American Journal of Analytical Chemistry, 2018, 9, 406-422
http://www.scirp.org/journal/ajac
ISSN Online: 2156-8278
ISSN Print: 2156-8251
DOI: 10.4236/ajac.2018.99032 Sep. 14, 2018 406 American Journal of Analytical Chemistry
Additional Arguments for a Correction of the
Debye-Hückel, Maxwell-Boltzmann Equations
for Dilute Electrolyte Equilibria
Peter van der Weg
Unilever Research & Development, Vlaardingen, The Netherlands
Abstract
Peter Debye and Erich Hückel had developed a theory for the ionic activity
coefficients in dilute solutions of strong electrolytes some 95 years ago [1].
Their limiting law still stands and is confirmed as close to reality in many ex-
periments. In a previous article [2], it is shown that these limiting activity coef-
ficients arise because the electrical contribution in the electrochemical poten-
tial of ionic species is overestimated traditionally with a factor 2. The smaller
value removes inconsistencies in the models and complies better with the ba-
sic electrostatic principles. In this article further evidence is given in support
of this alternative description. As consequence the dilute activity coefficients
become unity, e.g. are removed, which means that the electrochemical poten-
tial of ions in dilute solutions is expressed directly in concentration, instead
of activity, which simplifies modelling in such dilute solutions.
Keywords
Debye-Hückel, Electrolyte, Activity Coefficients, Electrochemical Potential,
Debye, Hückel
1. Introduction
The behavior of a strong electrolyte in the limit of high dilution is given by the
formulae due to Debye and Hückel [1]. Modifications to the theories were dis-
cussed in 2009 [2]. This publication gives a discussion and additional informa-
tion in support of the theory.
2. Thermodynamics
For the energy of a phase we can write:
How to cite this paper: van der Weg, P.
(2018) Additional Arguments for a Correc-
tion of the Debye-Hückel, Maxwell- Boltzmann
Equations for Dilute Electrolyte Equilibria.
American Journal of Analytical Chemistry,
9, 406-422.
https://doi.org/10.4236/ajac.2018.99032
Received: May 16, 2018
Accepted: September 11, 2018
Published: September 14, 2018
Copyright © 2018 by author and
Scientific Research Publishing Inc.
This work is licensed under the Creative
Commons Attribution International
License (CC BY 4.0).
http://creativecommons.org/licenses/by/4.0/
Open Access