Effect of variable relative permittivity on the thermodynamics of asymmetric valency aqueous salts

Fuente: arXiv
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Main Authors: Quiñones, A. O., Abbas, Z., Outhwaite, C. W., Bhuiyan, L. B.
Format: Preprint
Published: 2025
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author Quiñones, A. O.
Abbas, Z.
Outhwaite, C. W.
Bhuiyan, L. B.
author_facet Quiñones, A. O.
Abbas, Z.
Outhwaite, C. W.
Bhuiyan, L. B.
contents Experimentally determined empirical formulae for the concentration dependent relative permittivity of aqueous solutions of MgCl$_{2}$ and NiCl$_{2}$ are utilized to calculate the osmotic coefficient and the mean activity coefficient of these salts for a range of concentrations. The systems are modelled using the primitive model of electrolytes and analyzed using the symmetric Poisson-Boltzmann theory, the modified Poisson-Boltzmann theory, the mean spherical approximation, and the Monte Carlo simulations. Generally, the mean spherical approximation and the modified Poisson-Boltzmann theory reproduce the benchmark simulation data well up to $\sim $1.6 mol/dm$^{3}$ or more in many instances, while the symmetric Poisson-Boltzmann results show discrepancies starting from $\sim $0.25 mol/dm$^{3}$. Both the simulations and the theories tend to deviate from the corresponding experimental results beyond $\sim $1 mol/kg.
format Preprint
id arxiv_https___arxiv_org_abs_2503_19047
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Effect of variable relative permittivity on the thermodynamics of asymmetric valency aqueous salts
Quiñones, A. O.
Abbas, Z.
Outhwaite, C. W.
Bhuiyan, L. B.
Soft Condensed Matter
Experimentally determined empirical formulae for the concentration dependent relative permittivity of aqueous solutions of MgCl$_{2}$ and NiCl$_{2}$ are utilized to calculate the osmotic coefficient and the mean activity coefficient of these salts for a range of concentrations. The systems are modelled using the primitive model of electrolytes and analyzed using the symmetric Poisson-Boltzmann theory, the modified Poisson-Boltzmann theory, the mean spherical approximation, and the Monte Carlo simulations. Generally, the mean spherical approximation and the modified Poisson-Boltzmann theory reproduce the benchmark simulation data well up to $\sim $1.6 mol/dm$^{3}$ or more in many instances, while the symmetric Poisson-Boltzmann results show discrepancies starting from $\sim $0.25 mol/dm$^{3}$. Both the simulations and the theories tend to deviate from the corresponding experimental results beyond $\sim $1 mol/kg.
title Effect of variable relative permittivity on the thermodynamics of asymmetric valency aqueous salts
topic Soft Condensed Matter
url https://arxiv.org/abs/2503.19047