THE POLAR EFFECT IN THE REACTIONS OF ALKOXY AND PEROXY-RADICALS WITH ALCOHOLS

The kinetic data for the reactions of the tert-butoxy radical with C-H bonds of several alcohols are analyzed in terms of the parabolic model of the transition state. The kinetic parameters for this reaction are determined. The activation energies for the forward and reverse reactions are calculated for a number of alcohols. The polar effect is shown to reduce the activation energy by 2 kJ/mol. The same analysis is performed for the reactions of alkylperoxy and hydroxyalkylperoxy radicals with alcohols. The kinetic parameters for these reactions are calculated, the contribution of the polar effect to the activation energy is estimated for the reaction, and the activation energies for the reactions of peroxy radicals of different structures with a set of alcohols are obtained.