Behavior of molybdenum in pyrochemical reprocessing: A spectroscopic study of the chlorination of molybdenum and its oxides in chloride melts / Volkovicha VA,Griffiths TR,Thied RC,Lewin B // JOURNAL OF NUCLEAR MATERIALS. - 2003. - V. 323, l. 1. - P. 93-100.

ISSN/EISSN:

0022-3115 / нет данных

Type:

Article

Abstract:

The high temperature reactions of molybdenum and its oxides with chlorine and hydrogen chloride in molten alkali metal chlorides were investigated between 400 and 700 degreesC. The melts studied were LiCl-KCl, NaCl-CsCl and NaClKCl and the reactions were followed by in situ electronic absorption spectroscopy measurements. In these melts Mo reacts with Cl(2) and initially produces MoC(6)(2-) and then a mixture of Mo(III) and Mo(V) chlorocomplexes, the final proportion depending on the reaction conditions. The Mo(V) content can be removed as MoCl(5) from the melt under vacuum or be reduced to Mo(III) by Mo metal. The reaction of Mo when HCl gas is bubbled into alkali chloride melts yields only MoCl(6)(3-). MoO(2) reacts in these melts with chlorine to form soluble MoOCl(5)(2-) and volatile MoO(2)Cl(2). MoO(3) is soluble in chloride melts and then decomposes into the oxychloride MoO(2)Cl(2), which sublimes or can be sparged from the melt, and molybdate. Pyrochemical reprocessing can thus be employed for molybdenum since, after various intermediates, the end-products are chloride melts containing chloro and oxychloro anions of molybdenum plus molybdate, and volatile chlorides and oxychlorides that can be readily separated off. The reactions were fastest in the NaCl-KCl melt. The X-ray diffraction pattern of MoO(2)Cl(2) is reported for the first time. (C) 2003 Elsevier B.V. All rights reserved.

Author keywords:

CHEMICAL-STATE; FISSION-PRODUCTS; ABSORPTION-SPECTROSCOPY; MOLTEN-SALT; SPECTRA; FUELS; COMPLEXES; CHEMISTRY

DOI:

10.1016/j.jnucmat.2003.08.039

Web of Science ID:

ISI:000186726300013

Соавторы в МНС:

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Другие поля

Поле	Значение
Month	NOV 15
Publisher	ELSEVIER SCIENCE BV
Address	PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS
Language	English
Keywords-Plus	CHEMICAL-STATE; FISSION-PRODUCTS; ABSORPTION-SPECTROSCOPY; MOLTEN-SALT; SPECTRA; FUELS; COMPLEXES; CHEMISTRY
Research-Areas	Materials Science; Nuclear Science \& Technology
Web-of-Science-Categories	Materials Science, Multidisciplinary; Nuclear Science \& Technology
Author-Email	t.r.griffiths@chem.leeds.ac.uk
ResearcherID-Numbers	Volkovich, Vladimir/K-8339-2012
ORCID-Numbers	Volkovich, Vladimir/0000-0003-4438-1194
Number-of-Cited-References	34
Usage-Count-Since-2013	8
Journal-ISO	J. Nucl. Mater.
Doc-Delivery-Number	746BK