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Diffusion of Na and Cs in montmorillonite

Published online by Cambridge University Press:  01 January 2024

Georg Kosakowski ,
Sergey V. Churakov  and
Tres Thoenen
Georg Kosakowski*
Affiliation:
Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
Sergey V. Churakov
Affiliation:
Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
Tres Thoenen
Affiliation:
Paul Scherrer Institut, 5232 Villigen PSI, Switzerland
*
* E-mail address of corresponding author: [email protected]
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Abstract

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The state and dynamics of water and cations in pure and mixed Na-Cs-montmorillonite as a function of the interlayer water content were investigated in the present study, using Monte Carlo and classical, molecular-dynamics methods. While highly idealized, the simulations showed that the swelling behavior of hetero-ionic Na-Cs-montmorillonite is comparable to the swelling of a homo-ionic Na- or Cs-montmorillonite. The mixed Na-Cs-montmorillonite is characterized by intermediate interlayer distances compared to homo-ionic Na- and Cs-montmorillonites. Dry, hetero-ionic Na-Cs-montmorillonite is characterized by a symmetric sheet configuration, as is homo-ionic Cs-montmorillonite.

We found that at low degrees of hydration the absolute diffusion coefficient of Cs+ is less than for Na+, whereas at greater hydration states the diffusion coefficient of Cs+ is greaterthan for Na+. An analysis of the relative diffusion coefficients (the ratio between the diffusion coefficient of an ion in the interlayer and its diffusion coefficient in bulk water) revealed that water and Na+ are always less retarded than Cs+. With large interlayer water contents, tetralayer or more, Na+ ions preferentially form outer-sphere complexes. The mobility perpendicular to the clay surface is limited and the diffusion is equivalent to two-dimensional diffusion in bulk water. In contrast, Cs+ ions preferentially form ‘inner-sphere complexes’ at all hydration states and their two-dimensional diffusion coefficient is less than in bulk water.

The question remains unanswered as to why experimentally derived relative diffusion coefficients of Cs+ in the interlayer of clays are about 20 times less than those we obtained by classical molecular dynamics studies.

Keywords

Cs+DiffusionMolecular DynamicsMontmorilloniteNa+SwellingWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 56 , Issue 2 , April 2008 , pp. 190 - 206
Copyright
Copyright © 2008, The Clay Minerals Society

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