MECHANISM OF THE RECOMBINATION OF PEROXYL RADICALS

On the basis of an analysis of published results for the kinetics, mechanism and products of the recombination reaction of peroxyl radicals of varying structure a new mechanism has been proposed for this reaction, in which the most important stages are the non-synchronous homolysis of the tetroxide formed by the dimerization of the peroxyl-radicals and the disproportionation in two directions of the radical pair RO..OOOR. It is shown that the dependence of the rate constant for the loss of peroxyl radicals on the inductive properties of the substituent R in the peroxyl radical ROO. which follows logically from the proposed mechanism is actually observed, while the nature and magnitude of the effect can be accounted for in terms of this mechanism.