Abstract
The main peculiarities of free radical reaction kinetics in organic solids are discussed from the point of view of a slightly modified free volume model of molecular mobility. The reaction and diffusion acts are supposed to occur predominantly in “diluted” microzones, the probability of “dilution” depending on the minimal volume needed for reaction or diffusion, and on the energy of a local molecular displacement. It is shown that even far separated radical pairs may react in a “static” way via the long range microdilution of the structure. The model explains the separation-dependent annealing of radical pairs as well as the stepwise annealing of large fractions of quasi-isolated centres and large capture radii for the diffusion limited reaction of the remaining species. Preliminary results concerning the pressure and plastification dependence of the rate constant are also in reasonable agreement with the proposed concept.
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