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.
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