32 Proceedings of the Royal Irish Acadeiny. 



As far as we have been able to trace, the nitrogen sulphides described 

 above are the only compounds of- this class hitherto isolated. The action of 

 ammonia on sulphur chloride was, therefore, further examined by us, in the 

 hope of supplementing the number of nitrogen sulphides already known. 

 Owin^ to the vigorous nature of the reaction between sulphur chloride and 

 the base, a diluent liquid is necessary. After preliminary experiments with 

 carbon disulphide, benzene,^ light petroleum, carbon tetrachloride, and 

 chloroform, the latter solvent was selected on account of its high state of 

 chlorination and its volatility. Sulphur monoehloride was used in the work, 

 as it is least lilcely to exert a chlorinating or oxidising effect on any of the 

 reaction products. In order to determine the course of the reaction, 

 a solution of ammonia in chloroform was prepared, and the strength of 

 the solution determined. A stream of dry ammonia gas was passed into 

 a litre of the solvent at 10° until no further absorption of the base occurred. 

 Titration showed that the chloroform contained 30'6 grams of ammonia 

 per litre (1-8 If). This solution was slowly added to 34 grams of sulphur 

 monocliloride, dissolved in 500 c.c. of ice-cold chloroform, until a permanent 

 alkalinity was developed. The mixture was mechanically stirred during 

 the reaction, and on the average 370 c.c. of the ammonia solution were 

 required for combination with the amount of sulphur chloride used. The 

 main products of the reaction were found to be ammonium chloride, sulphur 

 and nitrogen sulphide (N^S^), and the quantities of sulphur chloride and 

 ammonia employed lead to the equation given below. 370 c.c. of I'SN 

 ammonia correspond to 0-666 gram-molecules of the base, and this reacts 

 with O'o gram-molecules (34 grams) of sulphur monoehloride. It therefore 

 follows that four molecules of ammonia combine with three molecules of 

 sulphur monoehloride, hence the equation — 



12SC1 + I6NH3 = N,S, + 12XH,C1 + 4S,. 



As no nitrogen was evolved during the reaction, it is of interest to compare 

 this equation with that given by Euff and GeiseP for the action of sulphur 

 tetrachloride on ammonia — 



12SC], + I6NH3 = 32^,S, + 48HC1 + 2^^. 



From the equations it is seen that when acting on ammonia the various 

 chlorides of sulphur behave as a mixture of SCI3 with sulphur or chlorine. 

 If the state of chlorination is greater than in SCI3, oxidation by the 



1 Francis (Trans. Chem. Soc, 1904, 85, 259, 1535; 1905, 87, 1836) obtained a good 

 yield of lsjS4 by passing ammonia into a solution of sulphur dichloride in benzene. See 

 also Davis, ihid., 1905, 87, lb31. 



- Berichte d. Deutsch. Chem. Gesell., 1904, 37, 1573. 



