Electrochemical Properties of Uranium on the Liquid Gallium Electrode in LiCl-KCl Eutectic

Abstract

This work presents a study of electrochemistry of uranium on a liquid gallium in LiCl-KCl eutectic by applying a series of electrochemical techniques. The electrochemical window of the Ga electrode in LiCl-KCl eutectic is about −1.40 to −0.35 V vs. Ag/AgCl. The reduction of U(III) on liquid gallium starts at −0.86 V and is a one step process with the transfer of three electrons. The co-reductive cyclic voltammograms of U(III) and Ga(III) present a couple of sharp redox peaks at about −0.95 and −0.84 V, corresponding to the formation and dissolution of the intermetallic compound UGa3. In addition, the reduction of Ga(III) in LiCl-KCl melt is a two-step process: Ga(III) → Ga(I) → Ga. The activity coefficient and solubility of U in liquid Ga at the temperature range from 673 to 823 K were determined by coulometric titration and open circuit potential respectively. The Gibbs free energy for the formation of UGa3 was also calculated. The intermetallic compound UGa3 was deposited by potentiostatic electrolysis at −1.0 V in the LiCl-KCl -GaCl3-UCl3 and LiCl-KCl-UCl3 melt on solid W and liquid Ga electrodes at 773 K, respectively. The electrolysis efficiency is about 97% based on the ICP result. Scanning Electron Microscopy coupled with Energy Dispersive Spectroscopy (SEM-EDS) and X-ray diffraction (XRD) characterizations further identified the formation of UGa3.