The activity coefficient of high density systems with hard-sphere interactions: the application of the IGCMC method

Lamperski, Stanisław; Pluciennik, Monika

doi:10.1080/08927020903124577

Cited by 13 publications

(12 citation statements)

References 18 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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“…We have found earlier that the MSA and SPB results are very similar [26]. However, the advantage of MSA is that it yields an analytical solution for the activity coefficient.…”

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confidence: 80%

“…The IGCMC method is based on the grand-canonical MC simulation (GCMC), but its advantage over GCMC is that it allows evaluation of the mean and individual activity coefficient for a specified concentration of an electrolyte. The details of IGCMC are described in our previous papers [12,26]. Malasics et al [33,34] developed other algorithms to invert the GCMC simulation.…”

Section: The Methodsmentioning

confidence: 99%

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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

Lamperski

Pluciennik

2011

Molecular Physics

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“…The activity coefficients needed in the GCMC method were found from the inverse GCMC simulations [20,21]. For the symmetrical dimers, the GCMC results are supplemented with the DFT data.…”

Section: Model and Methodsmentioning

confidence: 99%

Interfacial properties of linear molecules modelled by dimer near a hard wall. A Monte Carlo and a density functional theory investigation

2014

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The density profile, g(x), and angular orientation function, , of a dimer molecule formed by two tangentially tethered hard spheres with both equal and different diameters, are studied by means of Monte Carlo (MC) simulation. Density functional theory (DFT) is used for the case where both sphere diameters are equal. For this case, the MC and DFT results for g(x) are in good agreement. At low densities, the contact value for g(x) is less than 1, its value at a large distance from the wall. This contrasts with a monomer hard-sphere fluid, where the contact value of g(x) is always greater than or equal to 1. This result is a consequence of the hindered rotation of dimers near the wall what lowers their entropy in comparison with its value in the bulk. This conjecture is confirmed by our MC studies of dimers formed by hard spheres of unequal size.

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The activity coefficient of high density systems with hard-sphere interactions: the application of the IGCMC method

Cited by 13 publications

References 18 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

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

Interfacial properties of linear molecules modelled by dimer near a hard wall. A Monte Carlo and a density functional theory investigation

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