A modified Poisson-Boltzmaan equation II. Models and solutions

Woelki, Stefan and Kohler, Hans-Helmut (2000) A modified Poisson-Boltzmaan equation II. Models and solutions. CHEMICAL PHYSICS, 261 (3). pp. 421-438. ISSN 0301-0104

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Abstract

The properties of the charged interface between a dielectric particle and a surrounding aqueous electrolyte solution are calculated numerically over a wide range of surface charge densities for plane, cylindrical and spherical geometries. As a basis for the calculations, we present detailed models for the partial molar volumes, the dielectric permittivity and the activities of the components. These models are combined with a generalized set of local balance thermodynamic and electrostatic differential equations derived in the first part of this series. The influences of volume effects, dielectric saturation, polarization and self-atmosphere potentials on surface potential and electrostatic energy of a charged particle are investigated. Deviations from the ordinary Poisson-Boltzmann theory become very important at surface charge densities above 0.2 Cm-2. Quite generally, self-atmosphere potentials are of minor importance. The most important correction of the ordinary Poisson-Boltzmann equation is due to dielectric saturation in combination with the volume effect. It is found that the electrostatic potential, the electric field and the concentration of the counterion near a charged surface strongly depend on the excluded volume of the counterion. This leads to a distinct counterion sensitivity of the Gibbs energy of the system. Assuming a positively charged surface, competition between the counterion pairs Cl-/Br- and Cl-/SO42- is investigated. For sufficiently high surface charge densities it is found that, in the immediate vicinity of the surface, the smaller Br--ion displaces the larger Cl--ion and the Cl--ion, in turn, displaces the larger SO42--ion, although the latter is divalent. (C) 2000 Elsevier Science B.V. All rights reserved.

Item Type: Article
Uncontrolled Keywords: THIN DOUBLE-LAYERS; electrostatic interactions; surfaces; colloids; ion specificity
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Analytische Chemie, Chemo- und Biosensorik
Depositing User: Dr. Gernot Deinzer
Date Deposited: 15 Mar 2022 10:44
Last Modified: 15 Mar 2022 10:44
URI: https://pred.uni-regensburg.de/id/eprint/42058

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