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Issue 15, 2017
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Electrochemical characterization of plutonium in n-tributyl phosphate

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This work investigates the electrochemical behavior of Pu(IV) and Pu(VI) complexes in n-tributylphosphate (TBP) as an entry to the electrochemical characterization of these complexes in organic extractants related to nuclear fuel reprocessing. Glassy carbon electrodes were used to show that Pu(IV) and Pu(VI) complexes display a reversible electrochemical reduction wave in TBP previously equilibrated with aqueous nitric acid solution. We investigated the reduction of Pu(IV) and Pu(VI) nitrato complexes extracted into TBP, with the aim to get thermodynamic (formal potential) and kinetic (diffusion coefficient) information about Pu(IV)/Pu(III) and Pu(VI)/Pu(V) redox couples in the TBP medium. The formal potentials of the two redox couples were respectively 0.510 ± 0.005 and 0.478 ± 0.005 V per SCE in TBP equilibrated with 3 mol L−1 nitric acid at room temperature. The diffusion coefficient values of Pu(IV) and Pu(VI) species were estimated to be 0.72 × 10−6 and 0.77 × 10−6 cm2 s−1 respectively. Also, the Pu(IV) reduction showed a Nernstian dependence on the logarithm of nitric acid concentration in the organic phase, featuring the exchange of nitrates upon reduction of Pu(IV).

Graphical abstract: Electrochemical characterization of plutonium in n-tributyl phosphate

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The article was received on 17 Dec 2016, accepted on 20 Feb 2017 and first published on 21 Feb 2017

Article type: Paper
DOI: 10.1039/C6DT04765C
Citation: Dalton Trans., 2017,46, 4943-4949
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    Electrochemical characterization of plutonium in n-tributyl phosphate

    M. A. Bahri, A. Ruas, E. Labbé and P. Moisy, Dalton Trans., 2017, 46, 4943
    DOI: 10.1039/C6DT04765C

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