Skip to main content
SpringerLink
Log in

Effect of Cation-Cation Complexes on Uranium(IV) Oxidation with Oxygen in Aqueous Solutions

  • Published:
Radiochemistry Aims and scope

Abstract

The reported data on the kinetics of U(IV) oxidation with oxygen in HClO4 and H2SO4 solutions, in near neutral media, and in bicarbonate solutions were analyzed. In acidic solutions at [U(IV)] = 0.005–0.02 M, the reaction rate –d[U(IV)]/dt = k[U(IV)][O2][H+]n, n varied from –1 to –2 with an increase in ionic strength from 0.5 to 4. UOH3+ and U(OH) 22+ ions react with O2, which brings about the appearance of UO2+ and HO2. UO2+ disproportionates and together with HO2 participates in a chain reaction. An increase in [H+] and [SO42–] reduces the proportion of UOH3+ and U(OH) 22+, accelerates U(V) disproportionation, and slows down oxidation. UO22+, U(OH) 22+, and USO42+ ions bind UO2+ into complexes, which inhibits U(IV) oxidation. At [U(IV)] > 0.02 M, the reaction slows down. In solutions of pH > 1.5, the reaction of U(OH) 22+ with O2 is accelerated by U(VI) ions; they form a complex with U(IV). The complex turns into U(V), which reacts with O2 faster than U(IV). In bicarbonate solutions, the kinetics of the oxidation reaction depends on [U(IV)]. The addition of U(VI) speeds up the process.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

REFERENCES

  1. Halpern, J. and Smith, J.G., Can. J. Chem., 1956, vol. 34, pp. 1419–1427.

    Article  CAS  Google Scholar 

  2. Weigel, F., The Chemistry of the Actinide Elements, London: Capman and Hall Ltd., 1957. https://doi.org/10.1002/ange.19590710318

    Book  Google Scholar 

  3. Bakac, A. and Espenson, J.H., Inorg. Chem., 1995, vol. 34, no. 7, pp. 1730–1753.

    Article  CAS  Google Scholar 

  4. Baker, B.F. and Newton, T.W., J. Phys. Chem., 1961, vol. 65, no. 10, pp. 1897–1899.

    Article  CAS  Google Scholar 

  5. Bhattacharyya, P.K. and Saini, R.D., Radiat. Phys. Chem., 1979, vol. 13, no. 1–2, pp. 57–63.

    CAS  Google Scholar 

  6. Elliot, A.J., Radamshi, S., and Pica, J., Can. J. Chem., 1986, vol. 64, p. 314

    Article  CAS  Google Scholar 

  7. Kern, D.M.H. and Orlemann, E.F., J. Am. Chem. Soc., 1949, vol. 71, no. 6, pp. 2102–2106.

    Article  CAS  Google Scholar 

  8. Orlemann, E.F. and Kern, D.M.H., J. Am. Chem. Soc., 1953, vol. 75, no. 12, p. 3068.

    Article  Google Scholar 

  9. Steele, H. and Taylor, R., Inorg. Chem., 2007, vol. 46, no. 16, p. 6311.

    Article  CAS  PubMed  Google Scholar 

  10. Newton, T.W. and Baker, F.B., Inorg. Chem., 1965, vol. 4, no. 8, pp. 1166–1170.

    Article  CAS  Google Scholar 

  11. Sobkovsky, J., Roczn. Chem. Ann. Soc. Chim. Polon., 1966, vol. 40, no. 2, pp. 271–280.

    Google Scholar 

  12. Koltunov, V.S., Elovskikh, N.N., Pankratova, Z.D., and Reshchikov, B.P., Zh. Fiz . Khim., 1974, vol. 48, no. 11, pp. 2739–2741.

    Google Scholar 

  13. Shilov, V.P. and Bukhtiyarova, T.N., Radiokhimiya,1991, vol. 33, no. 5, pp. 87–91.

    CAS  Google Scholar 

  14. Fedoseev, A.M., Peretrukhin, V.F., Orlova, M.M., and Krot, N.N., Radiokhimiya,1978, vol. 20, no. 6, pp. 804–808.

    CAS  Google Scholar 

  15. Sudarikov, B.N., Zakharov-Nartsissov, O.I., and Ochkin, A.V., Tr. MKhTI im., D.I. Mendeleeva, 1963, no. 43, pp. 78–81.

    Google Scholar 

  16. Bressat, R., Claudel, B., Feve, M., and Georgio, G., C.R. Acad. Sci., 1968. S 267, no. 12, p. 707–710.

    Google Scholar 

  17. Shilov, V.P., Yusov, A.B., Fedoseev, A.M., Peretrukhin, V.F., Gogolev, A.V., and Delegard, K.G., Radiochemistry, 2007, vol. 49, no. 5, pp. 470–475.

    Article  CAS  Google Scholar 

  18. Shilov, V.P., Yusov, A.B., Peretrukhin, V.F., Delegard, C.H., Gogolev, A.V., Fedosseev, A.M., and Kazansky, L.P., J. Alloys Compd., 2007. Vols. 444–445, pp. 333–338.

    Article  Google Scholar 

  19. Bion, L., Moisy, Ph., and Madic, C., Radiochim. Acta, 1995, vol. 69, no. 4, pp. 251–257.

    Article  CAS  Google Scholar 

  20. Gogolev, A.V., Shilov, V.P., Peretrukhin, V.F., Yusov, A.V., and Fedoseev, A.M., Radiochemistry, 2008, vol. 50, no. 4, pp. 349–359.

    Article  CAS  Google Scholar 

  21. Shilov, V.P., Yusov, A.B., Fedoseev, A.M., Peretrukhin, V.F., and Delegard, K.G., Radiochemistry, 2008, no. 5, pp. 460–465.

    Article  CAS  Google Scholar 

  22. Kanevskii, E.A., Goncharov, I.V., and Rengevich, V.B., Radiokhimiya,1965, vol. 7, no. 5, p. 579.

    CAS  Google Scholar 

Download references

ACKNOWLEDGMENTS

The authors are grateful to Ph. Moisy and E.V. Shilova for help in the selection of bibliographic material.

Author information

Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071, Moscow, Russia

    V. P. Shilov & A. M. Fedoseev

Authors
  1. V. P. Shilov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. M. Fedoseev
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to V. P. Shilov or A. M. Fedoseev.

Ethics declarations

The authors declare no conflict of interest.

Additional information

Translated from Radiokhimiya, No. 1, pp. 23–29, December, 2023 https://doi.org/10.31857/S0033831123010033

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shilov, V.P., Fedoseev, A.M. Effect of Cation-Cation Complexes on Uranium(IV) Oxidation with Oxygen in Aqueous Solutions. Radiochemistry 65, 21–27 (2023). https://doi.org/10.1134/S1066362223010034

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1066362223010034

Keywords:

Search

Navigation