Photolysis of Carbon Tetrachloride in the Presence of Ethyl Chloride at 25°C

Abstract

The photolysis of CCl₄ in the presence of C₂H₅Cl yielded at 25°C the following reaction products: CH₃Cl; C₂Cl₆; 1,1,1,3‐C₂H₃Cl₄; 1,1,1,2‐C₃H₄Cl₄; meso‐ and racemic 2,3‐C₄H₈Cl₂, and 1,3‐C₄H₈Cl₂. The formation of these products is explained by recombination and disproportionation reactions of the radicals produced in the reactions $${\mathrm{CCl}}_4\mathrm{+hv\to }{\mathrm{CCl}}_3+\mathrm{Cl},$$ $$\mathrm{Cl}+{\mathrm{CH}}_3{\mathrm{CH}}_2\mathrm{Cl}\to {\mathrm{CH}}_3\mathrm{CHCl}+\mathrm{HCl},$$ $$\mathrm{Cl}+{\mathrm{CH}}_3{\mathrm{CH}}_2\mathrm{Cl}\to {\mathrm{CH}}_2{\mathrm{CH}}_2\mathrm{Cl}+\mathrm{HCl}.$$ Data regarding various ratios of rate constants for recombination and disproportionation reactions of these free radicals are reported and discussed. Data on H atom abstraction by Cl atoms from ethyl chloride are also included.