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A Kirkwood–Buff theoretical approach to Debye–Hückel theory. Interpretation of electrolyte activity coefficients in both dilute and concentrated solutions

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Journal of the Chemical Society, Faraday Transactions 1 Vol - 85 Issue - 2

Journal of the Chemical Society, Faraday Transactions 1 Vol -79

Journal of the Chemical Society, Faraday Transactions 1 Vol -69

A Kirkwood–Buff theoretical approach to Debye–Hückel theory. Interpretation of electrolyte activity coefficients in both dilute and concentrated solutions

Content Provider	Royal Society of Chemistry (RSC)
Author	Newman, Kenneth E.
Copyright Year	1989
Abstract	A set of equations is developed for the thermodynamic properties of 1:1 electrolytes using as its starting point the non-linearized version of the Poisson–Boltzmann radial distribution function and Kirkwood–Buff theory to forge the connection with the salt chemical potential. It is shown that the Debye–Hückel (DH) limiting law arises not from the linear term in the exponential expansion of the distribution but from the square term. The extended DH equation arises as a direct consequence of the treatment, although the interpretation of the distance of closest approach term is slightly different. By including only two parameters, one representing the distance of closest approach and a constant to represent ion–solvent interactions, excluded-volume effects and/or higher-order ion–ion interactions, the theory is able to model the activity coefficients of aqueous KCl accurately from infinite dilution to 4 mol kg–1. The theory is compared with other approaches.
Starting Page	485
Ending Page	492
Page Count	8
File Format	PDF
ISSN	03009599
Volume Number	85
Issue Number	3
Journal	Journal of the Chemical Society, Faraday Transactions 1
DOI	10.1039/F19898500485
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Poisson Radial distribution function Forge Chemical potential Buff Kirkwood
Content Type	Text
Resource Type	Article
Subject	Chemistry

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