Radiation-induced dechlorination of carbon tetrachloride in cyclohexane and n-hexane mixtures. III. The kinetics of liquid-phase reactions of trichloromethyl radicals

The kinetics of gamma-radiation-induced free-radical chain reactions in solutions of carbon tetrachloride in mixtures of varying composition of cyclohexane and n-hexane was investigated in the temperature range of 296°–413°K. Trichloromethyl radicals were produced by the reaction of radiolytically generated alkyl radicals with the solute. The kinetics of the following reactions were studied: The following rate expression was obtained: The error limits are the standard deviation from the least mean-square Arrhenius plots. The present results, combined with previously measured activation parameters for hydrogen-atom abstraction from c-C₆H₁₂ and n-C₆H₁₄ by CCl₃ radicals relative to CCl₃ combination, afford experimental evidence that the decay of trichloromethyl species in alkane solutions is a diffusion-limited process. The thesis that activation energies of reactions (4) and (5) in the liquid phase are equal to their respective values in the gas phase is confirmed.