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

Hao, Liangyan; Sridar, Soumya; Xiong, Wei

doi:10.1016/j.molliq.2023.121869

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

Journal Article · Thu Apr 20 00:00:00 EDT 2023 · Journal of Molecular Liquids

DOI:https://doi.org/10.1016/j.molliq.2023.121869· OSTI ID:2259217

Hao, Liangyan ^[1]; Sridar, Soumya ^[1]; Xiong, Wei ^[1]

University of Pittsburgh, PA (United States)

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. Furthermore, the present study can provide insights into thermodynamic property evolution of the electrolyte and solubility limit of various impurities during the electrorefining process.

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Research Organization:: Univ. of Pittsburgh, PA (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP)

Grant/Contract Number:: NE0008958

OSTI ID:: 2259217

Alternate ID(s):: OSTI ID: 2259248

Journal Information:: Journal of Molecular Liquids, Vol. 382; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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