Theory and Applications of Electron Transfer at Electrodes and in Solution

Abstract

The theory of simple electron transfers at electrodes and in solution is reviewed, and various thermal fluctuations of coordinates leading to electron transfer are described. A simplified derivation is given of the free energy of such fluctuations. Implications of the theoretical equations for experiment are described, some of t relevant results having been summarized recently in Dahlem Konferenz Phys. Chem. Sci. Res. Rept., 1(1975)477. They include relations between rate constants of cross-reactions and self-exchange reactions, between rates of reactions at electrodes and those in solution, nonspecific solvent effects, chemiluminescence, and other properties. Approximate equations of the BEBO type are also given for Tafel slopes, Bronsted slopes and rates of cross-reactions, for systems involving rupture and formation of bonds.