An ab initio molecular dynamics investigation of the thermophysical properties of molten NaCl-MgCl2

Duemmler, Kai; Woods, Michael Ellis; Karlsson, Toni Y.; Gakhar, Ruchi; Beeler, Benjamin W.

doi:10.1016/j.jnucmat.2022.153916

An ab initio molecular dynamics investigation of the thermophysical properties of molten NaCl-MgCl₂

Journal Article · Thu Jul 21 00:00:00 EDT 2022 · Journal of Nuclear Materials

DOI:https://doi.org/10.1016/j.jnucmat.2022.153916· OSTI ID:1903510

Duemmler, Kai ^[1]; ^[2]; ^[2]; ^[2]; Beeler, Benjamin W. ^[3]

North Carolina State Univ., Raleigh, NC (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
North Carolina State Univ., Raleigh, NC (United States); Idaho National Lab. (INL), Idaho Falls, ID (United States)

Molten salts have many applications in the nuclear and solar energy industries for thermal storage and heat transfer applications. However, there is a knowledge gap in molten salt thermophysical properties which hinders the technical readiness level of molten salt applications, especially in the nuclear industry. A common method of investigating new materials is through ab initio Molecular Dynamics (AIMD) simulations which is an effective tool to investigate structural and thermophysical properties at realistic temperatures. NaCl-MgCl₂ is an inexpensive salt that is a good candidate for use as a heat transfer medium in solar power applications or in the secondary loop of a nuclear reactor. In this article, the thermophysical properties of NaCl-MgCl₂ are computed via AIMD calculations to supplement the limited experimental studies in the literature. Here a wide range of compositions and temperatures for the pseudo-binary NaCl-MgCl₂ were used to calculate the density, heat capacity, compressibility, enthalpy of mixing, and volumetric thermal expansion coefficient. AIMD is shown to accurately model the densities of molten NaCl-MgCl₂ as there is good agreement with the available literature. This work observed a transition to a monotonic increase of the density with respect to MgCl₂ composition occurring above 1100 K. The heat capacity values increase uniformly with respect to concentration of MgCl₂ at a rate of 2.85 J/mol-K per 10 mol% of MgCl₂. Select thermophysical properties are fit to a Redlich-Kister expansion for utilization in multiphysics simulations.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1903510

Alternate ID(s):: OSTI ID: 1962108

Report Number(s):: INL/JOU-22-66001-Rev001

Journal Information:: Journal of Nuclear Materials, Journal Name: Journal of Nuclear Materials Vol. 570; ISSN 0022-3115

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (29)

PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
Volume properties of the molten systems MF–K2TaF7 (MF = LiF, NaF and KF) Mlynáriková, Jarmila; Boča, Miroslav; Mikšíková, Eva Journal of Thermal Analysis and Calorimetry, Vol. 129, Issue 1 https://doi.org/10.1007/s10973-017-6137-3	journal	February 2017
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
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
Empirical estimation of densities in NaCl-KCl-UCl3 and NaCl-KCl-YCl3 molten salts using Redlich-Kister expansion Agca, Can; McMurray, Jake W. Chemical Engineering Science, Vol. 247 https://doi.org/10.1016/j.ces.2021.117086	journal	January 2022
Molten Salt-Directed Catalytic Synthesis of 2D Layered Transition-Metal Nitrides for Efficient Hydrogen Evolution Jin, Huanyu; Gu, Qinfen; Chen, Bo Chem, Vol. 6, Issue 9 https://doi.org/10.1016/j.chempr.2020.06.037	journal	September 2020
First-principles molecular dynamics modeling of the LiCl–KCl molten salt system Bengtson, Amelia; Nam, Hyo On; Saha, Saumitra Computational Materials Science, Vol. 83 https://doi.org/10.1016/j.commatsci.2013.10.043	journal	February 2014
Towards the calculations of redox potentials in molten LiCl-KCl eutectic by ensemble averages based on first principles molecular dynamics Song, Jia; Li, Xuejiao; Shi, Shuping Electrochimica Acta, Vol. 248 https://doi.org/10.1016/j.electacta.2017.07.090	journal	September 2017
Assessment of a novel ternary eutectic chloride salt for next generation high-temperature sensible heat storage Mohan, Gowtham; Venkataraman, Mahesh; Gomez-Vidal, Judith Energy Conversion and Management, Vol. 167 https://doi.org/10.1016/j.enconman.2018.04.100	journal	July 2018
Molten salt-promoted Ni–Fe/Al2O3 catalyst for methane decomposition Hu, Xiaoxiao; Hu, Yong; Xu, Qian International Journal of Hydrogen Energy, Vol. 45, Issue 7 https://doi.org/10.1016/j.ijhydene.2019.11.209	journal	February 2020
First-principles molecular dynamics modeling of the molten fluoride salt with Cr solute Nam, H. O.; Bengtson, A.; Vörtler, K. Journal of Nuclear Materials, Vol. 449, Issue 1-3 https://doi.org/10.1016/j.jnucmat.2014.03.014	journal	June 2014
Insight into dynamic interaction of molten MgCl2-NaCl-KCl with impurity water via FPMD simulations Li, Xuejiao; Liu, Weihua; Tang, Zhongfeng Journal of Molecular Liquids, Vol. 314 https://doi.org/10.1016/j.molliq.2020.113596	journal	September 2020
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
Assessing the environmental footprint of the production of rare earth metals and alloys via molten salt electrolysis Vahidi, Ehsan; Zhao, Fu Resources, Conservation and Recycling, Vol. 139 https://doi.org/10.1016/j.resconrec.2018.08.010	journal	December 2018
Corrosion mechanisms in molten salt thermal energy storage for concentrating solar power Bell, S.; Steinberg, T.; Will, G. Renewable and Sustainable Energy Reviews, Vol. 114 https://doi.org/10.1016/j.rser.2019.109328	journal	October 2019
Powerful predictability of FPMD simulations for the phase transition behavior of NaCl-MgCl2 eutectic salt Xu, Tingrui; Li, Xuejiao; Guo, Lili Solar Energy, Vol. 209 https://doi.org/10.1016/j.solener.2020.09.038	journal	October 2020
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
Densities and kinematic viscosities of some C6-C16 n-alkane binary liquid systems at 293.15 K Cooper, Elizabeth F.; Asfour, Abdul Fattah A. Journal of Chemical & Engineering Data, Vol. 36, Issue 3 https://doi.org/10.1021/je00003a008	journal	July 1991
Densities and excess molar volumes of binary and ternary melts of MgCl ₂ , CaCl ₂ and AlkCl Grjotheim, K.; Holm, J. L.; Lillebuen, B. Trans. Faraday Soc., Vol. 67, Issue 0 https://doi.org/10.1039/TF9716700640	journal	January 1971
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Fluoride-Salt-Cooled High-Temperature Reactor (FHR) Using British Advanced Gas-Cooled Reactor (AGR) Refueling Technology and Decay Heat Removal Systems That Prevent Salt Freezing Forsberg, Charles; Wang, Dean; Shwageraus, Eugene Nuclear Technology, Vol. 205, Issue 9 https://doi.org/10.1080/00295450.2019.1586372	journal	April 2019
The structures of molten magnesium and manganese (II) chlorides Biggin, S.; Gay, M.; Enderby, J. E. Journal of Physics C: Solid State Physics, Vol. 17, Issue 6 https://doi.org/10.1088/0022-3719/17/6/006	journal	February 1984
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Van der Waals Density Functional for General Geometries Dion, M.; Rydberg, H.; Schröder, E. Physical Review Letters, Vol. 92, Issue 24 https://doi.org/10.1103/PhysRevLett.92.246401	journal	June 2004
Thermodynamic Properties of MgCl2 ‐ NaCl Melts from EMF Measurements Karakaya, I.; Thompson, W. T. Journal of The Electrochemical Society, Vol. 133, Issue 4 https://doi.org/10.1149/1.2108658	journal	April 1986
The Molten Salt Reactor Adventure MacPherson, H. G. Nuclear Science and Engineering, Vol. 90, Issue 4 https://doi.org/10.13182/NSE90-374	journal	August 1985
Evaluation of Salt Coolants for Reactor Applications Williams, D. F.; Clarno, K. T. Nuclear Technology, Vol. 163, Issue 3 https://doi.org/10.13182/NT08-A3992	journal	September 2008

Similar Records

First-principles investigation of the thermophysical properties of NaCl, PuCl₃, and NaCl-PuCl₃ Molten salts

Journal Article · Wed Jan 10 23:00:00 EST 2024 · Journal of Nuclear Materials · OSTI ID:2283370

Empirical estimation of densities in NaCl-KCl-UCl₃ and NaCl-KCl-YCl₃ molten salts using Redlich-Kister expansion

Journal Article · Sat Sep 04 00:00:00 EDT 2021 · Chemical Engineering Science · OSTI ID:1823353

Synthesis and Thermophysical Property Determination of NaCl-PuCl3 Salts

Program Document · Thu Sep 22 00:00:00 EDT 2022 · OSTI ID:1906470

Related Subjects

36 MATERIALS SCIENCE
74 ATOMIC AND MOLECULAR PHYSICS
ab initio molecular dynamics
molten salts

An ab initio molecular dynamics investigation of the thermophysical properties of molten NaCl-MgCl2

Citation Formats

References (29)

Similar Records

Related Subjects

An ab initio molecular dynamics investigation of the thermophysical properties of molten NaCl-MgCl₂