Thermal Property Modeling and Assessment of the Physical Properties of FLiNaK

Schorne-Pinto, Juliano; Aziziha, Mina; Tisdale, Hunter B.; Mofrad, Amir M.; Birri, Anthony; Christian, Matthew S.; Ard, Johnathon C.; Booth, Ronald E.; Yingling, Jacob A.; Soldan Palma, Jorge Paz; Dixon, Clara; Loye, Hans-Conrad zur; Besmann, Theodore M.

doi:10.1021/acsaem.4c00321

Title: Thermal Property Modeling and Assessment of the Physical Properties of FLiNaK

Journal Article · 22 April 2024 · ACS Applied Energy Materials

DOI: https://doi.org/10.1021/acsaem.4c00321 · OSTI ID:2361191

^[1];

^[1]; Tisdale, Hunter B. ^[1]; Mofrad, Amir M. ^[1]; Birri, Anthony ^[2];

^[1]; Ard, Johnathon C. ^[1];

^[1]; Yingling, Jacob A. ^[1]; Soldan Palma, Jorge Paz ^[1]; Dixon, Clara ^[1];

^[1]; Besmann, Theodore M. ^[1]

Univ. of South Carolina, Columbia, SC (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Here, the thermodynamic properties of the LiF–NaF–KF system and its subsystems were re-evaluated using the CALPHAD method, focusing on the deviations from ideality in the heat capacity [C_p(T)] of mixtures, temperature-dependence of mixing enthalpies (Δ_mixH), vapor pressures of mixtures, and enthalpies of fusion (ΔH_fus) using reported values and measurements. The results of this work confirmed a pseudoternary eutectic at 732.9 K and 46.5LiF–11.5NaF–42KF mol % (FLiNaK) with determined Cp(T) = 69.822 + 0.000679T + 2,137,152T^–2 J mol^–1 K^–1 (732.9 < T < 1200 K) and ΔH_fus = 18,051 J mol^–1 in good agreement to the experimental values. The resulting accurate thermodynamic representation can be used to find relevant excess thermochemical properties in the whole pseudoternary space and provide insights into their composition and temperature dependence. A detailed evaluation of select thermophysical properties was also conducted to determine recommended density, thermal diffusivity, thermal conductivity, vapor pressures, and boiling point with calculated uncertainties over the temperature range of interest for FLiNaK–salt energy applications.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP); USDOE Office of Nuclear Energy (NE), Nuclear Energy Advanced Modeling and Simulation (NEAMS)

Grant/Contract Number:: AC05-00OR22725; NE0008985

OSTI ID:: 2361191

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 9 Vol. 7; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (74)

Ueber die Additivität der Atomwärmen Meyer, Stefan Annalen der Physik, Vol. 307, Issue 5 https://doi.org/10.1002/andp.19003070511	journal	January 1900
Isomorphismus der Kalium‐ und Natriumverbindungen Kurnakow, N. S.; Żmcżużnyj, S. F. Zeitschrift für anorganische Chemie, Vol. 52, Issue 1 https://doi.org/10.1002/zaac.19070520118	journal	January 1907
A rough hard-sphere model for the thermal conductivity of molten salts DiGuilio, R. M.; Teja, A. S. International Journal of Thermophysics, Vol. 13, Issue 5 https://doi.org/10.1007/BF00503912	journal	September 1992
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
Thermal Conductivity Characterization of Fluoride and Chloride Molten Salts Using a Modified Transient Hot-Wire Needle Probe Merritt, Brian; Seneca, Michael; Wright, Ben International Journal of Thermophysics, Vol. 43, Issue 10 https://doi.org/10.1007/s10765-022-03073-2	journal	August 2022
Thermal Properties of NaF–KF and NaF–KF–MgF2 Molten eutectic Mixtures: Experiment and Simulation Rudenko, A. V.; Redkin, A. A.; Galashev, A. Y. International Journal of Thermophysics, Vol. 45, Issue 4 https://doi.org/10.1007/s10765-024-03335-1	journal	February 2024
The modified quasi-chemical model: Part II. Multicomponent solutions Pelton, Arthur D.; Chartrand, Patrice Metallurgical and Materials Transactions A, Vol. 32, Issue 6 https://doi.org/10.1007/s11661-001-0226-3	journal	June 2001
Thermodynamic evaluation and optimization of the LiF-NaF-KF-MgF2-CaF2 system using the modified quasi-chemical model Chartrand, Patrice; Pelton, Arthur D. Metallurgical and Materials Transactions A, Vol. 32, Issue 6 https://doi.org/10.1007/s11661-001-0228-1	journal	June 2001
The modified quasi-chemical model: Part IV. Two-sublattice quadruplet approximation Pelton, Arthur D.; Chartrand, Patrice; Eriksson, Gunnar Metallurgical and Materials Transactions A, Vol. 32, Issue 6 https://doi.org/10.1007/s11661-001-0230-7	journal	June 2001
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
Thermal conductivity of molten alkali halides and their mixtures Smirnov, M. V.; Khokhlov, V. A.; Filatov, E. S. Electrochimica Acta, Vol. 32, Issue 7 https://doi.org/10.1016/0013-4686(87)90027-2	journal	July 1987
Ethalpies of mixing in some binary molten akali fluoride mixtures Macleod, A. C.; Cleland, J. The Journal of Chemical Thermodynamics, Vol. 7, Issue 2 https://doi.org/10.1016/0021-9614(75)90258-X	journal	February 1975
Enthalpies of mixing in some binary liquid alkali fluoride mixtures Hong, K. C.; Kleppa, O. J. The Journal of Chemical Thermodynamics, Vol. 8, Issue 1 https://doi.org/10.1016/0021-9614(76)90147-6	journal	January 1976
Recent advances in magnetic structure determination by neutron powder diffraction Rodríguez-Carvajal, Juan Physica B: Condensed Matter, Vol. 192, Issue 1-2 https://doi.org/10.1016/0921-4526(93)90108-I	journal	October 1993
Density and viscosity of the (LiFNaFKF)eutKBD4B2O3 melts Chrenková, M.; Daněk, V.; Silný, A. Journal of Molecular Liquids, Vol. 102, Issue 1-3 https://doi.org/10.1016/S0167-7322(02)00063-6	journal	January 2003
Fluoride salt coolant properties for nuclear reactor applications: A review Romatoski, R. R.; Hu, L. W. Annals of Nuclear Energy, Vol. 109 https://doi.org/10.1016/j.anucene.2017.05.036	journal	November 2017
Review of thermophysical property methods applied to fueled and un-fueled molten salts Magnusson, Jared; Memmott, Matthew; Munro, Troy Annals of Nuclear Energy, Vol. 146 https://doi.org/10.1016/j.anucene.2020.107608	journal	October 2020
Thermodynamic evaluation of the MF–LaF3 (M=Li, Na, K, Rb, Cs) systems Beneš, O.; Konings, R. J. M. Calphad, Vol. 32, Issue 1 https://doi.org/10.1016/j.calphad.2007.07.006	journal	March 2008
Reprint of: FactSage thermochemical software and databases, 2010–2016 Bale, C. W.; Bélisle, E.; Chartrand, P. Calphad, Vol. 55 https://doi.org/10.1016/j.calphad.2016.07.004	journal	December 2016
Molten salts database for energy applications Serrano-López, R.; Fradera, J.; Cuesta-López, S. Chemical Engineering and Processing: Process Intensification, Vol. 73 https://doi.org/10.1016/j.cep.2013.07.008	journal	November 2013
High-temperature molten-salt thermal energy storage and advanced-Ultra-supercritical power cycles Boretti, Alberto; Castelletto, Stefania Journal of Energy Storage, Vol. 42 https://doi.org/10.1016/j.est.2021.103143	journal	October 2021
Corrosion characteristics of reduced activation ferritic steel, JLF-1 (8.92Cr–2W) in molten salts Flibe and Flinak Kondo, Masatoshi; Nagasaka, Takuya; Xu, Qi Fusion Engineering and Design, Vol. 84, Issue 7-11, p. 1081-1085 https://doi.org/10.1016/j.fusengdes.2009.02.046	journal	June 2009
Thermal conductivity of high temperature fluoride molten salt determined by laser flash technique An, Xue-Hui; Cheng, Jin-Hui; Yin, Hui-Qin International Journal of Heat and Mass Transfer, Vol. 90 https://doi.org/10.1016/j.ijheatmasstransfer.2015.07.042	journal	November 2015
The high-temperature heat capacity of the (Li,Na)F liquid solution Beneš, O.; Konings, R. J. M.; Kuenzel, C. The Journal of Chemical Thermodynamics, Vol. 41, Issue 8 https://doi.org/10.1016/j.jct.2009.02.009	journal	August 2009
Thermodynamic investigation of the LiF–ThF4 system Capelli, E.; Beneš, O.; Beilmann, M. The Journal of Chemical Thermodynamics, Vol. 58 https://doi.org/10.1016/j.jct.2012.10.013	journal	March 2013
Physicochemical properties of the system (LiF+NaF+KF(eut.)+Na7Zr6F31): Phase equilibria, density and volume properties, viscosity and surface tension Barborík, Peter; Vasková, Zuzana; Boča, Miroslav The Journal of Chemical Thermodynamics, Vol. 76 https://doi.org/10.1016/j.jct.2014.03.024	journal	September 2014
Thermodynamic assessments or reassessments of 30 pseudo-binary and -ternary salt systems Ard, Johnathon C.; Schorne-Pinto, Juliano; Aziziha, Mina The Journal of Chemical Thermodynamics, Vol. 177 https://doi.org/10.1016/j.jct.2022.106931	journal	February 2023
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
Heat capacity and thermal conductivity of molten ternary lithium, sodium, potassium, and zirconium fluorides mixtures Khokhlov, V.; Korzun, I.; Dokutovich, V. Journal of Nuclear Materials, Vol. 410, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2010.12.306	journal	March 2011
Electrochemical separation of uranium in the molten system LiF–NaF–KF–UF4 Korenko, M.; Straka, M.; Szatmáry, L. Journal of Nuclear Materials, Vol. 440, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2013.04.078	journal	September 2013
Fundamental study on the vaporization of cesium and iodine dissolved in LiF-NaF-KF molten salt Sekiguchi, Y.; Uozumi, K.; Koyama, T. Journal of Nuclear Materials, Vol. 522 https://doi.org/10.1016/j.jnucmat.2019.05.014	journal	August 2019
The structure of molten FLiNaK Frandsen, Benjamin A.; Nickerson, Stella D.; Clark, Austin D. Journal of Nuclear Materials, Vol. 537 https://doi.org/10.1016/j.jnucmat.2020.152219	journal	August 2020
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
Investigation of the thermal conductivity of molten LiF-NaF-KF with experiments, theory, and equilibrium molecular dynamics Gallagher, Ryan C.; Birri, Anthony; Russell, Nick G. Journal of Molecular Liquids, Vol. 361 https://doi.org/10.1016/j.molliq.2022.119151	journal	September 2022
Synthesis and thermophysical property determination of NaCl-PuCl3 salts Karlsson, Toni Y.; Middlemas, Scott C.; Nguyen, Manh-Thuong Journal of Molecular Liquids, Vol. 387 https://doi.org/10.1016/j.molliq.2023.122636	journal	October 2023
Thermophysical and thermodynamic properties of NaF-BeF2-UF4-ZrF4 fuel salt Park, Jaewoo; Zhuo, Weiqian; Ridder, Cathleen Materials Today Communications, Vol. 37 https://doi.org/10.1016/j.mtcomm.2023.107211	journal	December 2023
A predictive approach for the compositional and temperature representation of thermal conductivity in multicomponent molten salt systems for advanced energy applications Yang, Huiqiang; Gallagher, Ryan C.; Phan, Anh-Thu Materials Today Energy, Vol. 38 https://doi.org/10.1016/j.mtener.2023.101441	journal	December 2023
Recommended values for the thermal conductivity of molten salts between the melting and boiling points Gheribi, Aïmen E.; Torres, Jesus A.; Chartrand, Patrice Solar Energy Materials and Solar Cells, Vol. 126 https://doi.org/10.1016/j.solmat.2014.03.028	journal	July 2014
Exploring crucible designs for differential scanning calorimetry measurements of fluoride salts Piro, M. H. A.; Lipkina, K.; Hallatt, D. Thermochimica Acta, Vol. 699 https://doi.org/10.1016/j.tca.2021.178860	journal	May 2021
Computational Thermodynamics Lukas, Hans; Fries, Suzana G.; Sundman, Bo https://doi.org/10.1017/CBO9780511804137	book	January 2007
Excess Heat Capacity in Liquid Binary Alkali-Fluoride Mixtures Beilmann, M.; Beneš, O.; Capelli, E. Inorganic Chemistry, Vol. 52, Issue 5 https://doi.org/10.1021/ic302168g	journal	February 2013
Molar Enthalpies of Mixing in the Molten Lithium Fluoride—Potassium Fluoride System Gilbert, Robert A. The Journal of Physical Chemistry, Vol. 67, Issue 5 https://doi.org/10.1021/j100799a052	journal	May 1963
Fusion properties and heat capacities of the eutectic lithium fluoride-sodium fluoride-potassium fluoride melt Rogers, Derek J.; Yoko, Toshinobu; Janz, George J. Journal of Chemical & Engineering Data, Vol. 27, Issue 3 https://doi.org/10.1021/je00029a041	journal	July 1982
Density and Viscosity of the (LiF + NaF + KF) _e _ut (1) + K ₂ TaF ₇ (2) + Ta ₂ O ₅ (3) Melts Cibulková, Jarmila; Chrenková, Marta; Vasiljev, Roman Journal of Chemical & Engineering Data, Vol. 51, Issue 3 https://doi.org/10.1021/je050490g	journal	March 2006
Radiant Transfer of Heat in Molten Inorganic Compounds at High Temperatures. Ewing, C. T.; Spann, J. R.; Miller, R. R. Journal of Chemical & Engineering Data, Vol. 7, Issue 2 https://doi.org/10.1021/je60013a028	journal	April 1962
New Scale Factors for Harmonic Vibrational Frequencies Using the B3LYP Density Functional Method with the Triple-ζ Basis Set 6-311+G(d,p) Andersson, M. P.; Uvdal, P. The Journal of Physical Chemistry A, Vol. 109, Issue 12 https://doi.org/10.1021/jp045733a	journal	March 2005
Thermal Conductivity of Molten Alkali Metal Fluorides (LiF, NaF, KF) and Their Mixtures Ishii, Yoshiki; Sato, Keisuke; Salanne, Mathieu The Journal of Physical Chemistry B, Vol. 118, Issue 12 https://doi.org/10.1021/jp411781n	journal	January 2014
Heat Capacity of Molten Halides Redkin, Alexander A.; Zaikov, Yurii P.; Korzun, Iraida V. The Journal of Physical Chemistry B, Vol. 119, Issue 2 https://doi.org/10.1021/jp509932e	journal	January 2015
Équilibres des systèmes binaires d’halogénures de sodium et potassium à l’état solide Journal de Chimie Physique, Vol. 61 https://doi.org/10.1051/jcp/1964611428	journal	January 1964
Enthalpies of Mixing in Binary Liquid Alkali Fluoride Mixtures Holm, J. L.; Kleppa, O. J. The Journal of Chemical Physics, Vol. 49, Issue 5 https://doi.org/10.1063/1.1670417	journal	September 1968
Heats of Dimerization of Alkali Fluoride Molecules Schoonmaker, Richard C.; Porter, Richard F. The Journal of Chemical Physics, Vol. 30, Issue 1 https://doi.org/10.1063/1.1729887	journal	January 1959
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Determination of thermal physical properties of alkali fluoride/carbonate eutectic molten salt An, Xue-Hui; Cheng, Jin-Hui; Su, Tao SOLARPACES 2016: International Conference on Concentrating Solar Power and Chemical Energy Systems, AIP Conference Proceedings https://doi.org/10.1063/1.4984415	conference	January 2017
Thermodynamic Properties of Synthetic Sapphire (α‐Al ₂ O ₃ ), Standard Reference Material 720 and the Effect of Temperature‐Scale Differences on Thermodynamic Properties Archer, Donald G. Journal of Physical and Chemical Reference Data, Vol. 22, Issue 6 https://doi.org/10.1063/1.555931	journal	November 1993
The curious temperature dependence of fluoride molten salt thermal conductivity Robertson, Sean G.; Wiser, Ralph; Yang, Wonseok Journal of Applied Physics, Vol. 131, Issue 22 https://doi.org/10.1063/5.0088059	journal	June 2022
The effect of corrosion product CrF₃on thermo-physical properties of FLiNaK Yin, Huiqin; Zhang, Peng; An, Xuehui Journal of Nuclear Science and Technology, Vol. 53, Issue 1 https://doi.org/10.1080/00223131.2015.1026859	journal	April 2015
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Development of Electrochemical Separation Methods in Molten LiF-NaF-KF for the Molten Salt Reactor Fuel Cycle SouČEk, Pavel; LisÝ, František; TulÁČKovÁ, Radka Journal of Nuclear Science and Technology, Vol. 42, Issue 12 https://doi.org/10.1080/18811248.2005.9711054	journal	December 2005
A Device for Measuring the Density and Liquidus Temperature of Molten Fluorides for Heat Transfer and Storage Cheng, Jin-Hui; Zhang, Peng; An, Xue-Hui Chinese Physics Letters, Vol. 30, Issue 12 https://doi.org/10.1088/0256-307X/30/12/126501	journal	December 2013
A profile refinement method for nuclear and magnetic structures Rietveld, H. M. Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71 https://doi.org/10.1107/S0021889869006558	journal	June 1969
Use of Interdiffusion to Determine Crystalline Solubility in Alkali Halide Systems Short, James M.; Roy, Rustum Journal of the American Ceramic Society, Vol. 47, Issue 3 https://doi.org/10.1111/j.1151-2916.1964.tb14375.x	journal	March 1964
Activities in Molten salt Mixtures of Potassium-Lithium-Halide Mixtures: a Preliminary Report Aukrust, E.; Björge, B.; Flood, H. Annals of the New York Academy of Sciences, Vol. 79, Issue 11 https://doi.org/10.1111/j.1749-6632.1960.tb42757.x	journal	January 1960
The Evaporation Behavior of Volatile Fission Products in FLiNaK Salt Taira, Masami; Arita, Yuji; Yamawaki, Michio The Open Access Journal of Science and Technology, Vol. 05, Issue 05 https://doi.org/10.11131/2017/101315	journal	January 2017
Electrochemical Studies of Uranium and Thorium in Molten LiF-NaF-KF at 500°C Clayton, F. R.; Mamantov, G.; Manning, D. L. Journal of The Electrochemical Society, Vol. 121, Issue 1 https://doi.org/10.1149/1.2396838	journal	January 1974
Current Status of Knowledge of the Fluoride Salt (FLiNaK) Heat Transfer Ambrosek, J.; Anderson, M.; Sridharan, K. Nuclear Technology, Vol. 165, Issue 2 https://doi.org/10.13182/NT165-166	journal	February 2009
Standards, calibration, and guidelines in microcalorimetry. Part 2. Calibration standards for differential scanning calorimetry* (IUPAC Technical Report) Della Gatta, Giuseppe; Richardson, Michael J.; Sarge, Stefan M. Pure and Applied Chemistry, Vol. 78, Issue 7 https://doi.org/10.1351/pac200678071455	journal	January 2006
Assessment of Candidate Molten Salt Coolants for the NGNP/NHI Heat-Transfer Loop Williams, D. F. https://doi.org/10.2172/1360677	report	June 2006
Status Report on the Molten Salt Thermodynamic Database (MSTDB) Development (FY20) Ard, Johnathan; Johnson, Kaitlin; Christian, M. https://doi.org/10.2172/1778080	report	September 2020
An Overview of the Molten Salt Thermal Properties Database–Thermophysical, Version 2.1.1 (MSTDB-TP v.2.1.1) Termini, Nick; Birri, Anthony; Henderson, Shane https://doi.org/10.2172/1988348	report	July 2023
An Overview of Liquid Fluoride Salt Heat Transport Systems Holcomb, David Eugene; Cetiner, Sacit M. https://doi.org/10.2172/990239	report	September 2010
Fluoride Salts and Container Materials for Thermal Energy Storage Applications in the Temperature Range 973 – 1400 K Misra, Ajay K.; Whittenberger, J. Daniel 22nd Intersociety Energy Conversion Engineering Conference https://doi.org/10.2514/6.1987-9226	conference	August 1987
Thermal Conductivity of FLiNaK in a Molten State Rudenko, Alexey; Redkin, Alexander; Il’ina, Evgeniya Materials, Vol. 15, Issue 16 https://doi.org/10.3390/ma15165603	journal	August 2022
Developing Practical Models of Complex Salts for Molten Salt Reactors Besmann, Theodore M.; Schorne-Pinto, Juliano Thermo, Vol. 1, Issue 2 https://doi.org/10.3390/thermo1020012	journal	July 2021
Phase Relations in the Systems NaF-LiF, NaF-KF, and NaF-RbF. Holm, Jan Lützow; Pikas, Anna-Lena; Ryhage, Ragnar Acta Chemica Scandinavica, Vol. 19 https://doi.org/10.3891/ACTA.CHEM.SCAND.19-0638	journal	January 1965

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