In situ spectroscopy and spectroelectrochemistry of uranium in high-temperature alkali chloride molten salts / Polovov Ilya B.,Volkovich Vladimir A.,Charnock John M.,Kralj Brett,Lewin Robert G.,Kinoshita Hajime,May Iain,Sharrad Clint A. // INORGANIC CHEMISTRY. - 2008. - V. 47, l. 17. - P. 7474-7482.

ISSN/EISSN:

0020-1669 / нет данных

Type:

Article

Abstract:

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 {[}UO(2)Cl(4)](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 {[}UO(2)Cl(4)](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.

Author keywords:

X-RAY; ABSORPTION-SPECTRA; AQUEOUS-SOLUTION; ELECTROCHEMICAL-BEHAVIOR; URANYL COMPLEXES; EUTECTIC MELT; 1073 K; EXAFS; RAMAN; COORDINATION

DOI:

10.1021/ic701415z

Web of Science ID:

ISI:000258709500011

Соавторы в МНС:

Другие поля

Поле	Значение
Month	SEP 1
Publisher	AMER CHEMICAL SOC
Address	1155 16TH ST, NW, WASHINGTON, DC 20036 USA
Language	English
Keywords-Plus	X-RAY; ABSORPTION-SPECTRA; AQUEOUS-SOLUTION; ELECTROCHEMICAL-BEHAVIOR; URANYL COMPLEXES; EUTECTIC MELT; 1073 K; EXAFS; RAMAN; COORDINATION
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Inorganic \& Nuclear
Author-Email	polovov@dpt.ustu.ru clint.a.sharrad@manchester.ac.uk
ResearcherID-Numbers	Volkovich, Vladimir/K-8339-2012 Sharrad, Clint/E-2499-2017
ORCID-Numbers	Volkovich, Vladimir/0000-0003-4438-1194 Sharrad, Clint/0000-0001-7372-8666
Funding-Acknowledgement	Nexia Solutions; INTAS
Funding-Text	We thank Nexia Solutions for financial support (to C.A.S. and V.A.V.) and INTAS for a fellowship (to I.B.P.).
Number-of-Cited-References	69
Usage-Count-Last-180-days	5
Usage-Count-Since-2013	43
Journal-ISO	Inorg. Chem.
Doc-Delivery-Number	341JD