Abstract
The thermodynamic stability of Ln(III) (Ln: La, Ce, Pr, Tb, and Er) and U(III) complexes in LiCl–KCl system at 923K was studied by electrochemical techniques. The Gibbs free energy change of the Ln3+/Ln0 and U3+/U0 redox reactions, ΔG3/0∘′, was investigated under various mole fraction of KCl, χK=0–0.65. In general, ΔG3/0∘′ increased linearly with the decrease of χK due to the distortion of octahedral symmetry of LnCl63- and UCl63-, but a few exceptions were found for lighter Ln elements, e.g., La and Ce, at smaller χK of 0–0.2. The discrepancy suggests an increase of the number of Cl− ions around La3+ and Ce3+.
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