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. Kekulé, in 1858, concluded that it was nitroacetonitrile, NO2·CH2·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:
The formulae of Kekulé, 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. Wöhler and K. Theodorovits (Ber., 1905, 38, p. 345), that only compounds containing two carbon atoms yielded fulminates, points to (HCNO)2; on the other hand, Wöhler (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
and also on the production from sodium nitromethane and mercuric chloride, thus CH2 : NO·Ohg → H2O + C : NOhg(hg = ½Hg). H. Wieland and F.C. Palazzo (1907) support this formula, finding that methyl nitrolic acid, NO2·CH : N·OH, yielded under certain conditions fulminic acid, and vice versa (Palazzo, 1907). M.Z. Jowitschitsch (Ann., 1906, 347, p. 233) 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 NO2·CH(CN)·CO·NH2. 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).
FULTON, ROBERT (1765-1815), American engineer, was born in 1765 in Little Britain (now Fulton, Lancaster county), Pa. His parents were Irish, and so poor that they could afford him only a very scanty education. At an early age he was bound apprentice to a jeweller in Philadelphia, but subsequently adopted portrait and landscape painting as his profession. In his twenty-second year, with the object of studying with his countryman, Benjamin West, he went to England, and there became acquainted with the duke of Bridgewater, Earl Stanhope and James Watt. Partly by their influence he was led to devote his attention to engineering, especially in connexion with canal construction; he obtained an English patent in 1794 for superseding canal locks by inclined planes, and in 1796 he published a Treatise on the Improvement of Canal Navigation. He then took up his residence in Paris, where he projected the first panorama ever exhibited in that city, and constructed a submarine boat, the “Nautilus,” which was tried in Brest harbour in 1801 before a commission appointed by Napoleon I., and by the aid of which he was enabled to blow up a small vessel with a torpedo. It was at Paris also in 1803 that he first succeeded in propelling a boat by steam-power, thus realizing a design which he had conceived ten years previously. Returning to America he continued his experiments with submarine explosives, but failed to convince either the English, French or United States governments of the adequacy of his methods. With steam navigation he had more success. In association with Robert R. Livingston (q.v.), who in 1798 had been granted the exclusive right to navigate the waters of New York state with steam-vessels, he constructed the “Clermont,” which, engined by Boulton & Watt of Birmingham, began to ply on the Hudson between New York and Albany in 1807. The privilege obtained by Livingston in 1798 was granted jointly to Fulton and Livingston in 1803, and by an act passed in 1808 the monopoly was secured to them and their associates for a period depending on the number of steamers constructed, but limited to a maximum of thirty years. In 1814-1815, on behalf of the United States government, he constructed the “Fulton,” a vessel of 38 tons with central paddle-wheels, which was the first steam warship. He died at New York on the 24th of February 1815. Among Fulton’s inventions were machines for spinning flax, for making ropes, and for sawing and polishing marble.
See C.D. Colden, Life of Robert Fulton (New York, 1817); Robert H. Thurston, History of the Growth of the Steam-Engine (New York, 1878); George H. Preble, Chronological History of Steam Navigation (Philadelphia, 1883); and Mrs A.C. Sutcliffe, Robert Fulton and the Clermont (New York, 1909).