Open Access. Powered by Scholars. Published by Universities.®
Articles 1 - 2 of 2
Full-Text Articles in Physics
Ion‐Pair Theory Of Concentrated Electrolytes. Iii. Variational Principle, Frank Stillinger, Ronald White
Ion‐Pair Theory Of Concentrated Electrolytes. Iii. Variational Principle, Frank Stillinger, Ronald White
Center for Advanced Mineral and Metallurgical Processing (CAMP)
Two major contributions are devised for that theory of concentrated electrolytes which by convention regards the ions as completely paired into uncharged dipolar “molecules.” First, a more satisfactory expression is obtained for the wavelength‐dependent static dielectric “constant” ε(k). Second, a variational principle for Helmholtz free energy F is displayed whose minimization with respect to the ion‐pair size distribution p(1) serves to determine both F and p(1). In anticipation of future numerical applications, a binary collision approximation is specified for the short‐range interaction aspect of the functional F[p(1)].
Ion‐Pair Theory Of Concentrated Electrolytes. Iv. Ion Atmosphere Charge Distribution, Frank Stillinger, Ronald White
Ion‐Pair Theory Of Concentrated Electrolytes. Iv. Ion Atmosphere Charge Distribution, Frank Stillinger, Ronald White
Center for Advanced Mineral and Metallurgical Processing (CAMP)
Arguments are presented indicating that the large‐size limiting behavior of the ion‐pair size distribution is qualitatively the same both with, and without, Coulomb interactions between ions. This in turn implies that the static dielectric response function ε0 / ε(k) derived in the preceding paper is nonanalytic at k = 0. The specific singular behavior of this response requires a branch cut along the imaginary k axis. It furthermore induces an r−8 tail in the ion atmosphere charge distribution at finite electrolyte concentration.