[ 31 ] 



IV. 



THE ACTION OF SULPHUE CHLOEIDE ON AMMONIA AND ON 



OEGANIC BASES. 



By ALEXANDEE KILLEN MACBETH, M.A., D.Sc, E.I.C, 



AKD 



HUGH GEAHAM, M.Sc, A.I.C. 



[Read January 22. Publislied Febru.iry 27, 1923.] 



The general similarity in chemical properties between sulphur and oxygen 

 is too well known to require anything other than a brief reference. The 

 elements form an analogous series of compounds in the fields of both organic 

 and inorganic chemistry ; and the consideration of these striking analogies 

 fostered the hope that it might be possible to prepare a series of nitrogen 

 sulphides corresponding to the oxides of oxygen. It was also hoped to 

 isolate some nitrogen-sulphur compounds parallel to the oxy-acids of nitrogen. 

 A memoir of Gregory^ appeared in the " Journal de Pharmacie," in which 

 he affirmed that he had isolated a new compound to which he assigned the 

 formula NS. Soubiernan- also described the preparation of the same 

 compound, and later work by Eordos and Gelis^ showed that this sulphur 

 nitride may be prepared by the action of ammonia on sulphur chloride 

 dissolved in carbon disulphide. They also pointed out that Gregory's 

 compound was probably contaminated by sulphur, as the amethyst coloration, 

 which he stated his compound gave on treatment with alcoholic potash, is 

 not given by pure nitrogen sulphide, but is readily obtained when the 

 compound is mixed with sulphur. Upwards of forty years afterwards, 

 Schenck* reviewed the methods for preparing nitrogen sulphide, and showed 

 that the substance did not possess the simple formula previously accepted 

 but existed as the polymer N4S4. In the same year Muthmann and Clever^ 

 prepared a second sulphide of nitrogen by heating N4S1 with carbon 

 disulphide under a pressure of five atmospheres, and established the formula 

 N2S5 for the compound. More recently, Burf^ has succeeded in transforming 

 the orange-coloured sulphur nitride N4S4 into a blue-coloured variety of the 

 same empirical formula. 



1 Journal de Pharmacie, 1836, 22, 301. * Ibid., 1896, 290, 171. 



2 Annalen der Chemie, 1838, 67, 71. ^ Zeitschrift anorg. Chemie, 189G, 13, 200. 



3 Annalen der Chemie, 1851, (3) 32, 385. « Trans. Clieni. Soc, 1910, 97, 1171. 



R.I. A. PKOC, VOL. SXXVI, SECT, B, [S] 



