Electrochemical and Spectroscopic Monitoring of Interactions of Oxide Ion with U (III) and Ln (III) (Ln = Nd, Ce, and La) in LiCl-KCl Melts

Abstract

© The Author(s) 2017. Published by ECS. All rights reserved. Using cyclic voltammetry and UV-vis absorption spectroscopic methods, we studied the precipitation reactions of trivalent uranium and lanthanides (Nd, Ce, and La) with the oxide ion in LiCl-KCl molten salts, which are likely side reactions during the electrorefining process for nuclear fuel treatment. The in situ electrochemical and spectroscopic monitoring demonstrated that U 3+ consumed O 2 − with the mole ratio of 2:1, whereas the lanthanide ions reacted with O 2 − with the mole ratio of 1:1. Raman spectroscopy and X-ray diffraction were also employed to analyze the precipitates, confirming that U 3+ was precipitated and oxidized into UO 2 , while the trivalent lanthanide ions formed oxychlorides (LnOCl). As a preliminary study of actinide co-precipitation, we also electrochemically monitored the precipitation reactions in a mixed melt containing uranium and lanthanides, demonstrating a higher reactivity of the former with the oxide ion in LiCl-KCl.