The Value of p and Its Potential Dependence

The results of the Marcus theory can be extended to electrode reactions by replacing the standard Gibbs energies by the standard electrochemical Gibbs energies, AG and AG. Equation (5.40) is thus rewritten as 

For charge transfer occurring at the electrode/solution interface, AG is not zero, since the reactant and the product are not identical. This could only lead to a value of (3 w 0.5 (commonly used in the analysis of the mechanism of electrode kinetics), for high values of the solvent reorganization energy, X, or for a relatively short range of overpotentials, where the condition 

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