On the formation of uranium(V) species in alkali chloride melts

Uranyl(V) species are normally unstable in solutions but are here shown to be stable in high-temperature chloride melts. Reactions leading to the formation of UO₂Cl₄ ^3- ions were studied, including thermal decomposition and chemical reduction of uranyl(VI) chlorospecies in various alkali chloride melts (LiCl, 3LiCl-2KCl, NaCl-KCl, and NaCl-2CsCl) at 550-850 °C. Decomposition of UO₂Cl₄ ^2- species under reduced pressure, with inert gas bubbling through the melt or using zirconium getter in the atmosphere results in the formation of UO ₂Cl₄ ^3- and UO₂. Elemental tellurium, palladium, silver, molybdenum, niobium, zirconium, and hydrogen, as well as niobium and zirconium ions were tested as the reducing agents. The outcome of the reaction depends on the reductant used and its electrochemical properties: uranyl(VI) species can be reduced to uranyl(V) and uranium(IV) ions, and to uranium dioxide.