Book ChapterDOI
Concept of Ion Association in the Theory of Electrolyte Solutions
M. Holovko
- pp 45-81
TLDR
In this article, the mass action law (MSA-MAL) approach for ion and ion-dipole models is used to revise the concept of ion association in the theory of electrolyte solutions.Abstract:
Analytical solution of the associative mean spherical approximation (AMSA) and the modified version of the mean spherical approximation — the mass action law (MSA-MAL) approach for ion and ion-dipole models are used to revise the concept of ion association in the theory of electrolyte solutions. In the considered approach in contrast to the traditional one both free and associated ion electrostatic contributions are taken into account and therefore the revised version of ion association concept is correct for weak and strong regimes of ion association. It is shown that AMSA theory is more preferable for the description of thermodynamic properties while the modified version of the MSA-MAL theory is more useful for the description of electrical properties. The capabilities of the developed approaches are illustrated by the description of thermodynamic and transport properties of electrolyte solutions in weakly polar solvents. The proposed theory is applied to explain the anomalous properties of electrical double layer in a low temperature region and for the treatment of the effect of electrolyte on the rate of intramolecular electron transfer. The revised concept of ion association is also used to describe the concentration dependence of dielectric constant in electrolyte solutions.read more
Citations
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Journal ArticleDOI
Application of the ionic association concept to the study of the phase behaviour of size-asymmetric ionic fluids in disordered porous media
TL;DR: In this article, the authors studied the phase behavior of a two-component size-asymmetric ionic fluid confined in a disordered porous matrix formed by uncharged hard spheres (HS) or overlapping (OHS) hard spheres.
Journal ArticleDOI
Yukawa fluid at a hard wall: field theory description
TL;DR: In this article, the authors adopt a field-theoretical approach to study the structure and thermodynamics of a spatially confined fluid interacting with the Yukawa potential, and derive analytic expressions for the pressure, the Helmholtz free energy, the correlation function, the density profile, and the adsorption.
Journal ArticleDOI
Vapour-liquid critical parameters of a 2:1 primitive model of ionic fluids confined in disordered porous media
TL;DR: In this paper, the vapour-liquid critical parameters of an ionic fluid confined in a disordered porous medium were studied by using the theory which combines the collective variables approach with an extension of the scaled particle theory.
Journal ArticleDOI
Phase behaviour in ionic solutions: Restricted primitive model of ionic liquid in explicit neutral solvent
Oksana Patsahan,T. Patsahan +1 more
TL;DR: In this article, the collective variable method was used to find free energy, pressure and partial chemical potentials in the random phase approximation (RPA) for a rather general model that takes into consideration solvent-solvent and solvent-ion interactions beyond the hard core.
Dissertation
Statistical physics of bulk and confined ionic liquids
TL;DR: In this paper, a model for the thermodynamics and kinetics of ion pairing in ionic liquids is proposed, which reveals that roughly 2/3 of ions are free, whilst those ion pairs that do exist are short-lived.
References
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Journal ArticleDOI
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Journal ArticleDOI
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TL;DR: In this paper, a new formulation of statistical thermodynamics is derived for classical fluids of molecules that tend to associate into dimers and possibly highers-mers due to highly directional attraction, and a breakup of the pair potential into repulsive and highly directionally attractive parts is introduced into the expansion of the logarithm of the grand partition function in fugacity graphs.
Journal ArticleDOI
Fluids with highly directional attractive forces. III. Multiple attraction sites
TL;DR: In this paper, the authors derived a reformulation of statistical thermodynamics for fluids of molecules which interact by highly directional attraction, which consists of a repulsive core and several sites of very short-ranged attraction.
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