504 



Dr. H. E. Armstrong on 



[June 16, 



the intention of applying the reaction to members of the several series of 

 organic haloid compounds. In the following are contained the results of 

 most of the experiments hitherto made ; and although in a less complete 

 form than I could wish, I am induced to make them now public, as for 

 several reasons it will be some time before I shall be enabled to continue 

 my experiments in this direction. 



Action of Sulphuric Anhydride on Carbonic Tetrachloride. 



In this, as in all the following experiments, the liquid was added to the 

 sulphuric anhydride by means of a drop-funnel provided with a glass stop- 

 cock. The anhydride was prepared by distillation of Nordhausen sulphuric 

 acid, and condensed in a wide-mouthed flask. This flask was connected, 

 by means of a cork provided with two borings, with an inverted Liebig's 

 condenser, and with the drop-funnel. 



The action set in immediately on allowing the carbonic tetrachloride to 

 drop on to the anhydride, and was accompanied from the beginning by a 

 constant evolution of gas. The smell and suffocating properties of this gas 

 characterized it at once as carbonic oxychloride ; it was entirely absorbed 

 by absolute alcohol, the absorption being accompanied by a great rise in 

 temperature. On the subsequent addition of water a heavier layer was 

 precipitated, which was separated from the wash-water and dried over calcic 

 chloride. It was then obtained as a colourless, mobile liquid, boiling 

 between 90° and 95° C, traces of which exercised a most irritating action 

 on the eyes. The B.P. of chlorocarbonic ether, with which it agrees in all 

 its properties, is given as 94° C. 



The rise in temperature on adding C Cl 4 to the anhydride was very con- 

 siderable ; and after one equivalent of the former to two of the latter was 

 present, it was only necessary to apply the heat of a water-bath for a short 

 time in order to complete the reaction ; there then remained a heavy, dark 

 brown-coloured liquid in the flask, on subjecting which to distillation a 

 small quantity C Cl 4 first passed over, whereupon the thermometer rose 

 rapidly, and between 130° and 150° the whole distilled over. After repeated 

 rectification the pure product was obtained of B.P. 14l°-145° (uncor- 

 rected) under a normal pressure. Thus prepared it is a colourless, heavy, 

 mobile liquid, constantly fuming in the air, and which refracts light 

 strongly. 



On analysis, the following numbers were obtained : — 



•342 grm. gave '7366 grm. BaS0 4 =29\56 S. 

 •296 grm. gave -3922 grm. AgCl =32'8 CL 



which results correspond with the formula S 2 O. Cl 2 , as is evident from the 

 following comparison of the analytical with the calculated numbers : — 



