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Many-electron Electrochemical Processes pp 1–19Cite as

Many-Electron Electrochemical Systems: Concepts and Definitions

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Part of the book series: Monographs in Electrochemistry ((MOEC))

Abstract

Hereby, an electrochemical process is defined as a many-electron one when the oxidation states of a reagent and final product differ by more than 1, thus requiring the transfer of more than one electron to transform, “electrochemically”, at a defined current flow, the reagent into the product.

Law < of Nature > is taken to be simple until the opposite is proven.

H. Poincaré

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Notes

  1. 1.

    Curious footnote on page 109 of [15] says:

    “In the first edition and in much of the literature, one finds n a used as the n value of the rate-determining step. As a consequence n a appears in many kinetic expressions. Since n a is probably always 1, it is a redundant symbol and has been dropped in this edition. The current–potential characteristic for a multistep process has often been expressed as <Butler–Volmer equation with αn a coefficient>. This is rarely, if ever, an accurate form of the i–E characteristic for multistep mechanisms.”

    At last!

  2. 2.

    Within this approach, a number of research works were carried out in Kiev in 1960–1980s. The ways to affect the nature of ionic-electronic transport were studied. As a result, direct electrolytic methods were developed for production of some nonferrous metals based on the phenomenon of suppressing electronic conductivity with some “heteropolar” additives like alkali metal sulphides, chlorides, and some other compounds [32–36].

  3. 3.

    The two last examples represent the FS intermediate between chemical and electrochemical ones, because the interaction follows the mechanism of electrochemical corrosion: overall current is zero, though partial currents flow with opposite sign, typical for corrosion situation. It seems that this kind of systems comprises also the processes of metal oxidation which obey Wagner’s theory (see Chap. 4).

  4. 4.

    Under this term we understand the regularities of the processes developing in the system in time on long-term scale, from tens minutes to several days or more, which results in relatively slow changes of macroscopic variables. A similar term is “dynamics”; it is used more often in physical papers and will be used in this book as well.

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Author information

Authors and Affiliations

  1. Kyiv Polytechnic Institute Chemical Technology Department, National Technical University of Ukraine, Kyiv, Ukraine

    Aleksandr A. Andriiko

  2. Centre of Electrochemical Surface Technology (CEST), Wiener Neustadt, Austria

    Yuriy O. Andriyko

  3. Institute of Physical Chemistry, Vienna University, Vienna, Austria

    Gerhard E. Nauer

Authors
  1. Aleksandr A. Andriiko
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  2. Yuriy O. Andriyko
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  3. Gerhard E. Nauer
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Andriiko, A.A., Andriyko, Y.O., Nauer, G.E. (2013). Many-Electron Electrochemical Systems: Concepts and Definitions. In: Many-electron Electrochemical Processes. Monographs in Electrochemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-35770-1_1

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