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Standard rate constants of charge transfer for Nb(V)/Nb(IV) redox couple in chloride-fluoride melts: Experimental and calculation methods

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Abstract

Standard rate constants k s of charge transfer for Nb(V)/Nb(IV) redox couple in NaCl-KCl (the equimolar mixture) -K2NbF7, KCl-K2NbF7, and CsCl-K2NbF7 melts are determined by using cyclic voltammetry. An unconventional series of the standard rate constants is found: k s (KCl) < k s (CsCl) < k s (NaCl-KCl). Ab initio calculations carried out by using a PC Gamess/Firefly quantum-chemical program showed that the charge transfer activation energy can change not monotonically in the Na-K-Cs series, in compliance with the reorganization energy relationship. This leads, in its turn, to nonmonotonic change in the charge transfer rate constants.

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Authors and Affiliations

  1. Tananaev Institute of Chemistry and Technology of Rare Elements and Minerals, Kola Science Center, Russian Academy of Sciences, ul. Fersmana 14, Apatity, Murmansk oblast, 184200, Russia

    A. V. Popova, V. G. Kremenetsky & S. A. Kuznetsov

  2. Kondratyuk National Technical University at Poltava, Poltava, Ukraine

    V. V. Solov’ev & L. A. Chernenko

  3. Petrozavodsk State University, Petrozavodsk, Russia

    O. V. Kremenetskaya & A. D. Fofanov

Authors
  1. A. V. Popova
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  2. V. G. Kremenetsky
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  3. V. V. Solov’ev
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  4. L. A. Chernenko
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  5. O. V. Kremenetskaya
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  6. A. D. Fofanov
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  7. S. A. Kuznetsov
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Corresponding author

Correspondence to S. A. Kuznetsov.

Additional information

Original Russian Text © A.V. Popova, V.G. Kremenetsky, V.V. Solov’ev, L.A. Chernenko, O.V. Kremenetskaya, A.D. Fofanov, S.A. Kuznetsov, 2010, published in Elektrokhimiya, 2010, Vol. 46, No. 6, pp. 714–722.

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Popova, A.V., Kremenetsky, V.G., Solov’ev, V.V. et al. Standard rate constants of charge transfer for Nb(V)/Nb(IV) redox couple in chloride-fluoride melts: Experimental and calculation methods. Russ J Electrochem 46, 671–679 (2010). https://doi.org/10.1134/S1023193510060121

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  • DOI: https://doi.org/10.1134/S1023193510060121

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