Absolute rate constants and arrhenius parameters for the addition of the methyl radical to unsaturated compounds: The methyl affinities revisited

Absolute rate constants and their Arrhenius parameters are reported for the addition of the methyl radical to 21 monosubstituted and 1,1-disubstituted alkenes and to 6 benzenes in 1,1,2-trifluoro-1,2,2-trichloroethane solution. They are used to convert relative reaction rates known as methyl affinities from the work of M. Szwarc and others for about 250 additional unsaturated compounds to the absolute scale. An analysis shows that the addition rates depend on the reaction enthalpy but also indicates a moderate nucleophilic polar effect for the liquid-phase reactions. It is pointed out that this polar effect may be smaller in the gas phase.