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On the dielectric decrement of electrolyte solutions: A dressed-ion theory analysis

Journal article
Authors Rasmus Persson
Published in Physical Chemistry Chemical Physics - PCCP
Volume 19
Issue 3
Pages 1982-7
ISSN 1463-9076
Publication year 2017
Published at Department of Chemistry and Molecular Biology
Pages 1982-7
Language en
Subject categories Physical Chemistry, Statistical mechanics


Based on the dressed-ion theory and a simple physical argument regarding the conductivity of the solution, we derive a relation between the ionic strength and dielectric constant of an electrolyte solution. At its simplest, this model gives the dielectric constant at low ionic strength $I$ as $\varepsilon_\mathrm{r}(I) = \varepsilon_\mathrm{r}(0) (1 + \alpha)^{-1}$ where $\alpha$ (the excess polarization) is directly related to the dressed-ion charge. One contribution to the origin of the dielectric decrement is thus seen to stem from the electrostatic screening of the ions in solution, with no solvent contributions necessary.

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