In Situ Spectroscopy and Spectroelectrochemistry of Uranium in High-Temperature Alkali Chloride Molten Salts

Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molte...

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Veröffentlicht in:Inorganic chemistry 2008-09, Vol.47 (17), p.7474-7482
Hauptverfasser: Polovov, Ilya B, Volkovich, Vladimir A, Charnock, John M, Kralj, Brett, Lewin, Robert G, Kinoshita, Hajime, May, Iain, Sharrad, Clint A
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Sprache:eng
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Zusammenfassung:Soluble uranium chloride species, in the oxidation states of III+, IV+, V+, and VI+, have been chemically generated in high-temperature alkali chloride melts. These reactions were monitored by in situ electronic absorption spectroscopy. In situ X-ray absorption spectroscopy of uranium(VI) in a molten LiCl−KCl eutectic was used to determine the immediate coordination environment about the uranium. The dominant species in the melt was [UO2Cl4]2−. Further analysis of the extended X-ray absorption fine structure data and Raman spectroscopy of the melts quenched back to room temperature indicated the possibility of ordering beyond the first coordination sphere of [UO2Cl4]2−. The electrolytic generation of uranium(III) in a molten LiCl−KCl eutectic was also investigated. Anodic dissolution of uranium metal was found to be more efficient at producing uranium(III) in high-temperature melts than the cathodic reduction of uranium(IV). These high-temperature electrolytic processes were studied by in situ electronic absorption spectroelectrochemistry, and we have also developed in situ X-ray absorption spectroelectrochemistry techniques to probe both the uranium oxidation state and the uranium coordination environment in these melts.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic701415z