Kinetics of partly diffusion-controlled reactions XIII: Cage effect in the photolysis of benzyl chloride

Abstract The cage recombination of free benzyl and chloride radicals after their formation via the photolysis of benzyl chloride is interpreted using a model of partly diffusion-controlled reactions. A kinetic model is presented which takes into account the non-contact of the species of interest at the moment of their formation. There is good agreement between the experimental results and the model presented. At the same time we show the presence of a secondary cage effect between benzyl radicals and radicals produced by the reaction of Cl • with the solvent.