Modified Linearized Poisson-Boltzmann Theory. Dynamic and Thermodynamic Properties of 1 : 1 Electrolytes

Abstract

Theoretical electrolyte conductivity and osmotic and activity coefficient relationships that work well over a large range of concentrations, up to 1 mol l^–1, are derived from a hypothetical modified linearized Poisson–Boltzmann distribution function. The distribution function is expressed in terms of modified Debye parameter &kgr; and normalization constant α. Both of these parameters are evaluated in terms of concentration and ion-size parameter, d, by the help of moment conditions. The modified Debye parameter &kgr; is also expressed as a function of the usual Debye parameter &kgr;_D. Also considered is the short-range part of the pair potential crucial to obtain at least qualitative agreement with experimental results of electrolytic solutions, and it is assumed that the short-range part of the potential is discontinuous at ion-size parameter