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Temporal Instabilities in Cathodic Processes at Liquid and Solid Electrodes

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Self-Organization in Electrochemical Systems I

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

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Abstract

Experimental examples and theoretical models of the oscillatory and mutistable behavior in cathodic processes of various species, studied at both liquid (mercury) and solid electrodes, are described. The following processes with the N-NDR characteristics are analyzed: (1) electroreduction of S2O 2−8 ions on mercury and solid (polycrystalline and single crystal) metal electrodes, under conditions when the Frumkin effect of the electric double layer is (or is not) operating; (2) electroreduction of IO −3 ions on polycrystalline Ag electrode, considered as an HN-NDR type oscillator due to the existence of an additional current carrier; (3) polarographic reduction of In(III)–SCN− complexes; (4) electroreduction of the Ni(II)–SCN− complexes at mercury electrodes, including novel application of the streaming Hg electrode; (5) electroreduction of the Ni(II)–N −3 complexes at a streaming mercury electrode, exhibiting rarely reported phenomenon of tristability; (6) polarographic electroreduction of Cu2+ in the presence of adsorbed inhibitor (“the inhibitor oscillator”); (7) electroreduction of H2O2 on metal (Ag, Au, Pt) polycrystalline and single-crystal electrodes, including suggestions for a new type of electrochemical oscillator (coupled NDR, CNDR), extending the classification scheme given in Sect. 3.5; (8) electroreduction of H2O2 on Cu-based and GaAs semiconductor electrodes, indicating the specific role of semiconducting phase played only in the latter case. Experimental and model results include both dc and ac (impedance) characteristics.

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Notes

  1. 1.

    Since x 2 is usually much smaller than the thickness of the diffusion layer, \( {\it c_{\rm{ox}}}{\hskip -7pt^{\rm b}} \) is considered a “surface concentration”, generally dependent on time t, and in diffusion-oriented problems is usually presented in the notation: \( {c_{\rm{ox}}}(0,t) \). Thus, here \( {\it c_{\rm{ox}}}{\hskip -7pt^{\rm b}} \approx {c_{\rm{ox}}}({\rm 0},t)[2] \).

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    Marek Orlik

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Orlik, M. (2012). Temporal Instabilities in Cathodic Processes at Liquid and Solid Electrodes. In: Self-Organization in Electrochemical Systems I. Monographs in Electrochemistry. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-27673-6_4

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