696 PROCEEDINGS OF THE AMERICAN ACADEMY. 



5. 445 g. oleum (93.2 per cent) were added to 496 g. CCI4 (138 per 

 cent) in two hours, and the product stood over night. 131 g. were 

 obtained up to 135° ; 497 g. from 135° to 150°, little being left in the 

 flask. A second fractionation increased the fraction from 135° tol51° to 

 534 g., melting at —120-1 15°, but redistillation gave 474 g. from 134° to 

 154°. This is 81 per cent of the theory. 134 g. of the product, with 

 65 g. salt (50 per cent excess) gave 31 g. boiling at 40-49° (19-23 mm.) 

 and melting at —37°. The sodium salt, with fuming acid, gave 65 g. 

 crude chlorsulphonic acid boiling at 80-85° (25 mm.). According to 

 Table III we should expect 45 g. and 89 g. respectively. 



6. 300 g. melted SO3 (98.9 per cent) were covered with 572 g. CCI4 

 in a one-liter flask provided with a long condenser and placed on a 

 sand bath. There was but slight action in the cold ; on gentle heating 

 for two hours the reaction was complete. After distilling off the excess 

 of CCI4, very little came over up to 135° ; nearly all distilled from 135° 

 to 141°. Yield 345 g. or 85 per cent. On treatment with 50 g. salt, 

 there was little evolution of hydrochloric acid, and, on distillation at 

 atmospheric pressure, most of the product came over at 149°. Re- 

 distillation at 76° (74 mm.) with a second quantity of salt gave a very 

 pure product, melting at —37° (corr.). This is Sample C, page 699. 



7. 150 g. sulphuric acid (85.9 per cent SO3) were added to 300 g. 

 CCI4 and heated for 10 hours. The product was homogeneous. On 

 distillation, 40 g. were obtained up to 120° and 74 g. from 120° to 158°, 

 which, from its appearance and action with selenium and tellurium, 

 was chiefly chlorsulphonic acid. The residue, 100 g., was sulphuric 

 acid. 



8. 150 g. sulphuric acid (77.0 per cent SO3) were added to 300 g. 

 CCI4 and heated for 10 hours. There was no evidence of phosgene 

 during the heating and the product separated into two layers. 279 g. 

 CCI4 were recovered, with faint odor of phosgene. The fraction from 

 90° to 140° weighed 5 g. ; that from 140° to 160°, 3 g., and neither gave 

 any test for chlorsulphonic acid. The residue, sulphuric acid, weighed 

 141 g. 



9. 100 g. sulphuric acid (82.0 per cent SO3) were heated with 200 g. 

 CCI4 for 5 hours. Phosgene was given off" and the product was homo- 

 geneous. After distilling off excess of CCI4, a fraction of 2.5 g. was 

 obtained from 150° to 153°; a second, of 22.5 g., from 153° to 160°. 

 Both were evidently chlorsulphonic acid, from appearance and tests. 

 The residue, sulphuric acid, weighed 80 g. 



It is clear that the two bodies are formed practically in proportion 

 to the hydration of the oleum used, provided the concentration of the 

 sulphur trioxide is at least 89 per cent. Below this percentage no 



