Guidelines for the Voltammetric Study of Electrode Reactions with Coupled Chemical Kinetics at an Arbitrary Electrode Geometry.

A powerful, unified, and simplifying mathematical approach for the theoretical treatment of first-order chemical kinetics coupled to interfacial charge transfers at electrodes of arbitrary geometry and size, both uniformly accessible and nonuniformly accessible to the electroactive species, is presented. The general CEC mechanism at spherical and disc electrodes is considered to test the validity and benefits of such an approach, based on the application of the so-called kinetic steady state, that enables the reduction of the multivariable problem of kinetic-diffusive differential equations to a single variable problem of a diffusion-only differential equation. This is solved both analytically and numerically, showing how this approach leads to general, simple, and efficient solutions for the study of the influence of coupled chemical kinetics on the voltammetric response. The voltammetry of the CEC mechanism is analyzed as a function of the kinetics and thermodynamics of the preceding and subsequent chemical reactions and of the electrode size (from macroelectrodes to ultramicroelectrodes) and shape (spherical and disc). Comparison with the responses of the CE, EC, and E mechanisms is included, proposing diagnosis criteria and procedures for quantitative analysis of experimental data.

Reversible surface two-electron transfer reactions in square wave voltcoulommetry: application to the study of the reduction of polyoxometalate [PMo12O40]3- immobilized at a boron doped diamond electrode.

Reversible surface two-electrons transfer reactions (stepwise processes) are analyzed using square wave voltcoulommetry (SWVC), which is a variety of square wave techniques based on the measurement of the transferred charge. Such reversible surface redox processes are exhibited by many two-redox center and multicenter biomolecules (proteins, enzymes, ...) and inorganic molecules like polyoxometalates (POMs), which have very interesting applications, mainly as electrocatalysts. Because of the stationary character of the response obtained, the key parameters that govern the cooperativity degree of the two reversible electron transfers (ETs) are the difference between their formal potentials, ΔE(0), and the square wave amplitude, |E(SW)|, whose combined effect sets the two peaks → one peak transition in the response. Working curves based on the variation of the peak parameters (peak potentials, half-peak widths, and peak heights) with ΔE(0) and |E(SW)| are given, from which the formal potentials and the total surface excess can be accurately determined. SWVC has been applied to the study of the reduction of polyoxometalate [PMo12O40](3-) adsorbed at a boron doped diamond electrode (BDD), for which three stable and well-defined reversible charge peaks, corresponding to three cooperative EE processes, are obtained in the interval (0.6, -0.2) V by using low square wave frequencies. From the analysis of these peaks, the values of the total surface excess and the formal potentials of the six ETs have been obtained in aqueous media for two electrolytes: HClO4 and LiClO4.