W. G. Mixter — Electrosynthesis. 221 



Amines and Oxygen. 



A mixture of 20 cc of oxygen and 10 cc of methylamine gas 

 contracted 12*4 CC , while hydrogen and oxygen contracted 6'4 CC , 

 a ratio of 194 to 100. Assuming the reaction to be 

 2NH 2 CH 3 + 4K) 2 = N 2 + 2C0 2 + 5H 2 

 4 vols. 9 vols. 2 vols, 

 and allowing for the nitrogen, we have 194 Xyf- =229 volumes, 

 of which TO are methylamine and 159 are oxygen. The solu- 

 tion of potassium hydroxide after the experiment reacted for 

 nitrous acid, and assuming 



2NH 2 CH 3 + 6^0 2 = 2NO a + 2C0 2 + 5H„0 

 4 vols. 13 vols, 



the 194 volumes consist of 46 of methylamine and 148 of 

 oxygen. The two reactions occur simultaneously and we may 

 consider that methylamine is oxidized somewhat slower than 

 hydrogen. 



The ratio observed between a mixture of hydrogen and 

 oxygen and one of dimethylamine and oxygen was 100 to 300 

 volumes with formation of nitrous acid. Calculated as for 

 methylamine we find TO volumes of dimethylamine oxidized 

 on the assumption that all of the nitrogen is set free, and 57 

 volumes, assuming the nitrogen to form NO Q . 



Trimethylamineand oxygen gave a very different result from 

 the two preceding, as no nitrous acid was detected. It may 

 have been formed and decomposed by the amine. For 100 

 volumes of hydrogen and oxygen 265 of trimethylamine and 

 oxygen combined, consisting of 42 of trimethylamine and 223 

 of oxygen. 



A mixture of aniline vapor and oxygen at 30° C. and 100 mm 

 pressure contracted very slowly when subjected to the glow 

 discharge and a brown condensation product was deposited on 

 the sides of the tube. No nitrous acid was detected in the 

 products. 



Cyanogen and Oxygen. 



A mixture of one volume of dry cyanogen and two volumes 

 of oxygen was subjected to the glow discharge. For a time it 

 increased a little in volume, and afterwards slowly contracted 

 to about the original bulk of the mixed gases. A solution of 

 barium hydroxide was added to absorb carbon dioxide and any 

 cyanogen left. The gases remaining after this treatment con- 

 tracted much and when again subjected to the discharge more 

 barium carbonate formed. Two tests were made, using potas- 

 sium hydroxide solution as an absorbent, with similar but unsat- 

 isfactory results. Scarcely more than a trace of nitrous acid 

 was detected. The changes caused by the glow discharge are 

 too complicated to admit of an accurate comparison with the 



