Free radical substitution in aliphatic compounds. Part 11—Reaction of trichloromethyl radicals with n-butane

Abstract

The light-induced reaction between bromotrichloromethane and n-butane has been studied in a series of gas-phase experiments. Taking a literature value for the recombination of trichloromethyl radicals, the value k₂= 7.6 × 10⁶ exp (–7530/RT) l. mole^–1 sec^–1 was determined: CCl₃˙+ RH→CCl₃H + R˙.(2) The difference in the rates of abstraction of primary and secondary hydrogen atoms is given by k^s₂/k^p₂= 0.67 exp(3640/RT). From experiments in which hydrogen bromide was added a value of k⁴⁶³⁰₅= 10^8.44±0.63 was determined: CCl₃˙+ HBr→CCl₃H+Br. (5)