Nitro-Explosives: A Practical TreatiseSanford, P. Gerald (Percy Gerald)
Science
Nitro-Explosives: A Practical Treatise
Sanford, P. Gerald (Percy Gerald)
Celluloid; Explosives
The principal compound of fulminic acid is the mercury salt commonly known
as fulminating mercury. It is prepared by dissolving mercury in nitric
acid, and then adding alcohol to the solution, 1 part of mercury and 12
parts of nitric acid of specific gravity 1.36, and 5-1/2 parts of 90 per
cent. alcohol being used. As soon as the mixture is in violent reaction, 6
parts more of alcohol are added slowly to moderate the action. At first
the mixture blackens from the separation of mercury, but this soon
vanishes, and is succeeded by crystalline flocks of mercury fulminate
which fall to the bottom of the vessel. During the reaction, large
quantities of volatile oxidation products of alcohol, such as aldehyde,
ethylic nitrate, &c., are evolved from the boiling liquid, whilst others,
such as glycollic acid, remain in solution. The mercury fulminate is then
crystallised from hot water. It forms white silky, delicate needles, which
are with difficulty soluble in cold water. In the dry state it is
extremely explosive, detonating on heating, or by friction or percussion,
as also on contact with concentrated sulphuric acid. The reaction that
takes place upon its decomposition is as follows:--
C_{2}N_{2}O_{2}Hg = Hg + 2CO + N_{2}
(284)
According to this equation 1 grm. of the fulminate should yield 235.8 c.c.
(= 66.96 litres for 284 grms.). Berthelot and Vicille have obtained a
yield of 234.2 c.c., equal to 66.7 litres for one equivalent 284 grms.
Dry fulminate explodes violently when struck, compressed, or touched with
sulphuric acid, or as an incandescent body. If heated slowly, it explodes
at 152 deg. C., or if heated rapidly, at 187 deg. C. It is often used mixed with
potassium chlorate in detonators. The reaction which takes place in this
case is 3C_{2}N_{2}O_{2}Hg + 2KClO_{3} = 3Hg + 6CO_{2} + 3N_{2} + 2KCl.
On adding copper or zinc to a hot saturated solution of the salt,
fulminate of copper or zinc is formed. The copper salt forms highly
explosive green crystals. There is also a double fulminate of copper of
ammonia, and of copper and potassium. Silver fulminite,
C_{2}N_{2}O_{2}Ag_{2}, is prepared in a similar manner to the mercury
salt. It separates in fine white needles, which dissolve in 36 parts of
boiling water, and are with difficulty soluble in cold water. At above
100 deg. C., or on the weakest blow, it explodes with fearful violence. Even
when covered with water it is more sensitive than the mercury salt. It
forms a very sensitive double salt with ammonia and several other metals.
With hydrogen it forms the acid fulminate of silver. It is used in
crackers and bon-bons, and other toy fireworks, in minute quantities. Gay
Lussac found it to be composed as follows:--Carbon, 7.92 per cent.;
nitrogen, 9.24 per cent.; silver, 72.19 per cent.; oxygen, 10.65 per
cent.; and he assigned to it the formula, C_{2}N_{2}Ag_{2}O_{2}. Laurent
and Gerhardt give it the formula, C_{2}N(NO_{2})Ag_{2}, and thus suppose
it to contain nitryl, NO_{2}.
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