The electrode reactions of the Ce3+/Ce couple in LiCl-KCl solutions containing 1 wt% CeCl3 at 773 K at solid W and liquid Cd electrodes were investigated through a voltammetric analysis. The reduction in the peak potentials of Ce was -2.04V and -1.47 Vat the solid W and liquid Cd electrodes, respectively. It was explained, using a W electrode ma LiCl-KCl-CeCl3-CdCl2 solution, that the large potential difference was related to the formation of intermetallic compounds between the Ce and Cd phases. Through these experiments, the Gibbs free energies of the formation of Ce-Cd intermetallic compounds, such as CeCd, CeCd2, CeCd3, CeCd4.46, CdCd6 and CeCd11, were successfully obtained at the Cd-coated W electrode using chronopotentiometry. Crown Copyright (C) 2012 Published by Elsevier Ltd. All rights reserved.