Abstract
The experimental data of various authors for the kinetics of recombination of free radicals have been analysed in conformity with Waite's rate equation for a diffusion controlled reaction and the constants in this equation have been determined. Depending on the external conditions, the diffusion coefficient characterizing the migration of reaction sites from cage to cage varies within the range 10 −21–10 −15 cm 2/ /sec in solid polymers. The effective kinetic dimensions of the cage, determined by the distance between radicals at which the probability of recombination is considerably greater than the probability that they will escape without interaction, assume values up to 80 Å. The lifetime in the cage varies from 10 2 to 10 5 sec. The ratio between the values of the effective cage radius and the diffusion coefficient depends on the contributions made by the different forms of motion (intramolecular motion, chemical transfer of a free valency, etc.) to the process of movement of the reaction sites. The conclusion that the effective cage dimensions may considerably exceed the distance between adjacent chains is confirmed by analysis of the data in the literature.
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