Activity Coefficients of Concentrated Salt Solutions: A Monte Carlo Investigation

Monte Carlo (MC) simulations were used to calculate single ion and mean ionic activity coefficients and water activity in concentrated electrolytes and at elevated temperatures. By using a concentration dependent dielectric constant, the applicability range of the MC method was extended to 3 mol·L⁻¹ or beyond, depending on the salt. The calculated activity coefficients were fitted to experimental data by adjusting only one parameter, i.e., the cation radius. Fitted ionic radii obtained by such a procedure indicate the extent of cation–anion interaction in a salt solution. For example, the fitted radii of Li⁺ and Na⁺ in LiClO₃ and NaClO₃ indicate that Li⁺ is strongly hydrated and has a weak interaction with the ClO₃⁻ ion whereas Na⁺ forms ion pairs and loses its hydration. The single ion activity coefficients for protons and chloride ions in HCl were calculated by MC simulations and compared with experimental values obtained by ion selective electrodes. The calculated single ion activity coefficients for protons and chloride ions are much lower and higher, respectively, than the experimental values. However, the mean activity coefficients of HCl obtained by the MC simulations, ion selective electrodes and vapor pressure measurements are in good agreement. In the case of NaCl and KCl the calculated single ion activity coefficients of Na⁺, K⁺, and Cl⁻ are much closer to the values obtained by ion selective electrodes. The results in HCl indicate that the hydrated proton is large and includes the chloride ion within the hydration shell, i.e., the apparent size of the chloride ion is negligible.