Thermodynamic properties of ZrCl4 with LiCl, NaCl, KCl, CsCl, MgCl2, and UCl3 for molten salt reactor applications

Jack A. Wilson; Mina Aziziha; Juliano Schorne-Pinto; Aiswarya Padinhare Manissery; Jorge Paz Soldan Palma; Clara M. Dixon; Ronald E. Booth; Hunter B. Tisdale; Yunping Zhoujin; Dmitry S. Maltsev; Sheng Dai; Phillip W. Halstenberg; Silu Huang; Rongying Jin; Hans Conrad zur Loye; Theodore M. Besmann

doi:10.1016/j.molliq.2025.128578

Thermodynamic properties of ZrCl₄ with LiCl, NaCl, KCl, CsCl, MgCl₂, and UCl₃ for molten salt reactor applications

Jack A. Wilson
, Mina Aziziha
, Juliano Schorne-Pinto
, Aiswarya Padinhare Manissery
, Jorge Paz Soldan Palma
, Clara M. Dixon
, Ronald E. Booth
, Hunter B. Tisdale
, Yunping Zhoujin
, Dmitry S. Maltsev
, Sheng Dai
, Phillip W. Halstenberg
, Silu Huang
, Rongying Jin
, Hans Conrad zur Loye
, Theodore M. Besmann

Research output: Contribution to journal › Article › peer-review

Abstract

A set of self-consistent Gibbs energy functions has been developed to describe the thermochemical behavior of the major reactive fission product ZrCl₄ with key components in chloride molten salt reactors (MSRs): LiCl–ZrCl₄, NaCl–ZrCl₄, KCl–ZrCl₄, CsCl–ZrCl₄, MgCl₂–ZrCl₄ and UCl₃–ZrCl₄. Low ZrCl₄ concentration phase equilibria most relevant to MSR applications have been confirmed via differential scanning calorimetry for NaCl–ZrCl₄, and X-ray diffraction analysis performed on equilibrated samples of NaCl–ZrCl₄, KCl–ZrCl₄, MgCl₂–ZrCl₄, and UCl₃–ZrCl₄. Within the framework of the modified quasi-chemical model in the quadruplet approximation, extrapolations of pseudo-binary models were generated to represent KCl–MgCl₂–ZrCl₄, KCl–NaCl–ZrCl₄, and MgCl₂–NaCl–ZrCl₄, which show agreement with phase equilibria data where available without the use of ternary interaction parameters. The optimized thermodynamic descriptions for these systems and others are available in the open-source compendium Molten Salt Thermal Properties Database – Thermochemical (MSTDB–TC).

Original language	English
Article number	128578
Journal	Journal of Molecular Liquids
Volume	437
DOIs	https://doi.org/10.1016/j.molliq.2025.128578
State	Published - Nov 1 2025

Funding

This research was supported by the U.S. Department of Energy Office of Nuclear Energy, Nuclear Energy University Programs under award number DE-NE0008985; the Molten Salt Reactor Program; and the Nuclear Energy Advanced Modeling and Simulation Program. ORNL is operated under DOE contract number DE-AC05-00OR22725, and the work at UTK and ORNL was supported as part of the Molten Salts in Extreme Environments (MSEE) Energy Frontier Research Center, funded by the DOE Office of Science, Basic Energy Sciences. Additionally, C. M. Dixon was supported by the Nuclear Regulatory Commission University Nuclear Leadership Program (UNLP) under contract 31310021 M0029.

Keywords

CALPHAD
Chloride salts
Molten salt
Phase diagrams
Thermodynamic assessment
Vapor pressure

Access to Document

10.1016/j.molliq.2025.128578

Cite this

Wilson, J. A., Aziziha, M., Schorne-Pinto, J., Padinhare Manissery, A., Paz Soldan Palma, J., Dixon, C. M., Booth, R. E., Tisdale, H. B., Zhoujin, Y., Maltsev, D. S., Dai, S., Halstenberg, P. W., Huang, S., Jin, R., zur Loye, H. C., & Besmann, T. M. (2025). Thermodynamic properties of ZrCl₄ with LiCl, NaCl, KCl, CsCl, MgCl₂, and UCl₃ for molten salt reactor applications. Journal of Molecular Liquids, 437, Article 128578. https://doi.org/10.1016/j.molliq.2025.128578

@article{ace7d664f1284613a7363137596b431f,

title = "Thermodynamic properties of ZrCl4 with LiCl, NaCl, KCl, CsCl, MgCl2, and UCl3 for molten salt reactor applications",

abstract = "A set of self-consistent Gibbs energy functions has been developed to describe the thermochemical behavior of the major reactive fission product ZrCl4 with key components in chloride molten salt reactors (MSRs): LiCl–ZrCl4, NaCl–ZrCl4, KCl–ZrCl4, CsCl–ZrCl4, MgCl2–ZrCl4 and UCl3–ZrCl4. Low ZrCl4 concentration phase equilibria most relevant to MSR applications have been confirmed via differential scanning calorimetry for NaCl–ZrCl4, and X-ray diffraction analysis performed on equilibrated samples of NaCl–ZrCl4, KCl–ZrCl4, MgCl2–ZrCl4, and UCl3–ZrCl4. Within the framework of the modified quasi-chemical model in the quadruplet approximation, extrapolations of pseudo-binary models were generated to represent KCl–MgCl2–ZrCl4, KCl–NaCl–ZrCl4, and MgCl2–NaCl–ZrCl4, which show agreement with phase equilibria data where available without the use of ternary interaction parameters. The optimized thermodynamic descriptions for these systems and others are available in the open-source compendium Molten Salt Thermal Properties Database – Thermochemical (MSTDB–TC).",

keywords = "CALPHAD, Chloride salts, Molten salt, Phase diagrams, Thermodynamic assessment, Vapor pressure",

author = "Wilson, \{Jack A.\} and Mina Aziziha and Juliano Schorne-Pinto and \{Padinhare Manissery\}, Aiswarya and \{Paz Soldan Palma\}, Jorge and Dixon, \{Clara M.\} and Booth, \{Ronald E.\} and Tisdale, \{Hunter B.\} and Yunping Zhoujin and Maltsev, \{Dmitry S.\} and Sheng Dai and Halstenberg, \{Phillip W.\} and Silu Huang and Rongying Jin and \{zur Loye\}, \{Hans Conrad\} and Besmann, \{Theodore M.\}",

note = "Publisher Copyright: {\textcopyright} 2025 Elsevier B.V.",

year = "2025",

month = nov,

day = "1",

doi = "10.1016/j.molliq.2025.128578",

language = "English",

volume = "437",

journal = "Journal of Molecular Liquids",

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Wilson, JA, Aziziha, M, Schorne-Pinto, J, Padinhare Manissery, A, Paz Soldan Palma, J, Dixon, CM, Booth, RE, Tisdale, HB, Zhoujin, Y, Maltsev, DS, Dai, S , Halstenberg, PW, Huang, S, Jin, R, zur Loye, HC & Besmann, TM 2025, 'Thermodynamic properties of ZrCl₄ with LiCl, NaCl, KCl, CsCl, MgCl₂, and UCl₃ for molten salt reactor applications', Journal of Molecular Liquids, vol. 437, 128578. https://doi.org/10.1016/j.molliq.2025.128578

TY - JOUR

T1 - Thermodynamic properties of ZrCl4 with LiCl, NaCl, KCl, CsCl, MgCl2, and UCl3 for molten salt reactor applications

AU - Wilson, Jack A.

AU - Aziziha, Mina

AU - Schorne-Pinto, Juliano

AU - Padinhare Manissery, Aiswarya

AU - Paz Soldan Palma, Jorge

AU - Dixon, Clara M.

AU - Booth, Ronald E.

AU - Tisdale, Hunter B.

AU - Zhoujin, Yunping

AU - Maltsev, Dmitry S.

AU - Dai, Sheng

AU - Halstenberg, Phillip W.

AU - Huang, Silu

AU - Jin, Rongying

AU - zur Loye, Hans Conrad

AU - Besmann, Theodore M.

PY - 2025/11/1

Y1 - 2025/11/1

N2 - A set of self-consistent Gibbs energy functions has been developed to describe the thermochemical behavior of the major reactive fission product ZrCl4 with key components in chloride molten salt reactors (MSRs): LiCl–ZrCl4, NaCl–ZrCl4, KCl–ZrCl4, CsCl–ZrCl4, MgCl2–ZrCl4 and UCl3–ZrCl4. Low ZrCl4 concentration phase equilibria most relevant to MSR applications have been confirmed via differential scanning calorimetry for NaCl–ZrCl4, and X-ray diffraction analysis performed on equilibrated samples of NaCl–ZrCl4, KCl–ZrCl4, MgCl2–ZrCl4, and UCl3–ZrCl4. Within the framework of the modified quasi-chemical model in the quadruplet approximation, extrapolations of pseudo-binary models were generated to represent KCl–MgCl2–ZrCl4, KCl–NaCl–ZrCl4, and MgCl2–NaCl–ZrCl4, which show agreement with phase equilibria data where available without the use of ternary interaction parameters. The optimized thermodynamic descriptions for these systems and others are available in the open-source compendium Molten Salt Thermal Properties Database – Thermochemical (MSTDB–TC).

AB - A set of self-consistent Gibbs energy functions has been developed to describe the thermochemical behavior of the major reactive fission product ZrCl4 with key components in chloride molten salt reactors (MSRs): LiCl–ZrCl4, NaCl–ZrCl4, KCl–ZrCl4, CsCl–ZrCl4, MgCl2–ZrCl4 and UCl3–ZrCl4. Low ZrCl4 concentration phase equilibria most relevant to MSR applications have been confirmed via differential scanning calorimetry for NaCl–ZrCl4, and X-ray diffraction analysis performed on equilibrated samples of NaCl–ZrCl4, KCl–ZrCl4, MgCl2–ZrCl4, and UCl3–ZrCl4. Within the framework of the modified quasi-chemical model in the quadruplet approximation, extrapolations of pseudo-binary models were generated to represent KCl–MgCl2–ZrCl4, KCl–NaCl–ZrCl4, and MgCl2–NaCl–ZrCl4, which show agreement with phase equilibria data where available without the use of ternary interaction parameters. The optimized thermodynamic descriptions for these systems and others are available in the open-source compendium Molten Salt Thermal Properties Database – Thermochemical (MSTDB–TC).

KW - CALPHAD

KW - Chloride salts

KW - Molten salt

KW - Phase diagrams

KW - Thermodynamic assessment

KW - Vapor pressure

UR - https://www.scopus.com/pages/publications/105016860130

U2 - 10.1016/j.molliq.2025.128578

DO - 10.1016/j.molliq.2025.128578

M3 - Article

AN - SCOPUS:105016860130

SN - 0167-7322

VL - 437

JO - Journal of Molecular Liquids

JF - Journal of Molecular Liquids

M1 - 128578

ER -