Diffusion-controlled reactions in mixed solvents

Abstract

Rate constants and activation energies of the reaction between solvated electrons and carbon tetrachloride in aqueous mixtures of methanol and ethanol were determined with the technique of pulse radiolysis. Rate constants for the reaction of hydronium ions with alkoxide ions were determined with kinetic conductance measurements. Diffusion coefficients of solvated electrons in water-alcohol mixtures were estimated. There is no linear correlation between rate constants and the sum of the diffusion coefficients of the reactants for solvated electron reactions, in aqueous mixtures of alcohols. The effect of the dielectric constant has to be considered to explain the effect of the solvent on the solvated electron reactions.