Electrochemical reactions with protonations at equilibrium Part V. THE 1 e, 1 H + homogeneous isotopic exchange reaction

Abstract

A theoretical analysis is presented of the homogeneous isotopic electron exchange reaction when a proton is involved in the reaction. The protonations are assumed to be much more rapid than the electron exchanges, i.e. they can be considered at equilibrium. It is shown that the reaction behaves as a single monoelectronic process. An apparent pH-dependent exchange rate constant is defined; its value becomes smaller than the actual exchange rate constants in the pH interval between the p K a's of the system. Applications to redox polymer modified electrodes are discussed.