Macbkth and Graham — Action of Sulphur Chloride on Ammonia. 35 



show the time that elapses before the colour develops. 5 e.c. of N/3 solutions 

 of the bases were used in each case : — 



N/lOO SeNHa 



Potassium 

 Hydroxide. 



Methylamine and 

 Ethylamine. 



Dimethylamine, 



Diethylamine, and 



Pipeiidine. 



1 c.c. 



2 c.c. 



3 c.c. 



i c.c. 



5 c.c. 



150 seconds. 

 80 „ 

 50 „ 

 35 , , 

 ■20 „ 



210 seconds. 

 .120 ,, 



83 „ 



60 „ 



55 ., 



240 seconds. 

 125 „ 



95 „ 



70 „ 



60 „ 



The view that the colorations referred to above are due to the formation 

 of a salt of a nitrogen-sulphur acid led to attempts to prepare such an acid 

 by the action of sulphuretted hj'drogen on solutions of nitrogen sulphide, 

 nitrogen sulphide aird sulphur, and the red sulphide of nitrogen. In no 

 case was any such product isolated, for either the original materials were 

 obtained on crystallisation, or, if the reaction had proceeded far, ammonium 

 polysulphide was formed. It was thought that the organic derivatives 

 might be more stable, as such derivatives of carbonic acid and sulphurous 

 acid are obtained as stable compounds. In accordance with this view, the 

 action of nitrogen sulphide (N4S4) on ethyl raercaptau was examined, but no 

 derivative of the desired nature was isolated. On adding ethyl mercaptan 

 to the sulphur nitride a vigorous reaction takes place, considerable heat is 

 developed, and ammonia is evolved. A deep-red liquid — which is probably 

 a solution of the nitrogen sulphide in the mercaptan — is formed in the 

 first stages of the reaction, but on further addition of the thioalcohol the 

 colour disappears, and the end products are a pale-yellow liquid and a 

 small amount of a white solid. The latter appears to be sulphur, and is 

 generally found to an extent of 3-4 per cent, of the amount of nitrogen 

 sulphide used. To trace the other products of the reaction, a weighed 

 amount of nitrogen sulphide was placed in the reacting vessel, and the 

 mercaptan was slowly run in. A flask (G) contained a known volume of 

 N/1 sulphuric acid, and the ammonia formed in the reaction was absorbed 

 in this medium. During the reaction a small amoimt of a white, evanescent 

 solid collected on the sides of the reacting vessel and in the tube leading 

 to C. (A small amount of this was collected in separate experiments, but it 

 was too unstable to be fully examined. It decomposes rapidly in air, giving 

 ofi" ammonia.) When the reaction was over, the reacting vessel was heated 



