# 1911 Encyclopædia Britannica/Hydroxylamine

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​HYDROXYLAMINE, NH$_2$OH, or hydroxy-ammonia, a compound prepared in 1865 by W. C. Lossen by the reduction of ethyl nitrate with tin and hydrochloric acid. In 1870 E. Ludwig and T. H. Hein (Chem. Centralblatt, 1870, 1, p. 340) obtained it by passing nitric oxide through a series of bottles containing tin and hydrochloric acid, to which a small quantity of platinum tetrachloride has been added; the acid liquid is poured off when the operation is completed, and sulphuretted hydrogen is passed in; the tin sulphide is filtered off and the filtrate evaporated. The residue is extracted by absolute alcohol, which dissolves the hydroxylamine hydrochloride and a little ammonium chloride; this last substance is removed as ammonium platino-chloride, and the residual hydroxylamine hydrochloride is recrystallized. E. Divers obtains it by mixing cold saturated solutions containing one molecular proportion of sodium nitrate, and two molecular proportions of acid sodium sulphite, and then adding a saturated solution of potassium chloride to the mixture. After standing for twenty-four hours, hydroxylamine potassium disulphonate crystallizes out. This is boiled for some hours with water and the solution cooled, when potassium sulphate separates first, and then hydroxylamine sulphate. E. Tafel (Zeit. anorg. Chem., 1902, 31, p. 289) patented an electrolytic process, wherein 50% sulphuric acid is treated in a divided cell provided with a cathode of amalgamated lead, 50% nitric acid being gradually run into the cathode compartment. Pure anhydrous hydroxylamine has been obtained by C. A. Lobry de Bruyn from the hydrochloride, by dissolving it in absolute methyl alcohol and then adding sodium methylate. The precipitated sodium chloride is filtered, and the solution of hydroxylamine distilled in order to remove methyl alcohol, and finally fractionated under reduced pressure. The free base is a colourless, odourless, crystalline solid, melting at about 30° C., and boiling at 58° C. (under a pressure of 22 mm.). It deliquesces and oxidizes on exposure, inflames in dry chlorine and is reduced to ammonia by zinc dust. Its aqueous solution is strongly alkaline, and with acids it forms well-defined stable salts. E. Ebler and E. Schott (J. pr. Chem., 1908, 78, p. 289) regard it as acting with the formula NH$_2$·OH towards bases, and as NH$_3$:O towards acids, the salts in the latter case being of the oxonium type. It is a strong reducing agent, giving a precipitate of cuprous oxide from alkaline copper solutions at ordinary temperature, converting mercuric chloride to mercurous chloride, and precipitating metallic silver from solutions of silver salts. With aldehydes and ketones it forms oximes (q.v.). W. R. Dunstan (Jour. Chem. Soc., 1899, 75, p. 792) found that the addition of methyl iodide to a methyl alcohol solution of hydroxylamine resulted in the formation of trimethyloxamine, N(CH$_3$)$_3$O.
Many substituted hydroxylamines are known, substitution taking place either in the α or β position βα (NH$_2$·OH). β-phenylhydroxyl-amine, C$_6$H$_5$NH·OH·, is obtained in the reduction of nitrobenzene in neutral solution (e.g. by the action of the aluminium-mercury couple and water), but better, according to C. Goldschmidt (Ber., 1896, 29, p. 2307) by dissolving nitrobenzene in ten times its weight of ether containing a few cubic centimetres of water, and heating with excess of zinc dust and anhydrous calcium chloride for three hours on a water bath. It also appears as an intermediate product in the electrolytic reduction of nitrobenzene in sulphuric acid solution. By gentle oxidation it yields nitrosobenzene. Derivatives of the type R$_2$N·OH result in the action of the Grignard reagent on amyl nitrite. Dihydroxy-ammonia or nitroxyl, NH(OH)$_2$, a very unstable and highly reactive substance, has been especially studied by A. Angeli (see A. W. Stewart, Recent Advances in Physical and Inorganic Chemistry, 1909).