SYMMETRICAL POISSON BOLTZMANN AND MODIFIED POISSON BOLTZMANN THEORIES

Symmetric pair and triplet ionic correlation functions in the electrolyte bulk are derived using Kirkwood's charging process. Four closures at the Poisson-Boltzmann level of approximation are considered for the pair distribution function and comparisons made with simulation thermodynamic properties for the following primitive model electrolytes: (i) 1:1 and 2:2 valencies with equal and unequal ion radii, (ii) 1 : 3 valency with equal ion radii. The modified Poisson-Boltzmann theory is extended to treat electrolytes with both unequal radii and/or unsymmetrical valencies.