Thermodynamic description of molten salt systems: KCl-LiCl-NaCl and KCl-LiCl-NdCl3

•The KCl-LiCl-NaCl system was thermodynamically optimized based on the SGTE Substance Database.•The surrounded-ion model was applied to calculate the mixing enthalpy in the KCl-LiCl-NdCl3 melt.•The KCl-LiCl-NdCl3 system was investigated using the CALPHAD method for the first time.•CALPHAD modeling can predict liquidus temperature variations of the KCl-LiCl based electrolyte during electrorefining. The mixture of KCl and LiCl has been used as electrolyte in the electrorefining process to recover uranium from used nuclear fuels due to the low melting point. However, lanthanides and sodium in the reactor waste continuously dissolve into it and thus alter its thermodynamic properties. To understand the thermodynamic behavior evolution of the electrolyte with the accumulation of impurities, thermodynamic modeling for KCl-LiCl-NaCl and KCl-LiCl-NdCl3 and four constituent binary systems in the entire composition space was performed using the CALPHAD (CALculation of PHAse Diagrams) approach. The ionic liquid was described by the two-sublattice model, where neutral species were introduced to consider short-range ordering (SRO) within the melt, whereas the solid solution was modeled based on the Compound Energy Formalism. Literature data on phase equilibria and thermochemical properties were critically evaluated and used during the optimization of thermodynamic parameters for KCl-LiCl-NaCl and KCl-LiCl-NdCl3 and their subsystems. The calculated phase diagrams and mixing enthalpies are in good agreement with the experimental data. The thermodynamic modeling for the KCl-LiCl-NdCl3 system was carried out for the first time. To fill the gap in experimental measurement, enthalpy of mixing for the KCl-LiCl-NdCl3 melt was estimated using the surrounded-ion model. These data then served as critical inputs for thermodynamic optimization. The present study can provide insights into thermodynamic property evolution of the electrolyte and solubility limit of various impurities during the electrorefining process.