Multi-electron electrochemical reaction

General Solution for Multi-electron Electrochemical Reactions. 185... 

In this section, the results corresponding to an EE process are generalized for a multi-electron electrochemical reaction of k steps (multi-E process) in agreement with the reaction scheme ... 

The electrochemical characterization of multi-electron electrochemical reactions involves the determination of the formal potentials of the different steps, as these indicate the thermodynamic stability of the different oxidation states. For this purpose, subtractive multipulse techniques are very valuable since they combine the advantages of differential pulse techniques and scanning voltammetric ones [6, 19, 45-52]. All these techniques lead to peak-shaped voltammograms, even under steady-state conditions. 

Here, the response of multi-electron electrochemical reactions in subtractive multipulse voltammetries is treated by first considering the situation in which all the electron transfers are reversible. The case corresponding to slow electron transfers with different types of stabilization of the intermediate species is also analyzed. 

Equations (6.15) and (6.16) cover an important gap in the electrochemical literature corresponding to multi-electron electrochemical reactions, since they provide the theoretical background for the study of these electrode processes in any electrochemical technique for electrodes of different geometry and size. 

Voltcoulommetry (DSCVC) and Square Wave Voltcoulommetry (SWVC) are also considered, since they are very valuable tools for the analysis of fast electrochemical reactions between surface-confined molecules. First, a simple mono-electronic electrochemical reaction is analyzed and, after that, the cases corresponding to multi-electron electrochemical reactions and chemical reactions coupled to the surface charge transfer, including electrocatalytic processes, are discussed. 

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