Abstract
The reactivity of RO 2 . peroxide radicals in oxidation reactions depends greatly on specific and nonspecific solvation by the solvent. With increasing dielectric constant (ɛ) of the medium, the rate constant for the interaction of RO 2 . radicals with methyl ethyl ketone (k2) and the rate constant of the recombination of RO 2 . radicals (k6) increase. The specific solvation of RO 2 . radicals due to hydrogen bonds of water diminishes their reactivity. Equilibrium constants for the solvation of peroxide radicals and all rate constants of chain propagation and termination reactions involving solvated and unsolvated RO 2 . radicals were measured. The change in composition of the oxidation products when methyl ethyl ketone was diluted with benzene or water is caused by nonspecific and specific solvation by the solvent affecting the chain propagation reaction.
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