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Thermal reduction of U(VI) in laser liquids based on phosphorus oxychloride

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Abstract

The kinetics of U(VI) reduction in laser liquids POCl3-SnCl4-235UO 2+2 -Nd3+ and POCl3-SbCl5-235UO 2+2 -Nd3+ at 340, 360, and 370 K under the conditions ensuring protection from light was studied. The molar extinction coefficients of U(IV) at λ = 549, 635, 670, and 1148 nm were determined. The rate of U(IV) accumulation increases with temperature and with Nd3+ and UO 2+2 concentrations. The observed rate constants of U(IV) accumulation in POCl3-SbCl5-235UO 2+2 -Nd3+ are 2–3 times lower than in POCl3-SnCl4-235UO 2+2 -Nd3+. The activation energy of the U(IV) accumulation in the temperature range 340–370 K was 128 and 131 kJ mol−1 for POCl3-SnCl4-235UO 2+2 -Nd3+ and POCl3-SbCl5-235UO 2+2 -Nd3+, respectively. The Stern-Volmer constant of intracomplex nonradiative excitation energy transfer Nd3+ → U4+ amounted to (9.1 ± 1.8) × 105 and (8.4 ± 1.2) × 105 l mol−1 s−1 for POCl3-SnCl4-235UO 2+2 -Nd3+ and POCl3-SbCl5-235UO 2+2 -Nd3+, respectively.

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Authors and Affiliations

  1. Leipunskii Institute of Energy Physics, State Scientific Center of the Russian Federation, pl. Bondarenko 1, Obninsk, Kaluga oblast, 249033, Russia

    G. V. Tikhonov & A. S. Chernyshov

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  1. G. V. Tikhonov
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  2. A. S. Chernyshov
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Correspondence to G. V. Tikhonov.

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Original Russian Text © G.V. Tikhonov, A.S. Chernyshov, 2010, published in Radiokhimiya, 2010, Vol. 52, No. 2, pp. 132–136.

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Tikhonov, G.V., Chernyshov, A.S. Thermal reduction of U(VI) in laser liquids based on phosphorus oxychloride. Radiochemistry 52, 152–157 (2010). https://doi.org/10.1134/S1066362210020062

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