Electrolyte solution structure and its effect on the properties of electric double layers with surface charge regulation

[Display omitted] The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these speci...

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Bibliographic Details
Published in:Journal of colloid and interface science 2017-02, Vol.488, p.180-189
Main Authors: Vangara, R., Brown, D.C.R., van Swol, F., Petsev, D.N.
Format: Article
Language:English
Subjects:
Charged interfaces
Electric double layer
Electrolyte solutions
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Summary:[Display omitted] The physical origin of charged interfaces involving electrolyte solutions is in the thermodynamic equilibrium between the surface reactive groups and certain dissolved ionic species in the bulk. This equilibrium is very strongly dependent on the precise local density of these species, also known as potential determining ions in the solution. The latter, however, is determined by the overall solution structure, which is dominated by the large number of solvent molecules relative to all solutes. Hence, the solvent contribution to the molecular structure is a crucial factor that determines the properties of electric double layers. Models that explicitly account for the solvent structure are often referred to as “civilized” as opposed to the “primitive” ones that consider the solvent as a structureless continuum. In the present paper, we demonstrate that for a physically correct description of charged interfaces that involve electrolyte solutions (electric double layers), the full solution structure needs to be taken into account in conjunction with the precise surface chemistry governed by the thermodynamic equilibrium. The analysis shows how the surface charge depends on various experimentally relevant parameters, many of which are outside the realm of simple electrostatics. We present results on the effects of solvent molecular dimensions, ionic solvation, surface chemistry, solvophilicity and solvophobicity.
ISSN:0021-9797
1095-7103
DOI:10.1016/j.jcis.2016.10.084