skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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 contributionmore » of distant opposite charges cannot be ignored except at the highest temperature due to unscreened long-range interactions.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1603993
Alternate Identifier(s):
OSTI ID: 1577887
Report Number(s):
LA-UR-19-27151
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
89233218CNA000001
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Yoon, Tae Jun, Patel, Lara A., Vigil, Matthew J., Maerzke, Katie A., Findikoglu, Alp T., and Currier, Robert P.. Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures. United States: N. p., 2019. Web. https://doi.org/10.1063/1.5128671.
Yoon, Tae Jun, Patel, Lara A., Vigil, Matthew J., Maerzke, Katie A., Findikoglu, Alp T., & Currier, Robert P.. Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures. United States. https://doi.org/10.1063/1.5128671
Yoon, Tae Jun, Patel, Lara A., Vigil, Matthew J., Maerzke, Katie A., Findikoglu, Alp T., and Currier, Robert P.. Mon . "Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures". United States. https://doi.org/10.1063/1.5128671. https://www.osti.gov/servlets/purl/1603993.
@article{osti_1603993,
title = {Electrical conductivity, ion pairing, and ion self-diffusion in aqueous NaCl solutions at elevated temperatures and pressures},
author = {Yoon, Tae Jun and Patel, Lara A. and Vigil, Matthew J. and Maerzke, Katie A. and Findikoglu, Alp T. and Currier, Robert P.},
abstractNote = {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.},
doi = {10.1063/1.5128671},
journal = {Journal of Chemical Physics},
number = 22,
volume = 151,
place = {United States},
year = {2019},
month = {12}
}

Works referenced in this record:

Spatial‐Decomposition Analysis of Electrical Conductivity
journal, October 2018


Effect of lattice relaxation on thermal conductivity of fcc-based structures: an efficient procedure of molecular dynamics simulation
journal, May 2017

  • Ha, Min Young; Choi, Garam; Kim, Dong Hyun
  • Modelling and Simulation in Materials Science and Engineering, Vol. 25, Issue 5
  • DOI: 10.1088/1361-651x/aa6a2d

On the concept of ionicity in ionic liquids
journal, January 2009

  • MacFarlane, Douglas R.; Forsyth, Maria; Izgorodina, Ekaterina I.
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 25
  • DOI: 10.1039/b900201d

Velocity Correlations in Aqueous Electrolyte Solutions from Diffusion, Conductance, and Transference Data. Part 1, Theory
journal, July 1977

  • Hertz, H. G.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 81, Issue 7
  • DOI: 10.1002/bbpc.19770810707

Reliable Viscosity Calculation from Equilibrium Molecular Dynamics Simulations: A Time Decomposition Method
journal, July 2015

  • Zhang, Yong; Otani, Akihito; Maginn, Edward J.
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 8
  • DOI: 10.1021/acs.jctc.5b00351

Conductivity of some rare earth chlorides in sub and supercritical aqueous solutions
journal, January 2003


A corresponding-state framework for the structural transition of supercritical fluids across the Widom delta
journal, April 2019

  • Yoon, Tae Jun; Ha, Min Young; Lee, Won Bo
  • The Journal of Chemical Physics, Vol. 150, Issue 15
  • DOI: 10.1063/1.5086467

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
journal, July 1997

  • Fernández, D. P.; Goodwin, A. R. H.; Lemmon, Eric W.
  • Journal of Physical and Chemical Reference Data, Vol. 26, Issue 4
  • DOI: 10.1063/1.555997

Structure of hard-sphere fluid and precursor structures to crystallization
journal, August 2005

  • O’Malley, Brendan; Snook, Ian
  • The Journal of Chemical Physics, Vol. 123, Issue 5
  • DOI: 10.1063/1.1992475

A network approach to unravel correlated ion pair dynamics in protic ionic liquids. The case of triethylammonium nitrate
journal, January 2017


Calculation of Osmotic Coefficients of Nonaqueous Electrolyte Solutions with the Help of Chemical Models
journal, November 1988

  • Barthel, J.; Kunz, W.; Lauermann, G.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 92, Issue 11
  • DOI: 10.1002/bbpc.198800329

Molecular dynamics simulation of the dielectric constant of water: The effect of bond flexibility
journal, June 2011

  • Raabe, Gabriele; Sadus, Richard J.
  • The Journal of Chemical Physics, Vol. 134, Issue 23
  • DOI: 10.1063/1.3600337

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Thermodynamics of aqueous association and ionization reactions at high temperatures and pressures
journal, August 1988

  • Mesmer, R. E.; Marshall, W. L.; Palmer, D. A.
  • Journal of Solution Chemistry, Vol. 17, Issue 8
  • DOI: 10.1007/bf00647417

VORO++ : A three-dimensional Voronoi cell library in C++
journal, December 2009

  • Rycroft, Chris H.
  • Chaos: An Interdisciplinary Journal of Nonlinear Science, Vol. 19, Issue 4
  • DOI: 10.1063/1.3215722

Roles of Water for Chemical Reactions in High-Temperature Water
journal, August 2002

  • Akiya, Naoko; Savage, Phillip E.
  • Chemical Reviews, Vol. 102, Issue 8
  • DOI: 10.1021/cr000668w

Ion-Pair Association Constant for LiOH in Supercritical Water
journal, September 2011

  • Plugatyr, Andriy; Carvajal-Ortiz, Ruth A.; Svishchev, Igor M.
  • Journal of Chemical & Engineering Data, Vol. 56, Issue 9
  • DOI: 10.1021/je2004808

Monte Carlo simulation of high-pressure phase equilibria in aqueous systems
journal, September 1998


Electrical conductivity measurements of aqueous sodium chloride solutions to 600�C and 300 MPa
journal, September 1994

  • Ho, Patience C.; Palmer, Donald A.; Mesmer, Robert E.
  • Journal of Solution Chemistry, Vol. 23, Issue 9
  • DOI: 10.1007/bf00974100

Electrical conductances of aqueous sodium chloride solutions from 0 to 800.degree. and at pressures to 4000 bars
journal, February 1968

  • Quist, Arvin S.; Marshall, William L.
  • The Journal of Physical Chemistry, Vol. 72, Issue 2
  • DOI: 10.1021/j100848a050

10 6 -particle molecular-dynamics study of homogeneous nucleation of crystals in a supercooled atomic liquid
journal, April 1990


Hydrothermal vents and the origin of life
journal, September 2008

  • Martin, William; Baross, John; Kelley, Deborah
  • Nature Reviews Microbiology, Vol. 6, Issue 11
  • DOI: 10.1038/nrmicro1991

Review of the theory of electrolytic conductance
journal, October 1978

  • Fuoss, Raymond M.
  • Journal of Solution Chemistry, Vol. 7, Issue 10
  • DOI: 10.1007/bf00643581

Biomass Gasification in Supercritical Water
journal, November 2000

  • Antal, Michael Jerry; Allen, Stephen Glen; Schulman, Deborah
  • Industrial & Engineering Chemistry Research, Vol. 39, Issue 11
  • DOI: 10.1021/ie0003436

The Lennard-Jones Fluid in the Liquid-Vapour Critical Region
journal, January 2015


Transport Properties of the Ionic Liquid 1-Ethyl-3-Methylimidazolium Chloride from Equilibrium Molecular Dynamics Simulation. The Effect of Temperature
journal, July 2006

  • Rey-Castro, Carlos; Vega, Lourdes F.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 29
  • DOI: 10.1021/jp062885s

Velocity correlations, cooperative effects and relative diffusion in simple liquids
journal, October 1983

  • Balucani, U.; Vallauri, R.; Murthy, C. S.
  • Journal of Physics C: Solid State Physics, Vol. 16, Issue 29
  • DOI: 10.1088/0022-3719/16/29/014

A Review of Challenges and Recent Progress in Supercritical Water Oxidation of Wastewater
journal, November 2016


Interaction potentials and their effect on crystal nucleation and symmetry
journal, January 1979

  • Hsu, C. S.; Rahman, Aneesur
  • The Journal of Chemical Physics, Vol. 71, Issue 12
  • DOI: 10.1063/1.438311

Supercritical Water Gasification of Biomass: A Literature and Technology Overview
journal, January 2015

  • Yakaboylu, Onursal; Harinck, John; Smit, K.
  • Energies, Vol. 8, Issue 2
  • DOI: 10.3390/en8020859

Graph Theory and Ion and Molecular Aggregation in Aqueous Solutions
journal, April 2018


Markoff Random Processes and the Statistical Mechanics of Time‐Dependent Phenomena. II. Irreversible Processes in Fluids
journal, March 1954

  • Green, Melville S.
  • The Journal of Chemical Physics, Vol. 22, Issue 3
  • DOI: 10.1063/1.1740082

Spatial-decomposition analysis of electrical conductivity in concentrated electrolyte solution
journal, July 2014

  • Tu, Kai-Min; Ishizuka, Ryosuke; Matubayasi, Nobuyuki
  • The Journal of Chemical Physics, Vol. 141, Issue 4
  • DOI: 10.1063/1.4890741

Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions
journal, May 2009

  • Fennell, Christopher J.; Bizjak, Alan; Vlachy, Vojko
  • The Journal of Physical Chemistry B, Vol. 113, Issue 19
  • DOI: 10.1021/jp809782z

Simulating water with rigid non-polarizable models: a general perspective
journal, January 2011

  • Vega, Carlos; Abascal, Jose L. F.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 44
  • DOI: 10.1039/c1cp22168j

A review of current progress of recycling technologies for metals from waste electrical and electronic equipment
journal, July 2016


Correlations from Ion Pairing and the Nernst-Einstein Equation
journal, April 2019


On the accurate calculation of the dielectric constant from molecular dynamics simulations: The case of SPC/E and SWM4-DP water
journal, April 2011


Conductance in electrolyte solutions using the mean spherical approximation
journal, April 1992

  • Bernard, Olivier; Kunz, Werner; Turq, Pierre
  • The Journal of Physical Chemistry, Vol. 96, Issue 9
  • DOI: 10.1021/j100188a049

Coordination numbers of alkali metal ions in aqueous solutions
journal, December 2006


Velocity correlation coefficients as an expression of particle–particle interactions in (electrolyte) solutions
journal, January 1978

  • Woolf, Lawrence A.; Harris, Kenneth R.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 74, Issue 0
  • DOI: 10.1039/f19787400933

Dielectric Polarization in Polar Substances
journal, June 1953

  • Harris, Frank E.; Alder, Berni J.
  • The Journal of Chemical Physics, Vol. 21, Issue 6
  • DOI: 10.1063/1.1699105

Ion Pairing
journal, November 2006

  • Marcus, Yizhak; Hefter, Glenn
  • Chemical Reviews, Vol. 106, Issue 11
  • DOI: 10.1021/cr040087x

Structure and Dynamics of NaCl Ion Pairing in Solutions of Water and Methanol
journal, December 2015

  • Kelley, Morgan; Donley, Amber; Clark, Sue
  • The Journal of Physical Chemistry B, Vol. 119, Issue 51
  • DOI: 10.1021/acs.jpcb.5b07492

Identification of structure in condensed matter with the topological cluster classification
journal, December 2013

  • Malins, Alex; Williams, Stephen R.; Eggers, Jens
  • The Journal of Chemical Physics, Vol. 139, Issue 23
  • DOI: 10.1063/1.4832897

Design and results of a first generation pilot plant for supercritical water desalination (SCWD)
journal, August 2018


Static Dielectric Constant from Simulations Revisited: Fluctuations or External Field?
journal, March 2014

  • Kolafa, Jiří; Viererblová, Linda
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 4
  • DOI: 10.1021/ct500025m

A proposed rigorous definition of coordination number
journal, September 1979

  • O'Keeffe, M.
  • Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 35, Issue 5
  • DOI: 10.1107/s0567739479001765

A computer simulation study of the liquid–vapor coexistence curve of water
journal, May 1993

  • Guissani, Yves; Guillot, Bertrand
  • The Journal of Chemical Physics, Vol. 98, Issue 10
  • DOI: 10.1063/1.464527

Design of a Process for Supercritical Water Desalination with Zero Liquid Discharge
journal, May 2015

  • Odu, Samuel O.; van der Ham, Aloijsius G. J.; Metz, Sybrand
  • Industrial & Engineering Chemistry Research, Vol. 54, Issue 20
  • DOI: 10.1021/acs.iecr.5b00826

Molecular dynamics simulation of the limiting conductance of NaCl in supercritical water
journal, August 1998


A parameter-free, solid-angle based, nearest-neighbor algorithm
journal, June 2012

  • van Meel, Jacobus A.; Filion, Laura; Valeriani, Chantal
  • The Journal of Chemical Physics, Vol. 136, Issue 23
  • DOI: 10.1063/1.4729313

Na + –Cl ion pair association in supercritical water
journal, December 1995

  • Chialvo, A. A.; Cummings, P. T.; Cochran, H. D.
  • The Journal of Chemical Physics, Vol. 103, Issue 21
  • DOI: 10.1063/1.470707

Determination of accurate, mean bond lengths from radial distribution functions
journal, January 2017

  • Sukhomlinov, Sergey V.; Müser, Martin H.
  • The Journal of Chemical Physics, Vol. 146, Issue 2
  • DOI: 10.1063/1.4973804

Molecular force fields for aqueous electrolytes: SPC/E-compatible charged LJ sphere models and their limitations
journal, April 2013

  • Moučka, Filip; Nezbeda, Ivo; Smith, William R.
  • The Journal of Chemical Physics, Vol. 138, Issue 15
  • DOI: 10.1063/1.4801322

Determination of Alkali and Halide Monovalent Ion Parameters for Use in Explicitly Solvated Biomolecular Simulations
journal, July 2008

  • Joung, In Suk; Cheatham, Thomas E.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 30
  • DOI: 10.1021/jp8001614

Structural and Dynamical Origins of Ionic Mobilities in Supercritical Water
journal, September 2001

  • Hyun, Jin-Kee; Johnston, Keith P.; Rossky, Peter J.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 38
  • DOI: 10.1021/jp011465u

Limiting Conductivities and Ion Association Constants of Aqueous NaCl under Hydrothermal Conditions: Experimental Data and Correlations
journal, August 2012

  • Zimmerman, G. H.; Arcis, H.; Tremaine, P. R.
  • Journal of Chemical & Engineering Data, Vol. 57, Issue 9
  • DOI: 10.1021/je300361j

The missing term in effective pair potentials
journal, November 1987

  • Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P.
  • The Journal of Physical Chemistry, Vol. 91, Issue 24
  • DOI: 10.1021/j100308a038