170 Van Name and Maryott — Chlorination of Benzene. 



2. Benzene dissolved in the same solution is readily chlorin- 

 ated by direct treatment with chlorine gas in the dark, yielding 

 addition and substitution compounds in proportions which 

 vary with the conditions. 



3. The addition of benzene to the acetic acid-lithium chloride 

 solution during electrolysis raised the anode potential, and by 

 an amount equal to or greater than that produced by a similar 

 amount of carbon tetrachloride. This indicates that benzene 

 has little or no depolarizing power toward chlorine, at least in 

 this case. Phenol, added under similar conditions, produced a 

 decided lowering of the anode potential. 



4. The rate of chlorination of benzene, when dissolved in the 

 same medium saturated with chlorine, was measured at 10*2°. 

 Simultaneous electrolysis did not accelerate the chlorination 

 perceptibly under conditions where a 10 per cent current yield 

 should have been evident. The current yield, if appreciable, 

 was therefore below 10 per cent. 



5. The products of 4 contained addition and substitution 

 chlorine in the ratio of about 2 to 3, this ratio increasing 

 slowly as the reaction progressed. The reaction velocity, 

 calculated on the assumption that monochlorbenzene and ben- 

 zene hexachloride were the sole products, showed a steady rise, 

 but the rate of chlorination of monochlorbenzene, separately 

 determined, appeared to be sufficient to account for this effect. 



6. No positive evidence of strictly electrolytic (i. e. anodic) 

 chlorination of benzene was obtained. 



