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

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 ^[2]; Xiong, Wei ^[2]

University of Pittsburgh, PA (United States); University of Pittsburgh
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.

View Accepted Manuscript (DOE)

Research Organization:: University 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, Journal Name: Journal of Molecular Liquids Vol. 382; ISSN 0167-7322

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Chemie der Seltenen Erden in geschmolzenen Alkalichloriden. I. Schmelzen von Alkalichloriden mit Lanthanchlorid und Neodymchlorid Förthmann, R.; Vogel, G.; Schneider, A. Zeitschrift für anorganische und allgemeine Chemie, Vol. 367, Issue 1-2 https://doi.org/10.1002/zaac.19693670103	journal	May 1969
Properties of double chlorides in the systems ACl/NdCl3 (ANa-Cs) Seifert, H. -J.; Fink, H.; Uebach, J. Journal of Thermal Analysis, Vol. 33, Issue 3 https://doi.org/10.1007/BF02138565	journal	September 1988
Thermodynamic calculation of phase diagrams of the 60 common-ion ternary systems containing cations Li, Na, K, Rb, Cs and anions F, Cl, Br, I Songster, J.; Pelton, A. D. Journal of Phase Equilibria, Vol. 12, Issue 5 https://doi.org/10.1007/BF02645064	journal	October 1991
A two-sublattice model for molten solutions with different tendency for ionization Hillert, Mats; Jansson, Bo; Sundman, Bo Metallurgical Transactions A, Vol. 16, Issue 2 https://doi.org/10.1007/BF02816052	journal	February 1985
Thermodynamic Assessments of the Pd–Sn and Pt–Sn Systems With the Modified Quasi-chemical Model for Liquid Cui, Senlin; Wang, Jian; Jung, In-Ho Metallurgical and Materials Transactions A, Vol. 53, Issue 12 https://doi.org/10.1007/s11661-022-06825-9	journal	October 2022
The modified quasichemical model I—Binary solutions Pelton, A. D.; Degterov, S. A.; Eriksson, G. Metallurgical and Materials Transactions B, Vol. 31, Issue 4 https://doi.org/10.1007/s11663-000-0103-2	journal	August 2000
A Review of Calphad Modeling of Ordered Phases Sundman, Bo; Chen, Qing; Du, Yong Journal of Phase Equilibria and Diffusion, Vol. 39, Issue 5 https://doi.org/10.1007/s11669-018-0671-y	journal	August 2018
Investigation on the Phase Diagram of LiCl-KCl-NdCl3 Pseudo-Ternary System Ghosh, Sajal; Ganesan, Rajesh; Sridharan, R. Journal of Phase Equilibria and Diffusion, Vol. 39, Issue 6 https://doi.org/10.1007/s11669-018-0695-3	journal	November 2018
Fundamental Issues Identified for Thermodynamic Description of Molten Salt Systems Xiong, Wei; Hao, Liangyan Journal of Phase Equilibria and Diffusion, Vol. 43, Issue 6 https://doi.org/10.1007/s11669-022-01018-8	journal	November 2022
The phase equilibrium diagram for the KCl-NaCl system Coleman, D. S.; Lacy, P. D. A. Materials Research Bulletin, Vol. 2, Issue 10 https://doi.org/10.1016/0025-5408(67)90149-3	journal	October 1967
Calorimetric investigation of NdCl3MCl liquid mixtures (where M is Na, K, Rb, Cs) Gaune-Escard, M.; Bogacz, A.; Rycerz, L. Thermochimica Acta, Vol. 236 https://doi.org/10.1016/0040-6031(94)80256-4	journal	May 1994
Empirical methods of predicting and representing thermodynamic properties of ternary solution phases Hillert, Mats Calphad, Vol. 4, Issue 1 https://doi.org/10.1016/0364-5916(80)90016-4	journal	January 1980
Entropies of phase transitions in the M3LnCl6 compounds (MK, Rb, Cs; LnLa, Ce, Pr, Nd) and K2LaCl5 Gaune-Escard, M.; Rycerz, L.; Szczepaniak, W. Journal of Alloys and Compounds, Vol. 204, Issue 1-2 https://doi.org/10.1016/0925-8388(94)90090-6	journal	February 1994
Phase equilibria of NdC13NaClKCl Hosoya, Yuji; Terai, Takayuki; Tanaka, Satoru Journal of Nuclear Materials, Vol. 247 https://doi.org/10.1016/S0022-3115(97)00056-1	journal	August 1997
Thermal analysis of pseudo-binary system: LiClKCI eutectic and lanthanide trichloride Nakamura, Kinya; Kurata, Masaki Journal of Nuclear Materials, Vol. 247 https://doi.org/10.1016/S0022-3115(97)00099-8	journal	August 1997
Thermo-Calc & DICTRA, computational tools for materials science Andersson, J-O; Helander, Thomas; Höglund, Lars Calphad, Vol. 26, Issue 2 https://doi.org/10.1016/S0364-5916(02)00037-8	journal	June 2002
Investigation on the phase diagram of the ternary system LaCl3–NaCl–LiCl Shujian, Tian; Shixiang, Liu; Chaogui, Zheng Journal of Alloys and Compounds, Vol. 279, Issue 2 https://doi.org/10.1016/S0925-8388(98)00654-9	journal	October 1998
Calculation of phase diagrams: Calphad Ågren, John Current Opinion in Solid State and Materials Science, Vol. 1, Issue 3 https://doi.org/10.1016/S1359-0286(96)80025-8	journal	June 1996
An attempt to correct the quasichemical model Hillert, Mats; Selleby, Malin; Sundman, Bo Acta Materialia, Vol. 57, Issue 17 https://doi.org/10.1016/j.actamat.2009.07.026	journal	October 2009
Optimization and calculation of the NdCl3–MCl (M=Li, Na, K, Rb, Cs) phase diagrams Sun, Yimin; Ye, Xinyu; Wang, Yu Calphad, Vol. 28, Issue 2 https://doi.org/10.1016/j.calphad.2004.07.004	journal	June 2004
A brief history of CALPHAD Spencer, P. J. Calphad, Vol. 32, Issue 1 https://doi.org/10.1016/j.calphad.2007.10.001	journal	March 2008
Experimental investigations and thermodynamic modelling of KCl–LiCl–UCl3 system Ghosh, Suddhasattwa; Prabhakara Reddy, B.; Nagarajan, K. Calphad, Vol. 45 https://doi.org/10.1016/j.calphad.2013.11.001	journal	June 2014
Thermodynamic assessment of the LiCl–KCl–CeCl3 system He, Maogang; Lu, Guangxuan; Kang, Zhangyang Calphad, Vol. 49 https://doi.org/10.1016/j.calphad.2015.01.006	journal	June 2015
Phase equilibria in the reciprocal NaCl–KCl–NaNO3–KNO3 system Sergeev, D.; Yazhenskikh, E.; Kobertz, D. Calphad, Vol. 51 https://doi.org/10.1016/j.calphad.2015.09.002	journal	December 2015
Emulation of short-range ordering within the Compound Energy Formalism: Application to the calcite-magnesite solid solution Liu, Xin; Vinograd, Victor L.; Nichenko, Sergii Calphad, Vol. 64 https://doi.org/10.1016/j.calphad.2018.11.012	journal	March 2019
Thermodynamic description of the constitutive binaries of the NaCl-KCl-UCl3-PuCl3 system Yin, Huiqin; Lin, Jian; Hu, Biao Calphad, Vol. 70 https://doi.org/10.1016/j.calphad.2020.101783	journal	September 2020
Experimental study and thermodynamic assessment of thermodynamic properties of pure Li2CO3 and K2CO3 Qi, Jia; Yazhenskikh, Elena; Ziegner, Mirko Calphad, Vol. 78 https://doi.org/10.1016/j.calphad.2022.102452	journal	September 2022
Thermodynamic modeling of KCl-PrCl3 and KCl-LiCl-PrCl3 systems Sridar, Soumya; Hao, Liangyan; Xiong, Wei Calphad, Vol. 81 https://doi.org/10.1016/j.calphad.2023.102552	journal	June 2023
Thermodynamic assessment of LiCl–NdCl3 and LiCl–PrCl3 quasi-binary systems Gong, Weiping; Gaune-Escard, Marcelle; Rycerz, L. Journal of Alloys and Compounds, Vol. 396, Issue 1-2 https://doi.org/10.1016/j.jallcom.2004.12.021	journal	June 2005
Experimental investigation and thermodynamic modelling of LiF-NdF3-DyF3 system Abbasalizadeh, A.; Sridar, S.; Chen, Z. Journal of Alloys and Compounds, Vol. 753 https://doi.org/10.1016/j.jallcom.2018.04.013	journal	July 2018
Thermodynamic measurements and assessments for LiCl-NaCl-KCl-UCl3 systems Yingling, J. A.; Schorne-Pinto, J.; Aziziha, M. The Journal of Chemical Thermodynamics, Vol. 179 https://doi.org/10.1016/j.jct.2022.106974	journal	April 2023
Calphad thermodynamic description of some binary systems involving U Berche, A.; Dupin, N.; Guéneau, C. Journal of Nuclear Materials, Vol. 411, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2011.01.043	journal	April 2011
Thermodynamic assessment of the LiF–ThF4–PuF3–UF4 system Capelli, E.; Beneš, O.; Konings, R. J. M. Journal of Nuclear Materials, Vol. 462 https://doi.org/10.1016/j.jnucmat.2015.03.042	journal	July 2015
Thermal analysis of projected molten salt compositions during FFTF and EBR-II used nuclear fuel processing Karlsson, Toni Y.; Fredrickson, Guy L.; Yoo, Tae-Sic Journal of Nuclear Materials, Vol. 520 https://doi.org/10.1016/j.jnucmat.2019.04.016	journal	July 2019
Development of the Molten Salt Thermal Properties Database − Thermochemical (MSTDB−TC), example applications, and LiCl−RbCl and UF3−UF4 system assessments Ard, Johnathon C.; Yingling, Jacob A.; Johnson, Kaitlin E. Journal of Nuclear Materials, Vol. 563 https://doi.org/10.1016/j.jnucmat.2022.153631	journal	May 2022
Coupled structural-thermodynamic modelling of the molten salt system NaCl-UCl3 van Oudenaren, G. I. L.; Ocadiz-Flores, J. A.; Smith, A. L. Journal of Molecular Liquids, Vol. 342 https://doi.org/10.1016/j.molliq.2021.117470	journal	November 2021
Structure-property relationships in actinide containing molten salts – A review: Understanding and modelling the chemistry of nuclear fuel salts Smith, A. L. Journal of Molecular Liquids, Vol. 360 https://doi.org/10.1016/j.molliq.2022.119426	journal	August 2022
Thermodynamic assessment of lithium halide reciprocal salt systems for energy applications Aziziha, Mina; Schorne-Pinto, Juliano; Yingling, Jacob A. Journal of Molecular Liquids, Vol. 364 https://doi.org/10.1016/j.molliq.2022.119973	journal	October 2022
Electrochemical processing of spent nuclear fuels: An overview of oxide reduction in pyroprocessing technology Choi, Eun-Young; Jeong, Sang Mun Progress in Natural Science: Materials International, Vol. 25, Issue 6 https://doi.org/10.1016/j.pnsc.2015.11.001	journal	December 2015
History and status of spent fuel treatment at the INL Fuel Conditioning Facility Fredrickson, Guy L.; Patterson, Michael N.; Vaden, DeeEarl Progress in Nuclear Energy, Vol. 143 https://doi.org/10.1016/j.pnucene.2021.104037	journal	January 2022
Thermodynamics of the NaCl–KCl system Sergeev, D.; Kobertz, D.; Müller, M. Thermochimica Acta, Vol. 606 https://doi.org/10.1016/j.tca.2015.03.003	journal	April 2015
Algebraic Representation of Thermodynamic Properties and the Classification of Solutions Redlich, Otto; Kister, A. T. Industrial & Engineering Chemistry, Vol. 40, Issue 2 https://doi.org/10.1021/ie50458a036	journal	February 1948
Heats of Formation of Some Solid Solutions of Alkali Halide Lister, M. W.; Meyers, N. F. The Journal of Physical Chemistry, Vol. 62, Issue 2 https://doi.org/10.1021/j150560a003	journal	February 1958
Studies of NaCl-KCl Solid Solutions. I. Heats of Formation, Lattice Spacings, Densities, Schottky Defects and Mutual Solubilities ^1,2 Barrett, W. T.; Wallace, W. E. Journal of the American Chemical Society, Vol. 76, Issue 2 https://doi.org/10.1021/ja01631a014	journal	January 1954
Liquidus measurements and coupled thermodynamic–phase-diagram analysis of the NaCl–KCl system Pelton, Arthur D.; Gabriel, Armand; Sangster, James Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 81, Issue 5 https://doi.org/10.1039/f19858101167	journal	January 1985
Modèle statistique de solution binaire de sels fondus à cation ou anion commun: I. — Traitement général d'un système AB — A'B Gaune-Escard, Marcelle; Mathieu, Jean-Claude; Desré, Pierre Journal de Chimie Physique, Vol. 69 https://doi.org/10.1051/jcp/1972691390	journal	January 1972
Description d’un processus de mélange et grandeurs thermodynamiques de systèmes binaires de sels fondus du type AB₂ — A'B Hatem, Gérard; Gaune-Escard, Marcelle Journal de Chimie Physique, Vol. 74 https://doi.org/10.1051/jcp/1977740754	journal	January 1977
Enthalpies of Mixing in Some Binary Liquid Halide Mixtures Hersh, Leroy S.; Kleppa, O. J. The Journal of Chemical Physics, Vol. 42, Issue 4 https://doi.org/10.1063/1.1696115	journal	February 1965
Investigations of the specific heat of solid bodies Kopp, Hermann Philosophical Transactions of the Royal Society of London, Vol. 155, p. 71-202 https://doi.org/10.1098/rstl.1865.0003	journal	January 1865
Experimental measurement and thermodynamic optimization of the phase diagram of LiCl-NaCl-KCl system Lu, Guangxuan; Lai, Tianwang; He, Maogang Chinese Science Bulletin, Vol. 65, Issue 7 https://doi.org/10.1360/TB-2019-0416	journal	November 2019
Association Model for the Description of the Thermodynamic Functions of Liquid Alloys Sommer, Ferdinand International Journal of Materials Research, Vol. 73, Issue 2 https://doi.org/10.1515/ijmr-1982-730202	journal	February 1982
Enthalpy of Mixing of the PrCl ₃ -LiCl and NdCl ₃ -LiCl Molten Salt Systems Rycerz, Leszek; Okamotoc, Yoshihiro; Gaune-Escard, Marcelle Zeitschrift für Naturforschung A, Vol. 60, Issue 3 https://doi.org/10.1515/zna-2005-0312	journal	March 2005
Thermal Properties of LiCl-KCl Molten Salt for Nuclear Waste Separation Sridharan, Kumar; Allen, Todd; Anderson, Mark https://doi.org/10.2172/1058922	report	November 2012
Phase Diagrams of LiCl-NdCl₃, NaCl-NdC₃, and CaCl₂-NdCl₃ Systems Igarashi, Kazuo; Kosaka, Mineo; Iwadate, Yasuhiko Denki Kagaku oyobi Kogyo Butsuri Kagaku, Vol. 58, Issue 5 https://doi.org/10.5796/kogyobutsurikagaku.58.469	journal	May 1990

Similar Records

Thermodynamic modeling of KCl-PrCl₃ and KCl-LiCl-PrCl₃ systems

Journal Article · Mon Apr 24 20:00:00 EDT 2023 · Calphad · OSTI ID:2259214

Related Subjects

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
Chloride salt
Ionic liquid
Mixing enthalpy
Phase diagram
Pyroprocessing

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

Citation Formats

References (54)

Similar Records

Related Subjects

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