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The Role of Chlorine Dioxide in the Electroreduction of Chlorates at Low pH

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Abstract

The specific features of the electroreduction of chlorates in strongly acidic aqueous solutions are studied by carrying out the electrolysis of 12.5 mM solution of sodium chlorate in 8 M sulfuric acid under potentiostatic conditions at the limiting cathodic current. The periodically collected optical spectrum of solution reveals the main contribution made by chlorine dioxide ClO2. It is shown that both the current and the chlorine dioxide concentration vary in time by one and the same law corresponding to the autocatalytic redox-mediator mechanism. When the current passes through a sharp maximum typical of this mechanism, a considerable part of the total concentration of chlorine atoms in the system pertains to chlorine dioxide; hence, this component plays the key role in the process of chlorate electroreduction. The virtually complete conversion of initial chlorate to chloride is observed.

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ACKNOWLEDGMENTS

We are grateful to A.D. Davydov and A.D. Modestov for their important comments on this paper.

Funding

This study was supported by the Russian Scientific Foundation (grant no. 20-63-46041).

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Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia

    D. V. Konev, O. A. Goncharova & M. A. Vorotyntsev

  2. Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia

    D. V. Konev & O. A. Goncharova

  3. Lomonosov Moscow State University, Moscow, Russia

    Yu. V. Tolmachev

  4. University of Massachusetts, Amherst, МА, USA

    Yu. V. Tolmachev

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  1. D. V. Konev
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  2. O. A. Goncharova
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  3. Yu. V. Tolmachev
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  4. M. A. Vorotyntsev
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Translated by T. Safonova

A tribute to outstanding electrochemist Oleg Aleksandrovich Petrii (1937–2021).

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Konev, D.V., Goncharova, O.A., Tolmachev, Y.V. et al. The Role of Chlorine Dioxide in the Electroreduction of Chlorates at Low pH. Russ J Electrochem 58, 978–988 (2022). https://doi.org/10.1134/S1023193522110088

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