Potential difference across a double layer containing an asymmetric electrolyte in the mean spherical approximation

1984 ◽  
Vol 88 (16) ◽  
pp. 3682-3684 ◽  
Author(s):  
Antoine F. Khater ◽  
Douglas Henderson ◽  
Lesser Blum ◽  
L. B. Bhuiyan
Keyword(s):  
Double Layer ◽  
Potential Difference ◽  
Spherical Approximation ◽  
Mean Spherical Approximation ◽  
The Mean

Perturbation theory, the mean spherical approximation, and the electrical double layer

1981 ◽  
Vol 59 (13) ◽  
pp. 1903-1905 ◽  
Author(s):  
Douglas Henderson ◽  
Lesser Blum
Keyword(s):  
Perturbation Theory ◽  
Double Layer ◽  
Electrical Double Layer ◽  
Electric Double Layer ◽  
Potential Difference ◽  
Spherical Approximation ◽  
Mean Spherical Approximation ◽  
The Mean

Simple arguments, based on perturbation theory, are used to derive expressions for the energy of a bulk ionic fluid and the potential difference in an electric double layer. These expressions are identical to those obtained from the much more elaborate mean spherical approximation.

scholarly journals A modified Poisson–Boltzmann study of the singlet ion distribution at contact with the electrode for a planar electric double layer

2010 ◽  
Vol 75 (4) ◽  
pp. 425-446 ◽  
Author(s):  
Whasington Silvestre-Alcantara ◽  
Lutful B. Bhuiyan ◽  
Christopher W. Outhwaite ◽  
Douglas Henderson
Keyword(s):  
Double Layer ◽  
Spherical Approximation ◽  
Mean Spherical Approximation ◽  
Ion Distribution ◽  
Simulation Data ◽  
Ion Distributions ◽  
Restricted Primitive Model ◽  
Theoretical Predictions ◽  
Poisson Boltzmann ◽  
The Mean

The properties of the singlet ion distributions at and around contact in a restricted primitive model double layer are characterized in the modified Poisson–Boltzmann theory. Comparisons are made with the corresponding exact Monte Carlo simulation data, the results from the Gouy–Chapman–Stern theory coupled to an exclusion volume term, and the mean spherical approximation. Particular emphasis is given to the behaviour of the theoretical predictions in relation to the contact value theorem involving the charge profile. The simultaneous behaviour of the coion and counterion contact values is also examined. The performance of the modified Poisson–Boltzmann theory in regard to the contact value theorems is very reasonable with the contact characteristics showing semi-quantitative or better agreement overall with the simulation results. The exclusion-volume-treated Gouy–Chapman– Stern theory reveals a fortuitous cancellation of errors, while the mean spherical approximation is poor.

Some Explicit Results for the Mean Spherical Approximation for Mixtures of Yukawa Fluids

2008 ◽  
Vol 73 (3) ◽  
pp. 424-438 ◽  
Author(s):  
Douglas J. Henderson ◽  
Osvaldo H. Scalise
Keyword(s):  
Integral Equation ◽  
Spherical Approximation ◽  
Mean Spherical Approximation ◽  
Inverse Temperature ◽  
Temperature Expansion ◽  
Yukawa Fluid ◽  
The Mean ◽  
Full Solution ◽  
Insight Into ◽  
Reasonable Model

The mean spherical approximation (MSA) is of interest because it produces an integral equation that yields useful analytical results for a number of fluids. One such case is the Yukawa fluid, which is a reasonable model for a simple fluid. The original MSA solution for this fluid, due to Waisman, is analytic but not explicit. Ginoza has simplified this solution. However, Ginoza's result is not quite explicit. Some years ago, Henderson, Blum, and Noworyta obtained explicit results for the thermodynamic functions of a single-component Yukawa fluid that have proven useful. They expanded Ginoza's result in an inverse-temperature expansion. Even when this expansion is truncated at fifth, or even lower, order, this expansion is nearly as accurate as the full solution and provides insight into the form of the higher-order coefficients in this expansion. In this paper Ginoza's implicit result for the case of a rather special mixture of Yukawa fluids is considered. Explicit results are obtained, again using an inverse-temperature expansion. Numerical results are given for the coefficients in this expansion. Some thoughts concerning the generalization of these results to a general mixture of Yukawa fluids are presented.

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