Specific features of reduction of plutonium(VI) ozonation products in solutions of various nature alkalis

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The decomposition processes of plutonium hydroxo compounds formed under ozonation conditions in MOH (M = Li, Na, K) solutions of various concentrations were studied by UV–Vis spectroscopy using a modified nonlinear least squares method. The influence of the nature of alkali on the kinetics and mechanisms of spontaneous reduction of alkaline solutions of hydroxo compounds of plutonium(VII) was discovered. This influence and the “anomalies” in the UV–Vis spectra for ozonized plutonium solutions are associated with the presence in the systems of iron compounds in the form of impurities in commercially available LiOH, NaOH and KOH (analytically pure, chemically pure, and ultrapure grade). Even trace amounts of impurities in alkaline solutions of plutonium compounds change the mechanisms of their reduction through the active participation of iron in redox processes. They include the oxidation of iron to ferrate(VI) ions FeO42–, followed by reduction to Fe3+, probably through the stage of formation of an intermediate with a hydroxo derivative of plutonium(VI). As a result of the analysis of large arrays of spectral data, the spectra of individual components corresponding to compounds of plutonium(VI, VII) and iron (VI) were isolated.

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Sobre autores

D. Pankratov

Moscow State University

Autor responsável pela correspondência
Email: pankratov@radio.chem.msu.ru

Department of Chemistry

Rússia, Leninskie gory 1, str. 3, Moscow, 119991

A. Romanchuk

Moscow State University

Email: pankratov@radio.chem.msu.ru

Department of Chemistry

Rússia, Leninskie gory 1, str. 3, Moscow, 119991

S. Kalmykov

Moscow State University

Email: pankratov@radio.chem.msu.ru

Department of Chemistry

Rússia, Leninskie gory 1, str. 3, Moscow, 119991

V. Dolzhenko

Moscow State University

Email: pankratov@radio.chem.msu.ru

Department of Chemistry

Rússia, Leninskie gory 1, str. 3, Moscow, 119991

Yu. Kiselev

Moscow State University

Email: pankratov@radio.chem.msu.ru

Department of Chemistry

Rússia, Leninskie gory 1, str. 3, Moscow, 119991

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2. Fig. 1. Changes in the absorption spectra for plutonium hydroxocomplexes spontaneously recovering after ozonation (at CPu = 1.5 × 10–3 M) in a 5 M NaOH solution, recorded at intervals of 3.6 min (a), and the optical density of solutions at 510 and 605 nm (b) over time.

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3. Fig. 2. Changes in the absorption spectra for plutonium hydroxocomplexes spontaneously recovering after ozonation (at CPu = 2.4 × 10–3 M) in a 2 M LiOH solution, recorded at intervals of ~4 min (a), and the optical density of solutions at 510 and 605 nm (b) over time.

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4. Fig. 3. Results of mathematical decomposition of a series of absorption spectra for solutions of plutonium hydroxocomplexes in NaOH (CPu = 1.5 × 10–3 M, CNaOH = 5 M) spontaneously recovering after ozonation into spectra of individual components (a) and changes in the content of components over time (b).

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5. Fig. 4. Results of mathematical decomposition of a series of absorption spectra for solutions of plutonium hydroxocomplexes in LiOH (CPu = 2.4 × 10–3 M, ClOH = 2 M) spontaneously recovering after ozonation into spectra of individual components (a) and changes in the content of components over time (b).

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