pH-dependent redox potential: how to use it correctly in the activation energy analysis

The activation barrier (the activation free energy) for the reaction's elementary act proper does not depend on the presence of reactants outside the reaction complex. The barrier is determined directly by the concentration-independent configurational free energy. In the case of redox reactants with pH-dependent redox potential, only the pH-independent quantity, the configurational redox potential enters immediately into expression for activation energy. Some typical cases of such reactions have been discussed (e.g., simultaneous proton and electron detachment, acid dissociation followed by oxidation, dissociation after oxidation, and others). For these mechanisms, the algorithms for calculation of the configurational redox potential from the experimentally determined redox potentials have been described both for the data related to a dissolved reactant or to a prosthetic group of an enzyme. Some examples of pH-dependent enzymatic redox reactions, in particular for the Rieske iron-sulfur protein, have been discussed.