Abstract
The behavior of Pu(VI) and Pu(V) in CH3COOH (HAc)-H2O solutions was studied by spectrophotometry. The absorption spectrum of Pu(VI) does not change on adding HAc to a concentration of 5 M in the presence of 0.5–1.0 M HClO4, but in solutions containing less than 0.001 M mineral acid, changes in the spectrum are observed at HAc concentration of 0.6 M.he major absorption band of PuO 2+2 ions, caused by an f-f transition, with increasing [HAc] is shifted from 830.6 to 836 nm, with a simultaneous decrease in the absorption intensity, which is due to formation of 1: 1 complexes of Pu(VI) with Ac− ions. In anhydrous HAc, the peak intensity increases again, owing to total change in the composition of the solvation shell. Pu(V) is unstable in 1–17 M HAc solutions and disproportionates to form Pu(VI) and Pu(IV). The Pu(V) loss follows a second-order rate law with respect to [Pu(V)] and accelerates with increasing HAc concentration. The reaction products exert opposite effects on the reaction rate: Pu(IV) accelerates the consumption of Pu(V), whereas Pu(VI) does not affect the process in dilute HAc solutions but decelerates the disproportionation in concentrated solutions owing to formation of a cation-cation complex with Pu(V).
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Original Russian Text © A.V. Gogolev, A.A. Bessonov, V.P. Shilov, A.B. Yusov, A.M. Fedoseev, 2009, published in Radiokhimiya, 2009, Vol. 51, No. 2, pp. 115–120.
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Gogolev, A.V., Bessonov, A.A., Shilov, V.P. et al. Disproportionation of Pu(V) in the CH3COOH-H2O system. Radiochemistry 51, 132–137 (2009). https://doi.org/10.1134/S1066362209020052
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DOI: https://doi.org/10.1134/S1066362209020052