Редколлегия Физикохимия Поверхности и Защита Материалов - On Prerequisites for Electronic Mechanism of Electrode Reactions

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Abstract — Equilibrium state of a two-phase system (metal–solution) is conventionally considered (see e.g. [1–3]) as a reversible process of the charge transfer by a metal cation through the interface boundary (this concept is applied to both first-kind electrodes and second-kind electrodes reversible in the anion of the metal salt, as well as redox electrodes, which may be reduced to the first-kind electrodes using the Luther rule). However, it is actually an electron that is the main charged component in all these exchanges. The exchange processes cannot be directly measured at the molecular level, while the electron current in the external circuit of the galvanic cell can be measured quite accurately. The current and potential (the potential difference between the studied and auxiliary electrodes) are the main characteristics of the electrode processes. Theoretical analysis of these phenomena by an example of electrolysis is the object of the present study.