Sonochemical redox reactions of Pu( iii ) and Pu( iv ) in aqueous nitric solutions - Université de Montpellier
Article Dans Une Revue Dalton Transactions Année : 2015

Sonochemical redox reactions of Pu( iii ) and Pu( iv ) in aqueous nitric solutions

Résumé

The behavior of Pu(IV) and Pu(III) was investigated in aqueous nitric solutions under ultrasound irradiation (Ar, 20 kHz). In the absence of anti-nitrous reagents, ultrasound has no effect on Pu(IV), while Pu(III) can be rapidly oxidized to Pu(IV) due to the autocatalytic formation of HNO$_2$ induced by HNO$_3$ sonolysis. In the presence of anti-nitrous reagents (sulfamic acid or hydrazinium nitrate), Pu(IV) can be sonochemically reduced to Pu(III). The reduction follows a first order reaction law and leads to a steady state where Pu(IV) and Pu(III) coexist in solution. The reduction process is attributed to the sonochemical generation of H$_2$O$_2$ in solution. The kinetics attributed to the reduction of Pu(IV) are however higher than those related to the formation of H$_2$O$_2$ which, after several hypotheses, is explained by the sonochemical erosion of the titanium-based sonotrode. Titanium particles thereby generated can be solubilized under ultrasound and generate Ti(III) as an intermediate species, a strong reducing agent able to react with Pu(IV).

Domaines

Radiochimie
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Dates et versions

hal-02076929 , version 1 (25-08-2020)

Identifiants

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Matthieu Virot, Laurent Venault, Philippe Moisy, Sergey I. Nikitenko. Sonochemical redox reactions of Pu( iii ) and Pu( iv ) in aqueous nitric solutions. Dalton Transactions, 2015, 44 (6), pp.2567-2574. ⟨10.1039/C4DT02330G⟩. ⟨hal-02076929⟩
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