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

Title: Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

Abstract

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to the transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.

Authors:
 [1];  [1];  [2];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. BP America, Houston, TX (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
Work for Others (WFO)
OSTI Identifier:
1240099
Report Number(s):
SAND2016-1151J
Journal ID: ISSN 1932-7447; 619208
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 3; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Greathouse, Jeffery A., Cygan, Randall T., Fredrich, Joanne T., and Jerauld, Gary R. Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.5b10851.
Greathouse, Jeffery A., Cygan, Randall T., Fredrich, Joanne T., & Jerauld, Gary R. Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers. United States. https://doi.org/10.1021/acs.jpcc.5b10851
Greathouse, Jeffery A., Cygan, Randall T., Fredrich, Joanne T., and Jerauld, Gary R. 2016. "Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers". United States. https://doi.org/10.1021/acs.jpcc.5b10851. https://www.osti.gov/servlets/purl/1240099.
@article{osti_1240099,
title = {Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers},
author = {Greathouse, Jeffery A. and Cygan, Randall T. and Fredrich, Joanne T. and Jerauld, Gary R.},
abstractNote = {In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to the transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.},
doi = {10.1021/acs.jpcc.5b10851},
url = {https://www.osti.gov/biblio/1240099}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 3,
volume = 120,
place = {United States},
year = {Wed Jan 20 00:00:00 EST 2016},
month = {Wed Jan 20 00:00:00 EST 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 68 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A review and comparison of fracture mineral investigations and their application to radioactive waste disposal
journal, May 2009


Stabilization of As, Cr, Cu, Pb and Zn in soil using amendments – A review
journal, January 2008


Mechanochemistry: A review of surface reactions and environmental applications
journal, October 2012


Application, chemistry, and environmental implications of contaminant-immobilization amendments on agricultural soil and water quality
journal, January 2011


‘Geo’chemical research: A key building block for nuclear waste disposal safety cases
journal, December 2008


Analysis of the FEBEX multi-barrier system including thermoplasticity of unsaturated bentonite: ANALYSIS OF THE FEBEX MBS INCLUDING THERMOPLASTICITY AND UNSATURATION
journal, November 2011

  • Dupray, Fabrice; François, Bertrand; Laloui, Lyesse
  • International Journal for Numerical and Analytical Methods in Geomechanics, Vol. 37, Issue 4
  • https://doi.org/10.1002/nag.1103

Geochemical evidence for efficient aquifer isolation over geological timeframes
journal, September 2003


The performance of natural clay as a barrier to the diffusion of municipal solid waste landfill leachates
journal, March 2012


Membrane Behavior of Compacted Clay Liners
journal, October 2010


Long-term performance of contaminant barrier systems
journal, November 2005


Connecting the Molecular Scale to the Continuum Scale for Diffusion Processes in Smectite-Rich Porous Media
journal, March 2010


Molecular Dynamics Simulations of Water Structure and Diffusion in Silica Nanopores
journal, May 2012


Mobility of Na and Cs on Montmorillonite Surface under Partially Saturated Conditions
journal, August 2013


Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field
journal, January 2004


Water and ions in clays: Unraveling the interlayer/micropore exchange using molecular dynamics
journal, November 2007


On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation
journal, July 2009


Molecular Dynamic Study of the Swelling Behavior of Na-Montmorillonite
journal, May 2013


Hysteresis in Clay Swelling Induced by Hydrogen Bonding:  Accurate Prediction of Swelling States
journal, January 2006


Molecular Simulations of Swelling Clay Minerals
journal, June 2004


Biodegradation and mineral weathering controls on bulk electrical conductivity in a shallow hydrocarbon contaminated aquifer
journal, November 2005


Determination of hydrate stability zone using electrical conductivity data of salt aqueous solution
journal, April 2007


Implementation of a Morse potential to model hydroxyl behavior in phyllosilicates
journal, April 2009


Computer Simulation of Interlayer Molecular Structure in Sodium Montmorillonite Hydrates
journal, July 1995


Molecular Simulation of Structure and Diffusion at Smectite–Water Interfaces: Using Expanded Clay Interlayers as Model Nanopores
journal, July 2015


Molecular Dynamics Simulations of Water and Sodium Diffusion in Smectite Interlayer Nanopores as a Function of Pore Size and Temperature
journal, December 2013


An ab Initio and Classical Molecular Dynamics Investigation of the Structural and Vibrational Properties of Talc and Pyrophyllite
journal, August 2007


Structure, Energetics, and Dynamics of Smectite Clay Interlayer Hydration: Molecular Dynamics and Metadynamics Investigation of Na-Hectorite
journal, March 2013


Nanoscale Elastic Properties of Montmorillonite upon Water Adsorption
journal, October 2012


Molecular dynamics simulation of uranyl(vi) adsorption equilibria onto an external montmorillonite surface
journal, January 2005


Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study
journal, February 2006


Molecular Dynamics Modeling of Ion Adsorption to the Basal Surfaces of Kaolinite
journal, April 2007


A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions
journal, September 2006


A molecular dynamics simulation of a water model with intramolecular degrees of freedom
journal, January 1987


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


Hydration and Mobility of Interlayer Ions of (Na x , Ca y )-Montmorillonite: A Molecular Dynamics Study
journal, December 2014


Temperature effect in a montmorillonite clay at low hydration—microscopic simulation
journal, September 2004


Water Dynamics in Hectorite Clays: Infuence of Temperature Studied by Coupling Neutron Spin Echo and Molecular Dynamics
journal, April 2011


Anisotropy of Water Dynamics in Clays: Insights from Molecular Simulations for Experimental QENS Analysis
journal, July 2013


Properties of flexible water models
journal, October 1991


Na + –Na + and Cl –Cl ion pairs in water: Mean force potentials by constrained molecular dynamics
journal, August 1991


Pressure and temperature dependence of self-diffusion in water
journal, January 1978


Neutron Time-of-Flight Quantification of Water Desorption Isotherms of Montmorillonite
journal, February 2012


Diffusion of Water in Clays on the Microscopic Scale:  Modeling and Experiment
journal, February 2006


Self-Diffusion of Sodium Ions in Compacted Sodium Montmorillonite
journal, January 1998


Diffusion Behavior of Ca 2+ Ions in Compacted Na-Montmorillonite
journal, January 2000


Diffusion of Interlayer Cations in Swelling Clays as a Function of Water Content: Case of Montmorillonites Saturated with Alkali Cations
journal, May 2015


Hydrogen Bond Energy of the Water Dimer
journal, January 1996


Linking the Diffusion of Water in Compacted Clays at Two Different Time Scales: Tracer Through-Diffusion and Quasielastic Neutron Scattering
journal, April 2009


Computer simulations of NaCl association in polarizable water
journal, March 1994


Solvent Structure, Dynamics, and Ion Mobility in Aqueous Solutions at 25 °C
journal, May 1998


Works referencing / citing this record:

Swelling of clay minerals: dual characteristics of K + ions and exploration of critical influencing factors
journal, January 2019