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Influence of the electrolysis conditions and composition of electrolytes in the M2WO4-M2W2O7-UO2WO4 system (M = Li, Na, K, Cs) on the oxygen coefficient of uranium oxide

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Abstract

The oxygen coefficient (O/U atomic ratio) of the cathodic product prepared by potentiostatic electrolysis of tungstate melts was studied in relation to the electrolyte composition, deposition potential, temperature of electrolysis, and cation of the solvent salt. With increasing temperature, the oxygen coefficient of the cathodic product increases. With shifting the deposition potential toward more negative potentials, with increasing concentration of W2O 2−7 anions, and with decreasing concentration of UO2WO4 in the tungstate electrolytes, uranium oxides with smaller oxygen coefficients are formed. The oxygen coefficient decreases with increasing radius of the salt cation, other conditions being equal. The abnormal behavior of melts based on Li2WO4 is probably due to lower activity of O2− anions capable to form strong Li3O+ complexes with lithium cations in the melt. The experimental results can be accounted for using the model of the ionic composition of uranyl-containing tungstate melts based on the concepts of complexation and stepwise solvolysis of uranyl ions.

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References

  1. Afonichkin, V.K., Komarov, V.E., and Vakarin, S.V., Elektrokhimiya, 1993, vol. 29, no. 11, pp. 1356–1359.

    CAS  Google Scholar 

  2. Afonichkin, V.K., Komarov, V.E., Khrustova, L.G., and Vakarin, S.V., Radiokhimiya, 2001, vol. 43, no. 3, pp. 224–229.

    Google Scholar 

  3. Mokhosoev, M., Alekseev, F.P., and Lutsyk, V.I., Diagrammy sostoyaniya molibdatnykh i vol’framatnykh sistem (Phase Diagrams of Molybdate and Tungstate Systems), Novosibirsk: Nauka, 1978.

    Google Scholar 

  4. Nomure, Y., Kamegashira, N., and Naito, K., J. Cryst. Growth, 1981, vol. 52, pp. 279–284.

    Article  Google Scholar 

  5. Afonichkin, V.K., Khokhlova, A.M., Komarov, V.E., and Leont’ev, V.N., Abstracts of Papers, VIII Kol’skii seminar po elektrokhimii redkikh metallov (VIII Kola Workshop on Electrochemistry of Rare Metals), Apatity, 1995, pp. 5–6.

  6. Afonichkin, V.K., Leont’ev, V.N., and Komarov, V.E., Elektrokhimiya, 1993, vol. 29, no. 3, pp. 341–347.

    CAS  Google Scholar 

  7. Afonichkin, V.K., Komarov, V.E., Khokhlova, A.M., and Leont’ev, V.N., Abstracts of Papers, X Vsesoyuznaya konferentsiya po fizicheskoi khimii i elektrokhimii ionnykh rasplavov i tverdykh elektrolitov (XI All-Union Conf. on Physical Chemistry and Electrochemistry of Ionic Melts and Solid Electrolytes), Yekaterinburg, 1992, pp. 47–48.

  8. Afonichkin, V.K., Komarov, V.E., and Khrustova, L.G., Abstracts of Papers, III Rossiiskaya konferentsiya po radiokhimii (III Russian Conf. on Radiochemistry), St. Petersburg, 2000, pp. 18–19.

  9. Afonichkin, V.K., Komarov, V.E., Khrustova, L.G., and Vakarin, S.V., Abstracts of Papers, Problemy elektrokristallizatsii metallov (Problems of Electrolytic Crystallization of Metals), Yekaterinburg, 2000, pp. 56–57.

  10. Cordfunke, E.H.P., J. Inorg. Nucl. Chem., 1965, vol. 31, no. 5, pp. 1542–1543.

    Article  Google Scholar 

  11. Afonichkin, V.K., Komarov, V.E., Leont’ev, V.N., and Nekrasova, N.P., Elektrokhimiya, 1996, vol. 32, no. 7, pp. 800–805.

    Google Scholar 

  12. Zakhar’yash, S.M., Cand. Sci. (Chem.) Dissertation, Sverdlovsk, 1982.

  13. Smirnov, V.M., Elektrodnye potentsialy v rasplavlennykh khloridakh (Electrode Potentials in Molten Chlorides), Moscow: Nauka, 1973.

    Google Scholar 

  14. Voronov, N.M., Sofronova, R.M., and Voitekhova, E.A., Vysokotemperaturnaya khimiya okislov urana i ikh soedinenii (High-Temperature Chemistry of Uranium Oxides and Their Compounds), Moscow: Atomizdat, 1971.

    Google Scholar 

  15. Iwai, S., Ossaka, J., and Okada, K., Kobutsugaku Zasshi, 1980, vol. 14 (Tokubetsugo 2), pp. 60–70.

    CAS  Google Scholar 

  16. Miyake, M., Ossaka, J., Iwai, S., et al., J. Chem. Soc., Faraday Trans., 1978, vol. 74, no. 10, pp. 1880–1884.

    CAS  Google Scholar 

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Authors and Affiliations

  1. Institute of High-Temperature Electrochemistry, Ural Division, Russian Academy of Sciences, Yekaterinburg, Russia

    V. K. Afonichkin, V. E. Komarov & L. G. Khrustova

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  1. V. K. Afonichkin
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  2. V. E. Komarov
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  3. L. G. Khrustova
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Original Russian Text © V.K. Afonichkin, V.E. Komarov, L.G. Khrustova, 2006, published in Radiokhimiya, 2006, Vol. 48, No. 2, pp. 128–133.

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Afonichkin, V.K., Komarov, V.E. & Khrustova, L.G. Influence of the electrolysis conditions and composition of electrolytes in the M2WO4-M2W2O7-UO2WO4 system (M = Li, Na, K, Cs) on the oxygen coefficient of uranium oxide. Radiochemistry 48, 141–147 (2006). https://doi.org/10.1134/S1066362206020068

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  • DOI: https://doi.org/10.1134/S1066362206020068

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