Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures

Yoon, Tae Jun; Patel, Lara A.; Vigil, Matthew J.; Maerzke, Katie A.; Findikoglu, Alp T.; Currier, Robert P.

doi:10.1063/1.5128671

Title: Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures

Journal Article · 08 December 2019 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5128671 · OSTI ID:1603993

^[1];

^[1]; Vigil, Matthew J. ^[1];

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

We have performed classical molecular dynamics (MD) simulations of aqueous sodium chloride (NaCl) solutions from 298 to 674 K at 200 bars to understand the influence of ion pairing and ion self-diffusion on electrical conductivity in high-temperature/high-pressure salt solutions. Conductivity data obtained from the MD simulation highlight an apparent anomaly, namely, a conductivity maximum as temperature increases along an isobar, which has been also observed in experimental studies. By examining both velocity autocorrelation and cross-correlation terms of the Green-Kubo integral, we quantitatively demonstrate that the conductivity anomaly arises mainly from a competition between the single-ion self-diffusion and the contact ion pair formation. The velocity autocorrelation function in conjunction with structural analysis suggests that diffusive motion of ions is suppressed at high temperatures due to the persistence of an inner hydration shell. Here, the contribution of velocity cross-correlation functions between oppositely charged ions becomes significant at the onset of the conductivity decrease. Structural analysis based on Voronoi tessellation and pair correlation functions indicates that the fraction of contact ion pairs increases as temperature increases. Spatial decomposition of the electrical conductivity also indicates that the formation of contact ion pairs significantly decreases the electrical conductivity compared to Nernst-Einstein conductivity, but the contribution of distant opposite charges cannot be ignored except at the highest temperature due to unscreened long-range interactions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: LDRD

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1603993

Report Number(s):: LA-UR--19-27151

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 151; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (67)

Schallabsorption in Elektrolytlösungen als Folge chemischer Relaxation II. Meßergebnisse und Relaxationsmechanismen für 2—2‐wertige Elektrolyte Eigen, M.; Tamm, Und K. Zeitschrift für Elektrochemie, Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 66, Issue 2 https://doi.org/10.1002/bbpc.19620660206	journal	March 1962
Velocity Correlations in Aqueous Electrolyte Solutions from Diffusion, Conductance, and Transference Data. Part 1, Theory Hertz, H. G. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 81, Issue 7 https://doi.org/10.1002/bbpc.19770810707	journal	July 1977
Calculation of Osmotic Coefficients of Nonaqueous Electrolyte Solutions with the Help of Chemical Models Barthel, J.; Kunz, W.; Lauermann, G. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 92, Issue 11 https://doi.org/10.1002/bbpc.198800329	journal	November 1988
Spatial‐Decomposition Analysis of Electrical Conductivity Matubayasi, Nobuyuki The Chemical Record, Vol. 19, Issue 4 https://doi.org/10.1002/tcr.201800116	journal	October 2018
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Review of the theory of electrolytic conductance Fuoss, Raymond M. Journal of Solution Chemistry, Vol. 7, Issue 10 https://doi.org/10.1007/bf00643581	journal	October 1978
Thermodynamics of aqueous association and ionization reactions at high temperatures and pressures Mesmer, R. E.; Marshall, W. L.; Palmer, D. A. Journal of Solution Chemistry, Vol. 17, Issue 8 https://doi.org/10.1007/bf00647417	journal	August 1988
Electrical conductivity measurements of aqueous sodium chloride solutions to 600�C and 300 MPa Ho, Patience C.; Palmer, Donald A.; Mesmer, Robert E. Journal of Solution Chemistry, Vol. 23, Issue 9 https://doi.org/10.1007/bf00974100	journal	September 1994
Coordination numbers of alkali metal ions in aqueous solutions Varma, Sameer; Rempe, Susan B. Biophysical Chemistry, Vol. 124, Issue 3 https://doi.org/10.1016/j.bpc.2006.07.002	journal	December 2006
On the accurate calculation of the dielectric constant from molecular dynamics simulations: The case of SPC/E and SWM4-DP water Gereben, Orsolya; Pusztai, László Chemical Physics Letters, Vol. 507, Issue 1-3 https://doi.org/10.1016/j.cplett.2011.02.064	journal	April 2011
Design and results of a first generation pilot plant for supercritical water desalination (SCWD) van Wyk, Surika; Odu, Samuel O.; van der Ham, Aloijsius G. J. Desalination, Vol. 439 https://doi.org/10.1016/j.desal.2018.03.028	journal	August 2018
A review of current progress of recycling technologies for metals from waste electrical and electronic equipment Zhang, Lingen; Xu, Zhenming Journal of Cleaner Production, Vol. 127 https://doi.org/10.1016/j.jclepro.2016.04.004	journal	July 2016
A network approach to unravel correlated ion pair dynamics in protic ionic liquids. The case of triethylammonium nitrate Zentel, Tobias; Kühn, Oliver Journal of Molecular Liquids, Vol. 226 https://doi.org/10.1016/j.molliq.2016.06.094	journal	January 2017
Molecular dynamics simulation of the limiting conductance of NaCl in supercritical water Lee, S. H.; Cummings, P. T.; Simonson, J. M. Chemical Physics Letters, Vol. 293, Issue 3-4 https://doi.org/10.1016/s0009-2614(98)00766-0	journal	August 1998
Monte Carlo simulation of high-pressure phase equilibria in aqueous systems Errington, J. R.; Kiyohara, K.; Gubbins, K. E. Fluid Phase Equilibria, Vol. 150-151 https://doi.org/10.1016/s0378-3812(98)00273-8	journal	September 1998
Conductivity of some rare earth chlorides in sub and supercritical aqueous solutions Ismail, Ibrahim M.; Masuko, Yoshio; Tomiyasu, Hiroshi The Journal of Supercritical Fluids, Vol. 25, Issue 1 https://doi.org/10.1016/s0896-8446(02)00089-x	journal	January 2003
Design of a Process for Supercritical Water Desalination with Zero Liquid Discharge Odu, Samuel O.; van der Ham, Aloijsius G. J.; Metz, Sybrand Industrial & Engineering Chemistry Research, Vol. 54, Issue 20 https://doi.org/10.1021/acs.iecr.5b00826	journal	May 2015
Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method Zhang, Yong; Otani, Akihito; Maginn, Edward J. Journal of Chemical Theory and Computation, Vol. 11, Issue 8 https://doi.org/10.1021/acs.jctc.5b00351	journal	July 2015
Structure and Dynamics of NaCl Ion Pairing in Solutions of Water and Methanol Kelley, Morgan; Donley, Amber; Clark, Sue The Journal of Physical Chemistry B, Vol. 119, Issue 51 https://doi.org/10.1021/acs.jpcb.5b07492	journal	December 2015
Roles of Water for Chemical Reactions in High-Temperature Water Akiya, Naoko; Savage, Phillip E. Chemical Reviews, Vol. 102, Issue 8 https://doi.org/10.1021/cr000668w	journal	August 2002
Ion Pairing Marcus, Yizhak; Hefter, Glenn Chemical Reviews, Vol. 106, Issue 11 https://doi.org/10.1021/cr040087x	journal	November 2006
Static Dielectric Constant from Simulations Revisited: Fluctuations or External Field? Kolafa, Jiří; Viererblová, Linda Journal of Chemical Theory and Computation, Vol. 10, Issue 4 https://doi.org/10.1021/ct500025m	journal	March 2014
Biomass Gasification in Supercritical Water ^† Antal, Michael Jerry; Allen, Stephen Glen; Schulman, Deborah Industrial & Engineering Chemistry Research, Vol. 39, Issue 11 https://doi.org/10.1021/ie0003436	journal	November 2000
Conductance in electrolyte solutions using the mean spherical approximation Bernard, Olivier; Kunz, Werner; Turq, Pierre The Journal of Physical Chemistry, Vol. 96, Issue 9 https://doi.org/10.1021/j100188a049	journal	April 1992
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Electrical conductances of aqueous sodium chloride solutions from 0 to 800.degree. and at pressures to 4000 bars Quist, Arvin S.; Marshall, William L. The Journal of Physical Chemistry, Vol. 72, Issue 2 https://doi.org/10.1021/j100848a050	journal	February 1968
Ion-Pair Association Constant for LiOH in Supercritical Water Plugatyr, Andriy; Carvajal-Ortiz, Ruth A.; Svishchev, Igor M. Journal of Chemical & Engineering Data, Vol. 56, Issue 9 https://doi.org/10.1021/je2004808	journal	September 2011
Limiting Conductivities and Ion Association Constants of Aqueous NaCl under Hydrothermal Conditions: Experimental Data and Correlations Zimmerman, G. H.; Arcis, H.; Tremaine, P. R. Journal of Chemical & Engineering Data, Vol. 57, Issue 9 https://doi.org/10.1021/je300361j	journal	August 2012
Structural and Dynamical Origins of Ionic Mobilities in Supercritical Water Hyun, Jin-Kee; Johnston, Keith P.; Rossky, Peter J. The Journal of Physical Chemistry B, Vol. 105, Issue 38 https://doi.org/10.1021/jp011465u	journal	September 2001
Transport Properties of the Ionic Liquid 1-Ethyl-3-Methylimidazolium Chloride from Equilibrium Molecular Dynamics Simulation. The Effect of Temperature Rey-Castro, Carlos; Vega, Lourdes F. The Journal of Physical Chemistry B, Vol. 110, Issue 29 https://doi.org/10.1021/jp062885s	journal	July 2006
Transport Properties of the Ionic Liquid 1-Ethyl-3-Methylimidazolium Chloride from Equilibrium Molecular Dynamics Simulation. The Effect of Temperature Rey-Castro, Carlos; Vega, Lourdes F. The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp0680746	journal	August 2006
Determination of Alkali and Halide Monovalent Ion Parameters for Use in Explicitly Solvated Biomolecular Simulations Joung, In Suk; Cheatham, Thomas E. The Journal of Physical Chemistry B, Vol. 112, Issue 30 https://doi.org/10.1021/jp8001614	journal	July 2008
Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions Fennell, Christopher J.; Bizjak, Alan; Vlachy, Vojko The Journal of Physical Chemistry B, Vol. 113, Issue 19 https://doi.org/10.1021/jp809782z	journal	May 2009
Hydrothermal vents and the origin of life Martin, William; Baross, John; Kelley, Deborah Nature Reviews Microbiology, Vol. 6, Issue 11 https://doi.org/10.1038/nrmicro1991	journal	September 2008
On the concept of ionicity in ionic liquids MacFarlane, Douglas R.; Forsyth, Maria; Izgorodina, Ekaterina I. Physical Chemistry Chemical Physics, Vol. 11, Issue 25 https://doi.org/10.1039/b900201d	journal	January 2009
Simulating water with rigid non-polarizable models: a general perspective Vega, Carlos; Abascal, Jose L. F. Physical Chemistry Chemical Physics, Vol. 13, Issue 44 https://doi.org/10.1039/c1cp22168j	journal	January 2011
Velocity correlation coefficients as an expression of particle–particle interactions in (electrolyte) solutions Woolf, Lawrence A.; Harris, Kenneth R. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 74, Issue 0 https://doi.org/10.1039/f19787400933	journal	January 1978
Dielectric Polarization in Polar Substances Harris, Frank E.; Alder, Berni J. The Journal of Chemical Physics, Vol. 21, Issue 6 https://doi.org/10.1063/1.1699105	journal	June 1953
Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids Green, Melville S. The Journal of Chemical Physics, Vol. 22, Issue 3 https://doi.org/10.1063/1.1740082	journal	March 1954
Structure of hard-sphere fluid and precursor structures to crystallization O’Malley, Brendan; Snook, Ian The Journal of Chemical Physics, Vol. 123, Issue 5 https://doi.org/10.1063/1.1992475	journal	August 2005
VORO++ : A three-dimensional Voronoi cell library in C++ Rycroft, Chris H. Chaos: An Interdisciplinary Journal of Nonlinear Science, Vol. 19, Issue 4 https://doi.org/10.1063/1.3215722	journal	December 2009
Molecular dynamics simulation of the dielectric constant of water: The effect of bond flexibility Raabe, Gabriele; Sadus, Richard J. The Journal of Chemical Physics, Vol. 134, Issue 23 https://doi.org/10.1063/1.3600337	journal	June 2011
Interaction potentials and their effect on crystal nucleation and symmetry Hsu, C. S.; Rahman, Aneesur The Journal of Chemical Physics, Vol. 71, Issue 12 https://doi.org/10.1063/1.438311	journal	January 1979
A computer simulation study of the liquid–vapor coexistence curve of water Guissani, Yves; Guillot, Bertrand The Journal of Chemical Physics, Vol. 98, Issue 10 https://doi.org/10.1063/1.464527	journal	May 1993
Na ⁺ –Cl ⁻ ion pair association in supercritical water Chialvo, A. A.; Cummings, P. T.; Cochran, H. D. The Journal of Chemical Physics, Vol. 103, Issue 21 https://doi.org/10.1063/1.470707	journal	December 1995
A parameter-free, solid-angle based, nearest-neighbor algorithm van Meel, Jacobus A.; Filion, Laura; Valeriani, Chantal The Journal of Chemical Physics, Vol. 136, Issue 23 https://doi.org/10.1063/1.4729313	journal	June 2012
Molecular force fields for aqueous electrolytes: SPC/E-compatible charged LJ sphere models and their limitations Moučka, Filip; Nezbeda, Ivo; Smith, William R. The Journal of Chemical Physics, Vol. 138, Issue 15 https://doi.org/10.1063/1.4801322	journal	April 2013
Identification of structure in condensed matter with the topological cluster classification Malins, Alex; Williams, Stephen R.; Eggers, Jens The Journal of Chemical Physics, Vol. 139, Issue 23 https://doi.org/10.1063/1.4832897	journal	December 2013
Spatial-decomposition analysis of electrical conductivity in concentrated electrolyte solution Tu, Kai-Min; Ishizuka, Ryosuke; Matubayasi, Nobuyuki The Journal of Chemical Physics, Vol. 141, Issue 4 https://doi.org/10.1063/1.4890741	journal	July 2014
Determination of accurate, mean bond lengths from radial distribution functions Sukhomlinov, Sergey V.; Müser, Martin H. The Journal of Chemical Physics, Vol. 146, Issue 2 https://doi.org/10.1063/1.4973804	journal	January 2017
A corresponding-state framework for the structural transition of supercritical fluids across the Widom delta Yoon, Tae Jun; Ha, Min Young; Lee, Won Bo The Journal of Chemical Physics, Vol. 150, Issue 15 https://doi.org/10.1063/1.5086467	journal	April 2019
A Formulation for the Static Permittivity of Water and Steam at Temperatures from 238 K to 873 K at Pressures up to 1200 MPa, Including Derivatives and Debye–Hückel Coefficients Fernández, D. P.; Goodwin, A. R. H.; Lemmon, Eric W. Journal of Physical and Chemical Reference Data, Vol. 26, Issue 4 https://doi.org/10.1063/1.555997	journal	July 1997
A Review of Challenges and Recent Progress in Supercritical Water Oxidation of Wastewater Zhang, Sijie; Zhang, Zhonghua; Zhao, Rui Chemical Engineering Communications, Vol. 204, Issue 2 https://doi.org/10.1080/00986445.2016.1262359	journal	November 2016
Velocity correlations, cooperative effects and relative diffusion in simple liquids Balucani, U.; Vallauri, R.; Murthy, C. S. Journal of Physics C: Solid State Physics, Vol. 16, Issue 29 https://doi.org/10.1088/0022-3719/16/29/014	journal	October 1983
Velocity correlations, cooperative effects and relative diffusion in simple liquids Balucani, U.; Vallauri, R.; Murthy, C. S. Journal of Physics C: Solid State Physics, Vol. 17, Issue 11 https://doi.org/10.1088/0022-3719/17/11/524	journal	April 1984
Effect of lattice relaxation on thermal conductivity of fcc-based structures: an efficient procedure of molecular dynamics simulation Ha, Min Young; Choi, Garam; Kim, Dong Hyun Modelling and Simulation in Materials Science and Engineering, Vol. 25, Issue 5 https://doi.org/10.1088/1361-651x/aa6a2d	journal	May 2017
10 6 -particle molecular-dynamics study of homogeneous nucleation of crystals in a supercooled atomic liquid Swope, William C.; Andersen, Hans C. Physical Review B, Vol. 41, Issue 10 https://doi.org/10.1103/physrevb.41.7042	journal	April 1990
Correlations from Ion Pairing and the Nernst-Einstein Equation France-Lanord, Arthur; Grossman, Jeffrey C. Physical Review Letters, Vol. 122, Issue 13 https://doi.org/10.1103/physrevlett.122.136001	journal	April 2019
A proposed rigorous definition of coordination number O'Keeffe, M. Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 35, Issue 5 https://doi.org/10.1107/s0567739479001765	journal	September 1979
Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems Kubo, Ryogo Journal of the Physical Society of Japan, Vol. 12, Issue 6 https://doi.org/10.1143/jpsj.12.570	journal	June 1957
Graph Theory and Ion and Molecular Aggregation in Aqueous Solutions Choi, Jun-Ho; Lee, Hochan; Choi, Hyung Ran Annual Review of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1146/annurev-physchem-050317-020915	journal	April 2018
The Lennard-Jones Fluid in the Liquid-Vapour Critical Region Heyes, D. M. Computational Methods in Science and Technology, Vol. 21, Issue 04 https://doi.org/10.12921/cmst.2015.21.04.001	journal	January 2015
Supercritical Water Gasification of Biomass: A Literature and Technology Overview Yakaboylu, Onursal; Harinck, John; Smit, K. Energies, Vol. 8, Issue 2 https://doi.org/10.3390/en8020859	journal	January 2015
A parameter-free, solid-angle based, nearest-neighbor algorithm van Meel, Jacobus A.; Filion, Laura; Valeriani, Chantal arXiv https://doi.org/10.48550/arxiv.1202.5281	text	January 2012
Identification of structure in condensed matter with the topological cluster classification Malins, Alex; Williams, Stephen R.; Eggers, Jens arXiv https://doi.org/10.48550/arxiv.1307.5517	text	January 2013
A Network Approach to Unravel Correlated Ion Pair Dynamics in Protic Ionic Liquids. The Case of Triethylammonium Nitrate Zentel, Tobias; Kühn, Oliver arXiv https://doi.org/10.48550/arxiv.1603.05985	preprint	January 2016
Correlations from ion-pairing and the Nernst-Einstein equation France-Lanord, Arthur; Grossman, Jeffrey C. arXiv https://doi.org/10.48550/arxiv.1812.04772	text	January 2018

Similar Records

Maxwell–Stefan diffusion and dynamical correlation in molten LiF-KF: A molecular dynamics study

Journal Article · 2016 · AIP Conference Proceedings · OSTI ID:22608782

Chakraborty, Brahmananda; Ramaniah, Lavanya M.

Molten Ag2Se: A molecular dynamics study

Conference · 1988 · OSTI ID:6479010

Hornos, Y M.M.; Antonio, G A; Rino, J P; +3 more

Molecular dynamics simulation of mass and charge transport in superionic conductors, and structural correlations in chalcogenide glasses

Conference · 1988 · OSTI ID:6162366

Vashishta, P; Rino, J P; Kalia, R K

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures

Citation Formats

References (67)

Similar Records

Related Subjects