A mean spherical approximation study of the capacitance of an electric double layer formed by a high density electrolyte

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Title:A mean spherical approximation study of the capacitance of an electric double layer formed by a high density electrolyte
Creators:
Henderson, Douglas
Lamperski, Stanisław
Outhwaite, Christopher W.
Bhuiyan, Lutful Bari
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 75, 3, pp. 303-312
Uncontrolled Keywords:Grand canonical Monte Carlo simulations, High density electrolytes, Electric double layer, Capacitance, Electrochemistry, Mean spherical approximation

Abstract

In a recent grand canonical Monte Carlo simulation and modified Poisson–Boltzmann (MPB) theoretical study of the differential capacitance of a restricted primitive model double layer at high electrolyte densities, Lamperski, Outhwaite and Bhuiyan (<i>J. Phys. Chem. B</i> <b>2009</b>, <i>113</i>, 8925) have reported a maximum in the differential capacitance as a function of electrode charge, in contrast to that seen in double layers at lower ionic densities. The venerable Gouy–Chapman–Stern (GCS) theory always yields a minimum and gives values for the capacitance that tend to be too small at these higher densities. In contrast, the mean spherical approximation (MSA) leads to better agreement with the simulation results than does the GCS approximation at higher densities but the agreement is not quite as good as for the MPB approximation. Since the MSA is a linear response theory, it gives predictions only for small electrode charge. Nonetheless, the MSA is of value since it leads to analytic results. A simple extension of the MSA to higher electrode charges would be valuable.

Title:A mean spherical approximation study of the capacitance of an electric double layer formed by a high density electrolyte
Creators:
Henderson, Douglas
Lamperski, Stanisław
Outhwaite, Christopher W.
Bhuiyan, Lutful Bari
Uncontrolled Keywords:Grand canonical Monte Carlo simulations, High density electrolytes, Electric double layer, Capacitance, Electrochemistry, Mean spherical approximation
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:75
Number:3
Page Range:pp. 303-312
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc2009094UNSPECIFIED
ID Code:5399
Item Type:Article
Deposited On:04 May 2010 12:51
Last Modified:04 May 2010 10:51

Citation

Henderson, Douglas; Lamperski, Stanisław; Outhwaite, Christopher W.; Bhuiyan, Lutful Bari (2010) A mean spherical approximation study of the capacitance of an electric double layer formed by a high density electrolyte. Collection of Czechoslovak Chemical Communications, 75 (3). pp. 303-312.

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