Radiation‐induced dechlorination of carbon tetrachloride. II. The kinetics of liquid‐phase reactions of trichloromethyl radicals in n‐hexane solutions

Abstract

The kinetics of the gamma-radiation induced free-radical chain reaction in solutions of carbon tetrachloride in n-hexane (RH) was investigated in the temperature range of 297.5-373'K.Trichloromethyl radicals were produced by the reaction of radiolytically generated hexyl radicals with carbon tetrachloride. The kinetics of the following reactions were investigated:The following rate expression was obtained: log k3/k~1/2(cm3'2/mole1~~ . sec1I2) = 5.19 f 0.05 -(9.62 =t 0.10) e where e = 2.303 RT in kcal/mole. The error limits are the standard deviation from the least mean square Arrhenius plots. It is concluded that reaction (4) is diffusion controlled in the liquid phase, and that the activation energies in the gas and liquid phases of reaction (3) are equal.

Reactions of 34mCl Recoil Atoms with Liquid Mixtures of CCl4 and Aliphatic Compounds

“…This reaction has been observed in the radiolysis of mixtures of CCI4 and c-C 6 H 12 [21,22,28] and n-C 6 H 14 [39].…”

“…The activation energy of the Η-abstraction by CC1 3 radicals from C-C 6 H 12 [38] and n-C 6 H 14 [39] in the liquid phase is equal to that derived in the gasphase, whereas the rate constant in the liquid phase at room temperature is for C-C 6 H 12 about 20% higher than for n-C 6 H 14 [40].…”