168 Van Name and Maryott — Chlorination of Benzene. 



ing velocity at which the non-electrolytic chlorination must 

 have proceeded, upon the hypothesis of a 10 per cent current 

 yield. This is shown graphically in fig. 3, in which the lower 

 (dotted) line connects the values of k calculated in the manner 

 just described, and the black line the values actually observed. 



Fig. 3. 



~ l! — ~* 



— — * -^ e-^ 



120 Mm. 



600 



A little consideration will show that the deviations of the 

 lower curve from the upper must correspond approximately in 

 nature and magnitude (though opposite in direction) to the 

 effects which the assumed current yield would be expected to 









Table VII. 











Cone, of Benzene, a— x 



fcxlO 4 



fcxlO 4 



kxW 







10$ cur- 





10* 



100$ 



5% 



t 





rent yield 





vield 



yield 



yield 



min. 



found 



calc. 



found 



calc. 



calc. 



calc. 







1*7872 



1-7872 



2-42 



2*42 



2-42 



2-42 



120 



1-7359 



1-7359 



2*62 



2-49 



1-39 



2-56 



240 



1-6822 



1-6848 



2-80 



2-80 



2-80 



2*80 



360 



1-6266 



1-6266 



2-97 



2-80 



1-27 



2-88 



480 



1-5695 



1-5729 



2*95 



2-95 



2-95 



2*95 



600 



1-5149 



1-5149 











produce upon an otherwise constant or uniformly increasing 

 reaction velocity, such as that which the non-electrolytic 

 chlorination would naturally have under the comparatively 

 constant conditions of the experiment. For comparison, the 

 values of ~k for experiment 4, calculated as above but assuming 

 current yields of 100 per cent and of 5 per cent, are given in 

 the last two columns of Table YII. All these effects would 

 be slightly smaller if in addition to monochlorbenzene the 

 electrolytic reaction yielded any other, more highly chlorinated 

 product, in considerable quantity. 



As a whole, the reaction velocity experiments give no evi- 

 dence of effects comparable in size or kind to those which, 



