Reactions of free radicals with aromatic compounds in the gaseous phase. I. Kinetics of the reaction of methyl radicals with toluene

Abstract

The kinetics of abstraction of hydrogen atoms from the methyl group of the toluene molecule by methyl radicals at 430-540°K have been determined. The methyl radicals were produced by pyrolysis of di-t-butyl peroxide in a stirred-flow system. The kinetics ,agree substantially with those obtained by previous authors using photolytic methods for generating the methyl radicals. At toluene and methyl-radical concentrations of about 5 x 10^-7 and 10^-11 mole cm^-3 respectively the benzyl radicals resulting from the abstraction disappear almost entirely by combination with methyl radicals at the methylenic position. In this respect the benzyl radical behaves differently from the iso-electronic phenoxy radical, which previous work has shown to combine with a methyl radical mainly at ring positions. The investigation illustrates the application of stirred-flow technique to the study of the kinetics of free-radical reactions.