Accession Number:

ADA220713

Title:

Nonlocal Free Energy Density Functional Theory Applied to the Electrical Double Layer. 1. Symmetrical Electrolytes

Descriptive Note:

Technical rept. 10 Apr 1989-10 Apr 1990,

Corporate Author:

MINNESOTA UNIV MINNEAPOLIS DEPT OF CHEMICAL ENGINEERING AND MATERIALS SCIENCE

Report Date:

1990-04-10

Pagination or Media Count:

45.0

Abstract:

A theoretical study of the restricted primitive model of the electrical double layer using a free energy density functional theory is presented. The ion-ion hard-core repulsive contribution to the free energy is incorporated by a nonlocal excess hard-sphere free energy density functional. The electrostatic part of the ion-ion direct correlation function of the inhomogeneous electrolyte in the interfacial region is approximated by that of the homogeneous bulk electrolyte. The generalized van der Waals model and the Tarazona model are used to construct the respective excess hard-sphere free energy density functionals and compared with each other. Each model requires as input a hard equation of state. The Carnahan-Starling equation of state is chosen. The theory predicts correctly the layering effect of the counterions and the charge inversion phenomenon. The results for 11 and 22 electrolytes agree well with Monte Carlo simulations. The Tarazona model gives results in closer agreement with Monte Carlo data than does the generalized van der Waals model. The diffuse layer potentials predicted by the Tarazona model are not as accurate as those by the generalized hard-rod model which has been applied to the same problem in a previous study. jhd

Subject Categories:

  • Atomic and Molecular Physics and Spectroscopy

Distribution Statement:

APPROVED FOR PUBLIC RELEASE