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Osmotic coefficients, individual and mean activity coefficients of primitivemodel electrolyte solutions are computed at different molar concentrationsusing the symmetric Poisson-Boltzmann and modified Poisson-Boltzmann theories.The theoretical results are compared with an extensive series of Monte Carlosimulation data obtained by Abbas et al. [Fluid Phase Equilib., 2007, 260, 233;J. Phys. Chem. B, 2009, 113, 5905]. The agreement between modifiedPoisson-Boltzmann predictions with the "exact" simulation results is almostquantitative for monovalent salts, while being semi-quantitative or better forhigher and multivalent salts. The symmetric Poisson-Boltzmann results, on theother hand, are very good for monovalent systems but tend to deviate at higherconcentrations and/or for multi-valent systems. Some recent experimental valuesfor activity coefficients of HCl solution (individual and mean activities) andNaCl solution (mean activity only) have also been compared with the symmetricand modified Poisson-Boltzmann theories, and with the Monte Carlo simulations.

condensed matter physics

Thermodynamics of primitive model electrolytes in the symmetric and  modified Poisson-Boltzmann theories. A comparative study with Monte Carlo  simulations