Tetrethylphosphonium and their Decomposition by Heat. 189 



connected with a Liebig's condenser, to which an apparatus 

 for collecting gas was attached. On applying heal; to the 

 flask the crystals fused, and soon began to decompose with 

 effervescence. A few grammes of liquid passed over at a low 

 temperature, but the thermometer (in the distilling flask) 

 soon rose to 240°, between which temperature and 250° the 

 bulk of the contents of the flask distilled. 



The distillate consisted of two layers, the lower of which 

 was simply an aqueous solution of oxide of triethylphosphine; 

 the upper layer (which amounted to only a gramme or two) 

 had a strong odour of triethylphosphine. When shaken with 

 hydrochloric acid about two thirds of it was absorbed ; the 

 remaining third was not attacked, even when boiled with 

 strong hydrochloric acid. This latter had a distinct and cha- 

 racteristic odour, and its boiling-point lay between 90-100° C. 

 As it was not attacked when boiled with hydrate of barium 

 or caustic soda, and as carbonate of ethyl boils at 126° C, its 

 identity with that substance was clearly negatived. 



The gas evolved during the experiment caused a turbidity 

 with lime-water, and was in part absorbable by caustic potash 

 (to the extent of about one third the total volume). It there- 

 fore contained carbonic anhydride. The residue was not 

 acted upon by bromine ; and as it burnt with a luminous 

 flame, it probably consisted of a paraffin hydrocarbon, pre- 

 sumably butane. 



In order to ascertain the nature of the volatile liquid, which 

 accompanied the triethylphosphine, another experiment was 

 performed with a larger quantity of the carbonate. On sub- 

 mitting it to the action of heat the same phenomena were 

 observed as before, and a quantity of the volatile liquid (freed 

 from triethylphosphine), amounting to two grammes, was 

 obtained. 



After two or three fractionations its boiling-point was found 

 to be between 95°-102° C. Now this boiling-point agrees 

 fairly well with that of diethylketone (101° C), the formation 

 of which, along with the phosphine oxide, could be accounted 

 for by the equation — 



/C 2 H 5 

 (C 2 H 5 ) 3 P\\. 



X 



|>CO = 2 (C 2 H 5 ) 3 PO + (C 2 H 5 ) 2 CO. 



(C 2 H 5 ) 3 P<f 







C 2 H S 



