198 Drs. Letts and Collie on the Salts of 



Action of Heat on the Oxalate of Tetrethylphosphonium. 



This salt was prepared by the action of oxalate of silver on 

 a solution of the iodide of tetrethylphosphonium. The filtered 

 solution was evaporated over a water-bath, and the residue 

 dried in vacuo over sulphuric acid. It solidified to> a mass 

 of fine crystals. Some of these were allowed to remain in 

 vacuo till of constant weight, and then a combustion was 

 made. 



(I.) 0*270 grm. salt gave 0'553grm. C0 2 , and 



. 0-253 grm. H 2 0. = 55-85. 11 = 10-41. 



Another quantity of the solution of the oxalate was evapo- 

 rated in a distilling flask, and finally the temperature of the 

 solution was raised to 160° C, when no decomposition oc- 

 curred ; the liquid on cooling solidified to a mass of crystals. 

 Some of these were analyzed. 



(II.) 0*315 grm. salt gave 0*285 grm. H 2 0, and 



0-658 grm. C0 2 . C = 56'96. H=1(H)5. 



Found. 





Calculated for 



[P(C 2 H 5 ) 4 ] 2 C 2 4 . 



I. 



II? 



c 



. . 56-56 . . 



. 55-85 



56-96 



H 



. . 10-47 . . 



. 10-41 



10-05 



This salt, therefore, appears to be stable, and can be heated 

 to 160° 0. without any change. Decomposition, however, 

 begins slowly at about 200° C, and at 230° 0. gas is rapidly 

 evolved. 



6*5 grms. salt when subjected to the action of heat gave 

 650 cub. centims. of gases ; and the whole of the contents of 

 the flask distilled without charring. The distillate was chiefly 

 oxide of triethylphosphine, together with some triethylphos- 

 phine, and a liquid insoluble in water and hydrochloric acid, 

 which possessed a boiling-point 95°-105° C, and which gave 

 on oxidation acetic acid. It resembled in smell and pro- 

 perties the diethyl ketone, obtained when the carbonate was 

 heated, but it was formed only in small quantity. 



The 650 cub. centims. of gases were first treated with bro- 

 mine, when 100 cub. centims. were absorbed; caustic potash 

 further reduced these by 100 cub. centims., leaving 450 cub. 

 centim The remaining gases burnt with a bluish and 

 scarcely luminous flame. 



Several analyses were made of the gas evolved by the 

 decomposition of the oxalate, two of which are subjoined. 



