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Behavior of Np(V) in HCOOH Solutions Containing H2O and HClO4

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Abstract

Spectrophotometry has been used to examine the kinetics of Np(V) disproportionation in HCOOH solutions containing H2O and HClO4 at temperatures of 20–45°C. The reaction rate is described in the initial portion by the equation –d[Np(V)]/dt = k[Np(V)]2. The rate constant k sharply grows with increasing [HClO4] (order n = 3.5) and with decreasing content of H2O (n = –2.30. The appearing Np(VI) is slowly reduced to Np(V) by formic acid. The activation energy of the disproportionation reaction is 54 kJ mol–1. The mechanism includes the elimination of an H2O molecule from the H+aq ion and addition of a proton to NpO2+. The protonated Np(V) ions form a dimer which is an activated complex. The H transfer in this complex yields Np(IV) and Np(VI).

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ACKNOWLEDGMENTS

The authors are grateful to G.V. Sidorenko, doctor of science (chemistry) for his participation in the discussion of the results obtained in the study and helpful advice.

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Authors and Affiliations

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

    V. P. Shilov, A. V. Gogolev & A. M. Fedoseev

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  1. V. P. Shilov
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  2. A. V. Gogolev
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  3. A. M. Fedoseev
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Correspondence to V. P. Shilov.

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Translated from Zhurnal Prikladnoi Khimii, No. 1, pp. 13–17, December, 2020 https://doi.org/10.31857/S0033831121010020

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Shilov, V.P., Gogolev, A.V. & Fedoseev, A.M. Behavior of Np(V) in HCOOH Solutions Containing H2O and HClO4. Radiochemistry 63, 11–15 (2021). https://doi.org/10.1134/S1066362221010021

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  • DOI: https://doi.org/10.1134/S1066362221010021

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