Nonideality of Single and Mixed Electrolyte Solutions Up to Moderately High Concentration; Theory Based on Debye-Huckel Radial Distribution Function
Kondo, Kazuo
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https://hdl.handle.net/2142/69723
Description
Title
Nonideality of Single and Mixed Electrolyte Solutions Up to Moderately High Concentration; Theory Based on Debye-Huckel Radial Distribution Function
Author(s)
Kondo, Kazuo
Issue Date
1981
Department of Study
Chemical Engineering
Discipline
Chemical Engineering
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Engineering, Chemical
Abstract
Because of the complex nature of the solvent effect and of the mathematical difficulty in the treatment of the Coulombic long-range force, the theoretical treatments of the equilibrium properties of the electrolyte solution are not fully developed if one compares with those of the non-electrolyte solution.
Theories currently available can in general be classified into following two categories; the statistical mechanical theory and the semi-empirical theory. Both approaches have their inherent disadvantages. The present approach was intermediate between those approaches in order to compensate for the disadvantages of both.
The interionic potential of mean force was the addition of the primitive model and the square-well potential. Instead of numerically solving the integral equation, the radial distribution function was assumed to be given a priori as the Debye-Huckel radial distribution function. It was found that this radial distribution function agrees well with the result of the integral equation of hypernetted chain or the machine calculation of Monte Carlo up to a molarity of a few. The purturbation method was introduced for the solvent effect of the square-well potential. The pressure equation yielded the osmotic pressure, and this was converted to the activity coefficient with the aid of the Helmholtz energy. These equations derived were applicable to the system of an arbitrary number of solutes.
This set of equations was applied to the molal activity and osmotic coefficients in the Lewis-Randall system of completely dissociated electrolytes at 25(DEGREES)C. 22 1:1 type and 21 1:2 type electrolytes were tested and it was found that a unique parameter, the depth of square-well, explains both the activity and osmotic coefficient of single electrolyte up to the ionic strength of 3 with reasonably small standard deviation. This parameter had a significant physical meaning.
Those parameters were applied to the mixed electrolytes of 17 systems for osmotic coefficients and 24 systems for activity coefficients for the case of one ion in common. The standard deviations were comparable to those of the single electrolytes.
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