Statistical mechanics of electrolytes and polyelectrolytes. I. Symmetric electrolyte solutions

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Abstract
Simple ionic solutions are studied using the BBGKY hierarchy. An iterative estimation technique is developed which enables one to derive various well-known approximations. It is shown that in dilute symmetric electrolytes the Poisson–Boltzmann and the hypernetted chain equations are valid to a higher degree of accuracy than in asymmetric electrolytes and plasmas. The DHX, EXP, and the PY approximations are derived from the HNC equation. A perturbative correction to the EXP approximation is obtained which gives contact values of the correlation functions and excess internal energies close to those obtained by numerical solutions to the HNC equation for 1-1 electrolytes over a wide range of molar concentrations and for 2-2 electrolytes of relatively high concentration.

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