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Electrochemical and spectroscopic studies of tungsten species in the AlCl{sub 3}-NaCl{sub sat} melt

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/1.2044190· OSTI ID:82905
; ; ; ;  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
The electrochemical behavior of KWCl{sub 6} in the AlCl{sub 3}-NaCl{sub sat} melt at 175 to 200 C was investigated using multiple electrochemical methods: cyclic, normal pulse, square wave voltammetries, chronoamperometry, and exhaustive electrolysis. Electronic spectroscopy and x-ray diffraction methods were employed to characterize the products formed at different potentials. The melt was treated-with CCl{sub 4} to remove oxide impurities. It was found that the reduction sequence of W(V) was dependent on the scan rate, i.e., at fast scan rates three main redox couples were observed, while additional redox couples appeared in low scan rate voltammograms. To reach a better understanding of the mechanism, some low oxidation state tungsten compounds (K{sub 2}WCl{sub 6} and W{sub 6}Cl{sub 12}) were also examined. The reduction of W(V) to tungsten metal involves several intermediate oxidation states and cluster species, such as W(IV), unstable W(III), dimers W(IV, III) and W(III,II), [W{sub 6}Cl{sub 8}]{sup 4+} and its one-electron reduction product. Partial characterization of some of the intermediate reduction products has been achieved.
Sponsoring Organization:
USDOE
OSTI ID:
82905
Journal Information:
Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 6 Vol. 142; ISSN JESOAN; ISSN 0013-4651
Country of Publication:
United States
Language:
English