ACTION OF PHOSPHIDE OF SODIUM ON HALOID ETHERS, 195 
Sulphate of Tetrabenzyl-Phosphonium.—Nine grms. of the phosphonium 
chloride were dissolved in about a pint of hot water, the solution was 
then cooled somewhat, and sulphate of silver added until it ceased to be 
converted into chloride. The solution was then filtered and concentrated, 
and yielded a crop of very beautiful colourless rhombic plates of considerable 
size.* A determination of water of crystallisation and of sulphuric acid 
showed that these consisted of the normal sulphate crystallising with six mole 
cules of water. 
Salt dried at 120°. 
Sulphuric Acid (1 and 2 volumetrically by the chromate method, 3 gravimetrically). 
(1) 05745 grm. required 2°6 cc. } normal BaCl, =0:0520 SO;,=9:0 per cent. 
(2) 0:4203 __,, A OO es yes |, = 90 
(3) 05053 ,, gave 0131 grm. BaSO, = 07045 |), -=8:9 
” 
” 
Air-dried Salt, 
Sulphuric Acid. 
0°6865 grm. required 5°6 ce. + normal BaCl=0:056 SO;=8:2 per cent. 
Water (by heating to 125° C.). 
0:5704 lost 0:0574 H,O=10:0 per cent. 
Obtained. 
_—— 
Dry Salt. Undried. 
L tT, ir. Salt, 
Sulphuric anhydride, : 9:0 90 8:9 8:2 
Water, . 2 : , — — — 100 
Calculated. 
a 
{(C,H,),P},S0O,.  {(C,H,),P}.50,, 6H,0. 
Sulphuric anhydride, . ale elo) 8:1 
Water, : : : ; — 10°8 
The normal sulphate is one of the most soluble salts of the phosphonium. 
It has no definite melting point. It grows pasty at 195°, but is not completely 
fused until 220°. 
_ Action of Sulphuric Acid on Chloride of Tetrabenzyl-Phosphonum.—W hen 
* In our notice of these experiments in the “ Proceedings,” we stated that the action of sulphate of 
silver on the phosphonium chloride yields the acid sulphate, and not the normal sulphate of the 
phosphonium. There can be but little doubt that we did obtain and analyse the acid salt, but its forma- 
tion was probably due to the fact that we acted on a boiling solution of the chloride with sulphate of 
silver, and the filtered solution therefore contained a considerable quantity of the latter salt which we 
decomposed by sulphuretted hydrogen, thus setting free sulphuric acid which combined with the normal 
sulphate ; and as the acid sulphate thus formed is much less soluble than the normal sulphate, it is 
probable, as we analysed the first crop of crystals, that they consisted entirely of the acid sulphate. 
We have verified the correctness of this explanation by an experiment conducted in a similar manner. 
