Which mechanism operates in the electron-transfer process at liquid/liquid interfaces?

Abstract

We present a more general expression for the relationship of potential dependence, which implies that a change in the interfacial drop across the interface has little effect on the free energy of the reaction, but mainly affects the surface concentration of reactant in each phase. Abundant experimental results from several well-known groups are analyzed in great detail to confirm our conclusion. At the same time, we define a new parameter named Frumkin correction factor to describe this relationship of potential dependence, which expresses the thermodynamic effect of double diffuse layers within both phases in contrast with the so often suggested kinetic electron-transfer (ET) coefficient; we also find that it depends on two intimately related aspects: the charges of reactive species and the ratio of the diffuse layer potential to the total potential within each phase, so it is quite arbitrary to ignore the diffuse layer effect in the aqueous phase just because of its relatively small values. In addition, a fascinating question on the inverted region at liquid/liquid interfaces has been successfully interpreted by an opposite surface concentration effect, which was often considered as a kinetic Marcus inverse by most groups.