In situ Raman spectroscopy of samarium ions in molten LiCl-KCl eutectic

Abstract

A fiber-based Raman spectroscopy system was commissioned in an inert atmosphere for in situ analysis of high temperature molten salts. Speciation of samarium chloride was studied in the LiCl-KCl eutectic system at 500 °C. Raman spectra indicated trivalent samarium forms an octahedral SmCl63- complex with two detectable vibration modes. Chemical reduction experiments were conducted to investigate the coordination of divalent samarium in the same eutectic salt. The resulting spectra are reported and discussed in terms of complex formation and behavior of divalent samarium ions. Trivalent samarium was electrochemically reduced in situ and Raman spectra obtained were compared with those resulting from chemical reduction experiments. The spectra suggest divalent samarium ions form in LiCl-KCl only temporarily and spontaneously disproportionate into a mixture of trivalent samarium ions and metallic samarium.