Tetretliylplwspl ionium and their Decomposition by Heat. 203 



800 cub. centim., agreeing with the amount demanded by 

 theory, 860 cub. centim. 



The remainder of the distillate was dissolved in water, and 

 had a faintly acid reaction; on addition of caustic soda an oil 

 separated, which by its properties and boiling-point, 125°-133° 

 C, was triethylphosphine. The amount of free tertiary base 

 obtained was about three grammes. The hydrochlorate of tri- 

 ethylphosphine obtained by this reaction is a white cystalline 

 powdery solid, which scarcely melts when heated to about 

 210° C, at which temperature it sublimes or probably dis- 

 sociates, for if any air be in the tube dense white clouds are 

 formed of the oxide of triethylphosphine. As this reaction is 

 the only one which will yield considerable quantities of the 

 tertiary base from the phosphonium salt, another experiment 

 was made, with every precaution to see whether the yield was 

 quantitative. 



A solution of chloride was quickly evaporated, and finally 

 heated in a weighed distilling-flask till the temperature of the 

 liquid had risen to 180° C-; suddenly the whole frothed up and 

 solidified in the flask to a mass of white crystals. The amount 

 of salt thus obtained was 8 grms. This solid mass of crystals 

 did not melt till the temperature was about 270° C, and no 

 decomposition was noticed till the melted salt was at a tem- 

 perature of 340° C, and gas was not rapidly evolved till the 

 liquid was above 360° C. ; 910 cub. centims. of gases were 

 evolved, and the same w r hite distillate was obtained. There 

 was no charring, and the whole of the salt w r as distilled out of 

 the flask. 



The distillate was washed out of the condenser with a little 

 water and transferred to a flask, through which a current of 

 hydrogen was passed; excess of caustic soda was added, and 

 the triethylphosphine which separated was distilled in a current 

 of steam ; 4*3 grms. were obtained, the boiling-point of which 

 lay between 120°-135° C, and when added to ethyl iodide gave 

 the iodide of tetrethylphosphonium. 



Part of the gases were treated with bromine, when they 

 were completely absorbed, giving dibromide of ethylene, 

 B.P. 130°-135°'C. Another portion was analysed :— 



cub. centim. 



Gas taken . 4'2 



Gas + oxygen 25"6 



After explosion 17*0 



After addition of caustic potash . 8*7 



Or, 



r . , i ^ j Carbonic Anhydride 



Gas taken. Oxygen consumed. produced. 



4=2 c.c. 12-7 c.c. 8-3 



