Monte-Carlo simulation of mixed electrolytes next to a plane charged surface

Lamperski, Stanisław; Outhwaite, C.W.

doi:10.1016/j.jcis.2008.09.050

Cited by 19 publications

(10 citation statements)

References 17 publications

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“…At small charge densities the divalent cation predominates, but at large charge densities the small monovalent ion has the advantage because of entropic effects. Similar results were obtained by Biesheuven and van Soestbergen [26] and Lamperski and Outhwaite [27]. However, the latter authors carried out their MC simulations using a grand canonical ensemble similar to the earlier work by Torrie and Valleau [2].…”

Section: Monte Carlo Studies Of Unrestricted Electrolytes In the Diffsupporting

confidence: 79%

“…Furthermore the series approach for 1:1 electrolytes described their MC data very well [24]. Other recent work has involved mixed electrolytes [25][26][27]. Valisko et al [25] used MC simulations and density functional theory to study the effect of both cation size and charge on adsorption in the diffuse layer at negative charge densities.…”

Section: Monte Carlo Studies Of Unrestricted Electrolytes In the Diffmentioning

confidence: 99%

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Monte Carlo studies of ion size effects in the diffuse double layer

Fawcett

2009

Electrochimica Acta

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Section: Monte Carlo Studies Of Unrestricted Electrolytes In the Diffsupporting

confidence: 79%

Section: Monte Carlo Studies Of Unrestricted Electrolytes In the Diffmentioning

confidence: 99%

Monte Carlo studies of ion size effects in the diffuse double layer

Fawcett

2009

Electrochimica Acta

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“…They found that the adsorption of Cs + cations of the smallest hydrated radius, in comparison with the adsorption of larger Li + and divalent Mg 2+ , is stronger than one could expect. Earlier this behaviour was confirmed by the volume corrected Poisson-Boltzmann equation [19] and by the Monte Carlo simulations [20]. Also the present results indicate that adsorption of smaller ions, which have the lower activity coefficient and thus the lower chemical potential, should be enhanced.…”

Section: Discussionsupporting

confidence: 82%

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

Lamperski

Pluciennik

2010

Molecular Simulation

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“…However, the BMCSL model was unable to explain the Cs + -Mg 2+ data unless the diameter of the Mg 2+ ion is increased by 20% over its physical value. Furthermore, while the Monte Carlo simulation compared significantly better, it still underestimated the amount of Cs + in the double layer by between 14% and 24%, and it was suggested that other factors, including polarization, may be significant [45].…”

Section: Edl Structurementioning

confidence: 98%

“…For the Cs + -Li + system, a BMCSL-modified Poisson-Boltzmann model [12] and Monte Carlo simulations [45] both show that the difference between the sizes of ions can explain the experimental data: the smaller Cs + ions displace the larger Li + ions when the surface charge is high in order to minimize the energy of the system by allowing more counter-charge to approach the surface. However, the BMCSL model was unable to explain the Cs + -Mg 2+ data unless the diameter of the Mg 2+ ion is increased by 20% over its physical value.…”

Section: Edl Structurementioning

confidence: 99%

The influence of excluded volume and excess ion polarisability on the capacitance of the electric double layer

Minton

Lue

2016

Molecular Physics

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This version is available at https://strathprints.strath.ac.uk/55894/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. We apply a modified Poisson-Boltzmann theory which permits ions of different sizes and excess polarizabilities to the study of these properties' effects on the differential capacitance of the electric double layer. For a planar electrode, we find an analytical expression for the differential capacitance, which is examined in the limits of low and high applied potential. In the low potential limit, a reduction of the solution relative permittivity caused by the ion polarizability causes the differential capacitance to decrease above a certain concentration, relative to the Gouy-Chapman-Stern theory. A similar effect is observed for the excluded volume, but only if the ions are of different sizes. In the high potential limit, the differential capacitance decreases inversely with the square root of the applied voltage. In a mixed electrolyte, asymmetries in both ion size and excess polarizability alter the surface adsorption of species: at high potentials, smaller ions displace larger ions and less polarizable ions displace more polarizable ions. The extent of the displacement agrees favorably with experimental data. A further consequence of this displacement is the appearance of a second peak in the differential capacitance, which is enhanced by excess ion polarizability.

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Monte-Carlo simulation of mixed electrolytes next to a plane charged surface

Cited by 19 publications

References 17 publications

Monte Carlo studies of ion size effects in the diffuse double layer

Monte Carlo studies of ion size effects in the diffuse double layer

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

The influence of excluded volume and excess ion polarisability on the capacitance of the electric double layer

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