The thermodynamics of protolytic equilibria

The Thermodynamics of Protolytic Equilibria This gives the result... 

The general features discussed so far can explain the complexity of these reactions alone. However, thermodynamic and kinetic couplings between the redox steps, the complex equilibria of the metal ion and/or the proton transfer reactions of the substrate(s) lead to further complications and composite concentration dependencies of the reaction rate. The speciation in these systems is determined by the absolute concentrations and the concentration ratios of the reactants as well as by the pH which is often controlled separately using appropriately selected buffers. Perhaps, the most intriguing task is to identify the active form of the catalyst which can be a minor, undetectable species. When the protolytic and complex-formation reactions are relatively fast, they can be handled as rapidly established pre-equilibria (thermodynamic coupling), but in any other case kinetic coupling between the redox reactions and other steps needs to be considered in the interpretation of the kinetics and mechanism of the autoxidation process. This may require the use of comprehensive evaluation techniques. 

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