Abstract
The effect of the solvent structure on the rates of redox reactions in alcohol + water mixtures is discussed. Collision number varies with the viscosity which is related to structural changes in the solvent. For a temperature-independent reaction, like the oxidation of isopropanol by the anthraquinone-2-sulphonate ion, the rate gives a direct measure for the collision number, and the rate constant for this reaction at 0°C in t-BuOH + water mixtures varies with viscosity as predicted by the collision number. In contrast, the variation with solvent composition of the rate constant for the temperature-dependent oxidation of isopropanol by Mn3+aq is controlled by the effect of changes in the dielectric constant on the contribution of the ion-dipole interaction to the energy of activation. The application of collision theory and of transition state theory to this latter reaction are compared.
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