Macbeth and Graham — Action of Sulphur Chloride on Ammonia. 33 



excess chlorine results in the liberation of free nitrogen, while if the state 

 of chlorination is lower free sulphur is found as a reaction product. 



In order to obtain the nitrogen-sulphur compounds formed in the above 

 reaction, the experimental methods are somewhat modified. Ammonia 

 dissolved in chloroform is added to an ice-cold solution of sulphur chloride 

 in the same solvent until a permanent alkalinity is developed. The solvent 

 is then filtered to remove the precipitated sulphur and ammonium chloride, 

 and the residue well washed with chloroform. A further quantity of sulphur 

 chloride is added to the combined filtrates, and the ammonia solution again 

 added until alkalinity develops. The process is repeated until traces of 

 nitrogen sulphide are noticed in the precipitate, when the filtrates are 

 distilled until about three-quarters of the solvent is removed. The 

 concentrated solution is now treated with an excess of methylated spirit, 

 which precipitates most of the nitrogen sulphide together with sulphur. 

 On treatment of the precipitate with carbon disulphide, fairly pure nitrogen 

 sulphide (NiS;) is obtained. After concentrating the alcoholic filtrate, and 

 allowing it to cool at intervals, various forms of crystals separate out at 

 the different stages. Nitrogen sulphide and sulphur are first obtained, 

 but later characteristic square laminae form. Subsequently a red oil 

 separates, which solidifies to a low melting solid (10-11"), and is identical 

 with the sulphide of nitrogen (NsSs) described by Muthmanu and Clever. 

 By careful fractional crystallisation of the alcoholic filtrate the compound 

 which crystallises in the form of square plates may be obtained fairly free 

 from sulphur, and it may be further purified by repeated crystallisation 

 from carbon disulphide. The compound, for which we propose the name 

 heoxisidphamide, appears to have the formula SsNHj, and a comparison of 

 its properties with those of the compound SNH obtained by Wolbling' by 

 the reduction of nitrogen sulphide may be of interest : — 



SNH. 



SeNH^. 



Yellow leaflets. 



Colourless, square plates. 



M.P. 152^ 



M.P. 105°. 



Not acted on by cold KOH. 



Not acted on by cold aqueous KOH or 

 HNOs. 



Acted on by IINO3. 





Heated gives NHj. 



Heated gives NH3. 



» Zeitsch. anorg. Chem., 1908, 57, 281. 



[H-2] 



