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Electrochemical and quantum-chemical studies of chromium(III,II) fluoride complexes in alkali chloride melts

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Abstract

The standard rate constants (k s) of charge transfer on a glass carbon electrode were determined for the Cr(III)/Cr(II) redox pair in the NaCl-KCl-K3CrF6, KCl-K3CrF6, and CsCl-K3CrF6 systems at 973–1173 K by cyclic voltammetry. The k s constant was found to increase at elevated temperatures and the following nonmonotonic dependence of k s on the nature of the outer-spheric cation was found: k s (CsCl) > k s (NaCl-KCl) > k s (KCl). On the basis of quantum-chemical data for the M3CrF6 + 18MCl (M = Na, K) model systems, it was shown that the complex chromium particles with four or five outer-spheric sodium or potassium cations had maximum thermodynamic stability. Quantum-chemical calculations were performed to interpret the experimental data on the effect of the second coordination sphere of the complexes on the standard charge transfer rate constants.

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Authors and Affiliations

  1. Tananaev Institute of Chemistry and Technology of Rare Elements and Raw Materials, Russian Academy of Sciences, Kola Science Center, Russian Academy of Sciences, Apatity, Russia

    Yu. V. Stulov, V. G. Kremenetsky & S. A. Kuznetsov

Authors
  1. Yu. V. Stulov
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  2. V. G. Kremenetsky
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  3. S. A. Kuznetsov
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Correspondence to S. A. Kuznetsov.

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Original Russian Text © Yu.V. Stulov, V.G. Kremenetsky, S.A. Kuznetsov, 2014, published in Elektrokhimiya, 2014, Vol. 50, No. 9, pp. 907–916.

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Stulov, Y.V., Kremenetsky, V.G. & Kuznetsov, S.A. Electrochemical and quantum-chemical studies of chromium(III,II) fluoride complexes in alkali chloride melts. Russ J Electrochem 50, 815–823 (2014). https://doi.org/10.1134/S1023193514090109

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  • DOI: https://doi.org/10.1134/S1023193514090109

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