Free-radical substitution in aliphatic compounds. Part XII. The chlorination of n-hexane in the gas and liquid phases

Abstract

n-Hexane has been chlorinated in the gas phase, with nitrogen as diluent, and in the liquid phase with carbon tetrachloride as a solvent. The relative rates of chlorination at the primary and secondary positions are given by the expressions (k_s/k_p)_gas≈ 2·2 ± 0·6 exp (214 ± 127 cal./RT) and (k_s/k_p)_liquid= 0·8 ± 0·2 exp (597 ± 20 cal./RT). Possible explanations of this difference are discussed.