Abstract
1. The rate constants of the reactions of chain propagation and termination were measured in the oxidation of cyclohexane in solutions of acetic acid and ethyl acetate at various temperatures. 2. The change in the dielectric constant of the medium in the oxidation of cyclohexane in these solvents has no effect on the rate constant of the reaction of chain propagation and substantially influences the rate constant of recombination of radicals RO2, representing an interaction of two dipoles. 3. The electrostatic portion of the thermodynamic parameters in reactions of chain termination was evaluated. The values of the activation energy and entropy of activation under ideal conditions (when ɛ=1) and the value of E6 at ɛ=∞ were determined. The activation energy in the reaction of chain termination in the oxidation of cyclohexane is due entirely to nonspecific solvation of the peroxide radicals by the solvent.
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