GEOGRAPHICAL NAMES |
FULMINIC ACID, Hcno or H 2 C 2 N 2 0 2, an organic acid isomeric with cyanic and cyanuric acids; its salts, termed fulminates, are very explosive and are much employed as detonators. The free acid, which is obtained by treating the salts with acids, is an oily liquid smelling like prussic acid; it is very explosive, and the vapour is poisonous to about the same degree as that of prussic acid. The first fulminate prepared was the " fulminating silver "of L. G. Brugnatelli, who found in 1798 that if silver be dissolved in nitric acid and the solution added to spirits of wine, a white, highly explosive powder was obtained. This substance is to be distinguished from the black " fulminating 1 A name misapplied in the southern hemisphere to Diomedea naelanophrys, one of the albatrosses.
silver " obtained by C. L. Berthollet in 1788 by acting with ammonia on precipitated silver oxide. The next salt to be obtained was the mercuric salt, which was prepared in 1 799 by Edward Charles Howard, who substituted mercury for silver in Brugnatelli's process. A similar method is that of J. von Liebig (1823), who heated a mixture of alcohol, nitric acid and mercuric nitrate; the salt is largely manufactured by processes closely resembling the last. A laboratory method is to mix solutions of sodium nitromethane, CH 2: NO(ONa), and mercuric chloride, a yellow basic salt being formed at the same time. Mercuric fulminate is less explosive than the silver salt, and forms white needles (with 2H 2 O) which are tolerably soluble in water. The use of mercuric fulminate as a detonator dates from about 1814, when the explosive cap was invented. It is still the commonest detonator, but it is now usually mixed with other substances; the British service uses for percussion caps 6 parts of fulminate, 6 of potassium chlorate and 4 of antimony sulphide, and for time fuses 4 parts of fulminate, 6 of potassium chlorate and 4 of antimony sulphide, the mixture being damped with a shellac varnish; for use in blasting, a home office order of 1897 prescribes a mixture of 4 parts of fulminate and 1 of potassium chlorate. In 1900 Bielefeldt found that a fulminate placed on top of an aromatic nitro compound, such as trinitrotoluene, formed a useful detonator; this discovery has been especially taken advantage of in Germany, in which country detonators of this nature are being largely employed. Tetranitromethylaniline (tetryl) has also been employed (Brit. Pat. 13340 of 1905).. It has been proposed to replace fulminate by silver azoimide (Wdhler & Matter, Brit. Pat. 4468 of 1908), and by lead azoimide (Hyronimus, Brit. Pat. 1819 of 1908).
The constitution of fulminic acid has been investigated by many experimenters, but apparently without definitive results. The researches of Liebig (1823), Liebig and Gay-Lussac (1824), and of Liebig again in 1838 showed the acid to be isomeric with cyanic acid, and probably (Hcno) 2, since it gave mixed and acid salts. Kekule, in 1858, concluded that it was nitroacetonitrile, NO 2 CH 2 CN, a view opposed by Steiner (1883), E. Divers and M. Kawakita (1884), R. Scholl (1890), and by J. U. Nef (1894), who proposed the formulae: C: NOH N: CH CH: NO C: NOH, O ? N: COH, CH: NO, C: NOH. Steiner, Divers, Scholl, Nef.
The formulae of Kekule, Divers and Armstrong have been discarded, and it remains to be shown whether Nef's carbonyloxime formula (or the bimolecular formula of Steiner) or Scholl's glyoxime peroxide formula is correct. There is some doubt as to the molecular formula of fulminic acid. The existence of double salts, and the observations of L. Willer and K. Theodorovits (Ber., 1905, 3 8, P . 345), that only compounds containing two carbon atoms yielded fulminates, points to (Hcno) 2; on the other hand, Wohler (loc. cit. p. 1351) found that cryoscopic and electric conductivity measurements showed sodium fulminate to be NaCNO. Nef based his formula, which involves bivalent carbon, on many reactions; in particular, that silver fulminate with hydrochloric acid gave salts of formylchloridoxime, which with water gave hydroxylamine and formic acid, thus - C: NO OAg -)HC?C? Ag ?HC 'OH ?HCO 2 H-f-H 2 N OH, and also on the production from sodium nitromethane and mercuric chloride, thus CH 2: NOOhg - > H 2 O -I-C: NOhg (hg = 2 Hg). H. Wieland and F. C. Palazzo (1907) support this formula, finding that methyl nitrolic acid, NO 2 CH: N-OH, yielded under certain conditions fulminic acid, and vice versa (Palazzo, 1907). M. Z. Jowitschitsch (Ann., 1906, 347, p. 2 33) inclines to Scholl's formula; he found that the synthetic silver salt of glyoxime peroxide resembled silver fulminate in yielding hydroxylamine with hydrochloric acid, but differed in being less explosive, and in being soluble in nitric acid. H. Wieland and his collaborators regard " glyoxime peroxide " as an oxide of furazane (q.v.), and have shown that a close relationship exists between the nitrile oxides, furoxane, and fulminic acid (see Ann. Rep., London Chem. Soc., 1909, p. 84). Fulminuric acid, (Hcno) 3, obtained by Liebig by boiling mercuric fulminate with water, was synthesized in 1905 by C. Ulpiani and L. Bernardini (Gazetta, iii. 35, p. 7), who regard it as NO 2 -CH(CN)CONH 2. It deflagrates at 145°, and forms a characteristic cuprammonium salt.
The early history of mercuric fulminate and a critical account of its application as a detonator is given in The Rise and Progress of the British Explosives Industry (International Congress of Applied Chemistry, 1909). The manufacture and modern aspects are treated in Oscar Guttmann, The Manufacture of Explosives, and Manufacture of Explosives, Twenty Years' Progress (1909).
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