Studies of the Cage Effect of Solvent. IV. Dependence of the Cage Combination of Methyl Radicals on Solvent and on Temperature

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Abstract
Experimental results for the cage combination of methyl radicals, obtained by the photolysis of azomethane in various solvents, have been discussed with reference to the effects of solvent and temperature. An attempt to interpret the results by treating both the cage combination and the escape of methyl radical from the cage as though they were elementaly processes has been found to be not very successful, probably owing to the over-simplification involved in such a treatment. Another attempt to apply Noyes’s theory, that assumes diffusion in the viscous continuum, has been found to be rather satisfactory. However, a comparison of the theory with the experimental results indicates that the molecular structure of the medium, as well as the structure and property of individual molecules of the solvent, need to be taken into account for a better description of the matter.

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