion of the blood-red colour which it yields with alkalis (Duden,
Zoc. c i t . ) . A t lower dilutions of nitric acid, however, this reaction
is obvious on rendering the product alkaline.
When nitroform is produced by the routes indicated above, one
mole of acetylene yields one mole of nitroform and one mole of
carbon dioxide; hence as a maximum only 50 per cent. of the
carbon of the acetylelne would become nitroform.

E x P E R I M E N T AL.
The essential p a r k of the apparatus are shown in Fig. 2.
Acetylene is absorbed so readily, at least by sufficiently concen-
trated nitric acid a t moderate temperatures, that the Drechsel
bubbler ( A ) , in whioh the end of the inlet tube is somewhat con-
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stricted, serves as the reaction vemel; the bubbles of gas are broken
by a layer of glass beads. This bubbler, which is nearly full, is
immersed i n a bath maintained at a constant temperature,
usually 30°.
The second bubbler ( B ) , which is placed in a cooling-bath, con-
tains 30 C.C. of sulphuric acid (96-97 per cent.); all the oxides of
nitrogen coming from ( A ) are absorbed in (23). No nitrous or
nitric oxides have been found in the gas, which passes through the
sulphuric acid. Safety devices for meeting a development of
negative pressure or a sudden positive pressure are placed at a, b,
and c . Samples of gas for analysis can be drawn off from the pipe
line a t e and f.
The a’cetyleine, which was not purified, was dried by calcium

II

at: C

i
chloride. I n this apparatus, good absorption (more than 90 per
cent. under the best conditions) was obtained up. t o a speed of
400 C.C.per hour. Usually the speed was considerably less, about
150-200 C.C.per hour.
The nitric acid was prepared from a crude, fuming nitric acid
(D15 1’5), which contained much iodine as iodic acid, by distilling
from a n equal weight of sulphuric acid. The distillate had
D15 1.545; the acid contained 2-2 per cent. of “nitrous acid,” as
determined by potassium perm angan’ate .
Mercuric nitrate (0.5 gram:0*33 per cent?.) is placed in t h s
bubbler, then wate’r (7.5 C.C. when a 95 per cent. nitric acid is
used), and finally the nitric acid (138-6 grams=90 c.c.). The
mercuric nitrate dissolves completely; the quantlity of 95 per cent.
n i t r i o acid just given will dissolve 1.2-1-3 grams at the ordinary
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temperature. Absolute nitric acid dissolves very little mercuric

nitrate which, at the beginning 09 the experimefnt, is in suspension,
b u t dissolves later.
It is not advantageous to pass more) than 4-5-4.6 litres of
acetylene into A , although when absolute nitric acid is used this
may be increlased to 5 litrels. As the reaction proceeds, the nitric
acid is diluted; not only is the relaction then morel tardy, and hence
the absorption poorer, but oxidation of the acetyleinei, and hence
the evolution of carbon dioxide, becornea more prominent. A t the
early stages of the react$ion,very little gas leaves ( A ); later, oxideis
of nitrogen and carbon dioxide are evolved, towards the end of the
experiment vigorously.
The results of typical experiments are summarised in table IV.

TABLEIV.
I n all experiments, 0.33 per cent. of mercury nitrate was p r a e n t .
C,H, COB
Per- absorbed evolved Percent- Percent- Percent -
cent- by 100 by 100 age age age
age grams grams “t.n.m.” of C in of C in of C in
Ex- of of nitric Nitro- of nitric as a per- C2H2 be- C2H, be- C2H2. be-
peri- nitric acid. form. acid. centage coming coming cormng
ment. acid. Litres. Grams. Litres. of C,H,. “t.n.m.” CO,. b b O.S.”

30 ...... 95-0 3-068 10.3 4-38 436 28.94 71.04 0.0

31 ...... 97-5 3.163 10.5 4.34 430 28-8 68.5 2-3
32 ...... 100.0 3.456 11.0 4.87 410 27.6 70.5 2.4
33... ... 100.0 2.883 9.9 4.07 448 29.73 70.3 0.0

Preparation of Nitroform.-The product, is diluted 1 to 10, and

then the nitrous acid removed by ammonium nitrate, 20 grams to
100 C.C. of the diluted prolduct. The nitrolform is then extracted
by ether, preferably in a continuous apparatus. The &hereal
extract is concentrated and added to alcoholia ammonia. or alcoholic
potassium hydroxide, when the salt crystalliaes out. From 100
grams of the product prepared under the best conditions, about
15 grams of the crude ammonium salt can be obtained.
Analysis of the Product; Nitroform, Nitrous and Nitric AcicFs.
-The estimation of nitrous acid cannot be made directly on the
product, for other substances which reduce permanganate are
present. Two procedures have been followed. The permanganate
titra of the product diluted 1 in 10 is determined; then either the
nitrous acid is removed by aspiration or by boiling with ammonium
nitrate (Gailhat, J. €’harm. Chim., 1900, [vi], 12, 9 ; Gerlinger,
Zeitsch. angew. Chem., 1902, 14, 1250; they both use ammonium
chloride). I n the aspiration, it is not necessary t’o relmove the
whole of the nitrous acid, which is it very lengthy process. A t a
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given temperature and with a given air current, the percentage

loss of nitrous acid from the solution follows the well-known law,
and is independent of the initial concentration. A t 16O, w i t h the
rate of air current 0.1 litre per minute, trials w ith known solutions
of nitrous acid a t various concentrations in aqueous nitric acid, and
with kmwn solutions of nitroform and nitrous acid in 7-8 pelr
cent. nitric acid, show t h a t 73.3 (72.8-73-9) per cent. of nitrous
acid disappear i n one hour. After the partial removal of the
nitrous acid by aspiration or the complete removal by ammonium
nitrate, the residual permanganate titre is determined, whence the
‘‘ nitrous acid ” can be calculated. Determinations of the nitrous
acid made by these two methods agree fairly well, but the method
of aspiration is probably the inore trustworthy.
Determination of Nitroform.-Nitroform can be titrated in
aqueous solutioln by alkali hydroxide in the preselnce of phenol-
phthalein (Hantjzsch and Rinckenburger, Ber., 1899, 32,631). We
have devised a method, depending on the reduction of perman-
ganate in the prese’nce of sulphuric acid, which will be discussed
more fully in another place. Recently, Erich Schmidt (Ber., 1919,
52, [B], 400) has described a procedure in which nitron is used as
precipitant; this we have not yet tested, nor would it be easily
applicable t o our conditions, owing t o the presence of nitria acid.
The product contains, besides nitrous acid and nitroform, other
substancels (for example, oxalic acid) which reduce permanganate.
After removal of the nitrous acid, the nitroform may be extracted
with elther and then titrated, or, prefelrably, distilled off and
titrated with permanganate.
The following is a typical analysis: 2-5 C.C. of the ‘(product”
are added to 18-45 C.C. of N/Z-N-alkali hydroxide; 5 C.C. are
diluted with 10-15 C.C.of water, and 2-3 grams of ammonium
nitratel added. The mixture is gently boiled f o r several minutes
(five to ten), and then diluted t o 100 c.c., acidified with 5-10 C.C.
of 10 per cent. sulphurio acid, and distilled until the distillate is
colourle\ss (thirty minutes). The distillate may be: collected in
water or N/lO-alkali; it is finally titrated with N/lO-KMnO,.
One C . C . of N/lO-KMnO, is equivalent t o 151/80,000=0~0019gram
of nitroform.
After destruction of nitrous acid and extraction of nitroform by
ether, the rssidue still reduces permanganate. The reduction is
b u t small under conditions most favoarabla for the preparatioln of
nitrof orm or tetranitromethane. Some, and sometimes mostl, of
the reduction of the permanganate by the residue is t o be
attribut3eldto oxalia acid.
A rough estimate of the nitric acid in the product can be made
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by deducting from the total alkali titre the alkali titre equivalent
t o the permanganate tlitre of the diluted product. As this deiduc-
tion do= not amount to more than 10 per cent. of the total alkali
titre, a rough estimate of the nitric acid remaining is possible.
I n a typical experiment, in which 4.27 litres of acetylene werel
absorbed by 138.6 grams olf nitric acid (diluted t o 95 per cent.),
about 75 grams of nitric acid remaineld in the1 product,, which
weighed 123.5 grams. Deducting nitric acid, nitrous acid, and
n i t d o r m , the water i n the product comes t o 30 grams.
Analysis of Gases evolzted during t h e Interaction of Acetylene
and Nitric Acid.-The gas coming from the bubbler ( B ) is collected
over a neutral, saturated calcium chloride solution in a large
vessel of known capacity; the last part of the gas i n an experi-
ment is measured in a graduateid vessel. Both carbon dioxide and
acetylene are less readily soluble in saturated calcium chloride1 than
i n other saline solutions; a t 14O, carbon dioxide has a solubility
of 0.1 in 1, and acetylene 0.08 i n 1, by volume.
The gas evolved during the heating of the product with sulphuric
acid was collected in a similar manner. The liquid nearly filled
the flask, which was ground o n t o a narrow condenser tube; this
tube was carried o'n as a delivery tube for the evolved gas.
Table I V shows the large vollumes of gas (carbon dioxide)
collected. Nine-tenths, or rather more, are evolvetd during the
inteiraction of aceitylene and nitric acid when mercury is present,
and the relmaindeir during the heating with sulphuric acid. I n the
absence: of mercury, 2/3-3/4 of the gas passes off at the first
stage, and 1/4-1/3 a t the second stage. These ratios strictly
apply only to tlhe carbon dioxide, which, however, largely pre-
dominates, especidly i n the first stage, less exactly to the total
gas. The gas consists in the main of carbon dioxidel with small
percentages of acetylene and carbon monoxidei, and traces of air.
The gas given off in the heating contains much oxygen (up t o
40-50 per cest.) from the interaction of nitric and sulphuric
acids.
The gas was analysed in a " Bone and Wheeler" apparatus. The
acetylene was absorbed by a, 5 per cent. solution of potassium
bromide saturateld wit<hbromine ; the absorption is somewhat slow
towards the end, but complete. After removal of the bromine
vapour by the alkaline reagent, the carbon monoaide is absorbed
by the ammoniacal cuprolus chloride reagent. We have teisted
exhaustively this proceidure o n known mixtures of gases, and found
it quite accurate. Usually, the gas of the first stage will contain:
COz=75-80, C,H,=5-6, C O = a t most 1 per cent.
Preparation. of Z'e tranitrome t hune .-Originally, t et rani t ro-
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methane was prepared by Schischkov (Zoc. cit .) from trinitroaceto-

nitrile. Later, it was obtained in the exhaustive nitration of
aromatic hydrocarbons (Will, Ber., 1914, 47, 704 ; Claessen,
D.R.-P. 184229) by the action of diacetylorthonitric acid or acetyl
nitirate on acetic anhydride (Pictet and Genequand, Zoc. cit. ; Pictet
and Khotinsky, Compt. r e d . , 1907, 144, 210), or from nitrogen
pentoxide on acetic anhydride (Schenck, D.R.-P. 211198, 211199),
or from nitrio acid o n acetic anhydride (Farbenfabriken vorm. F.
Bayer & Co., D.R.-P. 224057; Berger, Compt. rend., 1910, 151,
813; Chattaway, T., 1910, 97,2099).
I n preparing tetranitromethane f rom a hydrocarbon by
elxhaustive nitration, it is obvious t h a t a low proportion of hydrogeln
t o carbon, such as obtains i n benzene, naphthalelne, or acetylene,
is dwirable in order to economise nitric acid. Not only does the
oxidation of a large proportion of hydrogen entail a correspond-
ing loss of nitric acid, but the nitrating agent becomes diluteid
with water, and hence less efficielnt. On these grounds, benzene o r
its derivatives, o r naphthalene derivatives, o r acetylene are the
most suitable substancee. For various reasons, acetylene would be
an excellent source of tetranitromethane. Whilst only some
4-5 per cent. of benzene nitrated can be converted into tetranitro-
methane, it has been shown in the foregoing t h a t some 37 per
cent. of the acetylene appears as this substance under suitable
conditions.
'The product from the interaction of acetylene and nitlric acid
contains very little tetranitromethane. If it is heated or first
mixed with phoephoric oxide, sulphuric acid, o r fuming sulphuric
acid and t;hen heateld, tetranitromethane is formed.
A satisfactory procedure, in which all the nitroform is converted
into tetranitromethane and the maximum yield is obtained, is t o
mix the product from 90 C.C. of 100 per cent. nitric acid with
190-380 grams of sulphuric acid o r sulphuric acid containing
25 per cent. of sulphur trioxide. The sulphuric acid is added to
the product, and care is taken t h a t the temperature does not rise.
The sulphuric acid from the bubbler ( B ) , which contains a little
nitroform, is also introduced. The mixture may be then directly
distilled, but it is preferable to heat it, finally to 90-95O, under
reflux until gas ceases to be evolved; this operation usually occupies
about four hours. For reasons given in the foregoing, it is
important t h a t the product is mixed with sulphuric acid as soon
as possible after t,he passagel of the aceltylene. That this mixture
should then be kept f o r some time before heating o r distilling is
immaterial.
On cooling, much of the tetranitrom&hane will appear as an
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oil, or even crystals; it may be collected by means of carbon tetra-

chloride or petroleum, but isolation by distillation is simplest.
The effect of certain variations in this procedure may be noted.
The proportion of sulphuric acid may even be reduceld below the
limits giveln in the foregoing without producing any considelrable
diminution in the yield. Even if the proportion H,SO, :HNO, =
0-75 : 1 by weight, the yield of tetranitrometlhane is olnly reduced
by 10 per cent. The heiating or the distillation of such a mixture
is, however, attelnded with risk, as sudden decompoeition, with
evolution of gas, may ensue. ,
The addition of 20-25 grams of nitric acid t o the mixture of
the product and sulphuric acid before heating or distilling leads
t o a n improvelment of the yield (some 10 per cent.), especially if
the conditions have otherwise been unfavourable; for example, i f
an excessive volume of acetylene has been passed into the nitric
acid, or the temperature has been low, o r the nitric acid too dilute.
Under the conditions outlined in the foregoing, such addition of
nitric acid has little, if any, effect.

As example8 of the operation, the two following may be cited.

The largest quantity of tetranitromethane (23.2 grams: 410 per
cent. on the acetylene) in one operation was obtained by passing
5 litres into 138.6 grams (90 c.c.) of absolute nitric acid at 30° with
0.55 gram of mercuric nitrate in suspension. A better yield, of
453 per cent., was obtained by passing 4 . 6 litres into the same
quantity of nitric acid diluted with water t o 95 per ceat. at the
same temperature and with the same quantity of mercuric nitrate
in solution ; the weight of tetranitromethane isolated was 22.3
grams.
The PzcrificatioB and Properties of Tetranitromethane.-The
crude material, after washing with water, is nearly colourless, and
melts a t 13.4-13.5O. Thorough washing with dilute aqueous
sodium carbonate does nolt change the melting point. After padial
freezing and pouring off the remaining liquid threle times, the sub-
stance m e h d a t 13*75O, and the melting point was not raised by
further fractionation. It has D:%'i1.65009.
COLLEGE
UNIVERSITY OF N. WALES,
BANGOR. [Received, Januavy 14th, 1920.7