On the theory of electrolytes: correlations, excluded volume and multiple-boundaries

The screening, the configurational correlations and the interaction correlations in the theory of binary electrolytes are examined, by exploiting the charge conservation and the properties of the equilibrium state. Validity conditions for the linearised Debye-Huckel screened potential are provided....

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Bibliographic Details
Published in:Physics and chemistry of liquids 2022-11, Vol.60 (6), p.827-838
Main Authors: Apostol, M., Cune, L. C.
Format: Article
Language:English
Subjects:
Boundary conditions
correlations
Debye-Huckel theory
Electrolytes
excluded volume
Solvation
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Summary:The screening, the configurational correlations and the interaction correlations in the theory of binary electrolytes are examined, by exploiting the charge conservation and the properties of the equilibrium state. Validity conditions for the linearised Debye-Huckel screened potential are provided. A non-zero ionic radius is employed in order to account for solvation effects, and limitations on the contribution of the ionic radius are derived. A possible stabilisation of the ions in equilibrium positions, arising from counterion configurational correlations, is analysed for associated electrolytes, and the corresponding correlation energy is derived. A van der Waals-type equation is presented for strong electrolytes. Some well-known technical difficulties of the theory of electrolytes are revisited, with emphasis on statistical-dynamical correlations, excluded volume and multiple-boundary conditions.
ISSN:0031-9104
1029-0451
DOI:10.1080/00319104.2022.2086674