Erratum to “Chemistry of vanadium chlorides in molten salts: An electronic absorption spectroscopy study” [J. Mol. Liqs. 103–104 (2003): 387–394

Abstract

Chloro- and oxychloro complex ions of vanadium, containing the metal in all its oxidation states, II, III, IV and V, have been obtained and examined in NaClKCl and NaClCsCl melts between 550 and 980 °C. Vanadium was introduced into the melt by anodic dissolution and by reacting the metal and oxides, V 2O 3, V 2O 4 and V 2O 5, with chlorine and hydrogen chloride. The spectra of vanadium(II) were recorded in silica cells as well as by reflection-absorption spectroscopy in a silica-free set up. Melts containing initially V(II) and V(III) chloro species were readily oxidised to V(IV) when exposed to air or when water was generated in the melt by reaction of oxide with HCl. The reaction of vanadium with chlorine was studied at Cl 2 flow rates and various temperatures, and yielded V(III) and V(IV) ions, with V(III)-containing melts prevailing at higher temperatures because the volatile VCl 4 was swept out with the Cl 2. Lower vanadium oxides (III and IV) in these melts react with HCl to produce mainly vanadyl complex ions, VOCl 5 3−.