Vanadium Speciation in Fused Alkali Chlorides

Electronic absorption spectra of vanadium ions were recorded between 450 and 750◦C in 3LiCl–2KCl, NaCl–KCl and NaCl–2CsCl based melts. Analysis of the spectra showed that vanadium in the oxidation states of +2 and +3 is present in the melts as complex chloro-ions. Vanadium(II) can form the complex ions in octahedral and tetrahedral coordination, the latter being favored by higher temperatures. Only six-coordinated V(III) ions were observed. Vanadium in the oxidation state of +4 can be present in chloride melts only in the form of vanadyl-based oxochloro-species. Main spectroscopic parameters of vanadium complex ions were determined. Electronic absorption spectroscopy was also applied for studying a variety of the red-ox processes in vanadium containing melts including electrochemical oxidation and reduction of various species, and reaction of vanadium containing melts with oxygen. © The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0201708jes] All rights reserved.

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