Comparison of Solvent Effects in the Kinetics of Simple Electron Transfer and Amalgam Formation Reactions

摘要

The effects of the solvent on the kinetic parameters of simple electron transfer and amalgam formation reactions are reviewed and compared. The parameters considered are the standard potential, the standard rate constant and the intrinsic transfer coefficient. The role of the solvent in double layer effects is also considered. Comparison of solvent effects on the standard rate constant reveals a major difference between the two reactions. This difference lends support to the conclusion that electron transfer is not involved in amalgam formation as the rate determining step. Instead, the rate determining step in amalgam formation involves movement of the reacting ion from one location in the double layer to another closer to the interface. The role of solvent dynamical processes in determining the rate constant is discussed with respect to the mass of the moving reactant and its interaction with the solvent environment. Keywords: Electrocatalysis thermodynamics, Transfer coefficients. (kr)