Individual activity coefficients of a solvent primitive model electrolyte calculated from the inverse grand-canonical Monte Carlo simulation and MSA theory

Lamperski, Stanisław; Pluciennik, Monika

doi:10.1080/00268976.2010.544264

Cited by 4 publications

(4 citation statements)

References 33 publications

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“…Lamperski and Pluciennik , simulated various electrolyte models including the solvent primitive model (in that model, water molecules are represented by neutral hard spheres) using the GCMC algorithm developed by Lamperski . Calculation of the individual activity coefficient is an especially hard problem for explicit water models because of the high density of the system.…”

Section: Previous Work On the Individual Activity Coefficientsmentioning

confidence: 99%

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Valiskó

Boda

2015

J. Phys. Chem. B

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We investigate the individual activity coefficients of pure 1:1 and 2:1 electrolytes using our theory that is based on the competition of ion-ion (II) and ion-water (IW) interactions (Vincze et al., J. Chem. Phys. 133, 154507, 2010). The II term is computed from Grand Canonical Monte Carlo simulations on the basis of the implicit solvent model of electrolytes using hard sphere ions with Pauling radii. The IW term is computed on the basis of Born's treatment of solvation using experimental hydration free energies. The two terms are coupled through the concentration-dependent dielectric constant of the electrolyte. With this approach we are able to reproduce the nonmonotonic concentration dependence of the mean activity coefficient of pure electrolytes qualitatively without using adjustable parameters. In this paper, we show that the theory can provide valuable insight into the behavior of individual activity coefficients too. We compare our theoretical predictions against experimental data measured by electrochemical cells containing ion-specific electrodes. As in the case of the mean activity coefficients, we find good agreement for 2:1 electrolytes, while the accuracy of our model is worse for 1:1 systems. This deviation in accuracy is explained by the fact that the two competing terms (II and IW) are much larger in the 2:1 case so errors in the two separate terms have less effects. The difference of the excess chemical potentials of cations and anions (the ratio of activity coefficients) is determined by asymmetries in the properties of the two ions: charge, radius, and hydration free energies.

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Section: Previous Work On the Individual Activity Coefficientsmentioning

confidence: 99%

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Valiskó

Boda

2015

J. Phys. Chem. B

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“…The nonideal properties of many bio-ions can be understood (in pure solutions of one type of salt) quite well by a simple model, in which hard spheres move in a dielectric with friction (13,44,52,56,67,107,128,150,155,159,161). This primitive model is taught in textbooks and discussed in reviews (4,7,51,53,106,109).…”

Section: Primitive Model Of Ionic Solutionsmentioning

confidence: 99%

Ionic Interactions Are Everywhere

Eisenberg

2013

Physiology

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“…Several noteworthy studies have been focused on the use of the MSA theory to develop models for use in simulations of electrolyte solutions. Lamperski and Płuciennik 38 proposed a model for electrolyte solutions in which the anions, cations, and solvent are represented as hard spheres (HSs) immersed in a dielectric continuum. Each of the ions was modeled with a single HS and a central point charge.…”

Section: Introductionmentioning

confidence: 99%

The Contribution of the Ion–Ion and Ion–Solvent Interactions in a Molecular Thermodynamic Treatment of Electrolyte Solutions

et al. 2022

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Developing molecular equations of state to treat electrolyte solutions is challenging due to the long-range nature of the Coulombic interactions. Seminal approaches commonly used are the mean spherical approximation (MSA) and the Debye−Huckel (DH) theory to account for ion−ion interactions and, often, the Born theory of solvation for ion−solvent interactions. We investigate the accuracy of the MSA and DH approaches using each to calculate the contribution of the ion−ion interactions to the chemical potential of NaCl in water, comparing these with newly computer-generated simulation data; the ion−ion contribution is isolated by selecting an appropriate primitive model with a Lennard-Jones force field to describe the solvent. A study of mixtures with different concentrations and ionic strengths reveals that the calculations from both MSA and DH theories are of similar accuracy, with the MSA approach resulting in marginally better agreement with the simulation data. We also demonstrate that the Born theory provides a good qualitative description of the contribution of the ion−solvent interactions; we employ an explicitly polar water model in these simulations. Quantitative agreement up to moderate salt concentrations and across the relevant range of temperature is achieved by adjusting the Born radius using simulation data of the free energy of solvation. We compute the radial and orientational distribution functions of the systems, thereby providing further insight on the differences observed between the theory and simulation. We thus provide rigorous benchmarks for use of the MSA, DH, and Born theories as perturbation approaches, which will be of value for improving existing models of electrolyte solutions, especially in the context of equations of state.

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Individual activity coefficients of a solvent primitive model electrolyte calculated from the inverse grand-canonical Monte Carlo simulation and MSA theory

Cited by 4 publications

References 33 publications

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Unraveling the Behavior of the Individual Ionic Activity Coefficients on the Basis of the Balance of Ion–Ion and Ion–Water Interactions

Ionic Interactions Are Everywhere

The Contribution of the Ion–Ion and Ion–Solvent Interactions in a Molecular Thermodynamic Treatment of Electrolyte Solutions

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