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

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 UGa 3 . 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 UGa 3 was also calculated. The intermetallic compound UGa 3 was deposited by potentiostatic electrolysis at −1.0 V in the LiCl-KCl -GaCl 3 -UCl 3 and LiCl-KCl-UCl 3 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 UGa 3 .