Tungsten chemistry in alkali chloride melts

Abstract

Speciation of tungsten in alkali chloride melts (based on NaCl-2CsCl, NaCl-KCl and 3LiCl-2KCl mixtures) was studied between 550 and 750æC using electronic absorption spectroscopy. Only W(IV) and W(V) chloro and oxychloro species can be stabilized under the conditions studied. Tungsten(IV) chloride ions are very sensitive to oxide/hydroxide impurities present in the melt. Anodic dissolution of W metal at anodic current densities in the range of 0.005 - 0.1 A/cm2 produces only [WCl6]2- ions that can be electrochemically (on a glassy carbon anode) oxidized to [WCl 6]-. Small amounts of oxide ions present in the melt result in a gradual conversion of W(IV) chloro species into W(IV) oxychloro species. In the presence of O2 in the atmosphere [WCl 6]2- is oxidized into the tungsten(V) species [WOCl 5]2-. Dissolution of tungsten hexachloride, WCl 6, in an NaCl-2CsCl melt initially yields [WCl6] 2- (due to disproportionation). Reaction of metallic tungsten with Pd(II)-containing melts results in the formation of [WCl6] 2- species. The main spectroscopic parameters of [WCl 6]2- and [WCl6]- complex ions were calculated. © 2007 Verlag der Zeitschrift für Naturforschung.