Solubility and activity coefficients of atmospheric surfactants in aqueous solution evaluated using COSMOtherm

Fatty acids (CH3(CH2)n−2COOH) and their salts are an important class of atmospheric surfactants. Here, we use COSMOtherm to predict solubility and activity coefficients for C2–C12 fatty acids with even number of carbon atoms and their sodium salts in binary water solutions and also in ternary water–inorganic salt solutions. COSMOtherm is a continuum solvent model implementation which can calculate properties of complex systems using quantum chemistry and thermodynamics. Calculated solubility values of the organic acids in pure water are in good agreement with reported experimental values. The comparison of the COSMOtherm-derived Setschenow constants for ternary solutions comprising NaCl with the corresponding experimental values from the literature shows that COSMOtherm overpredicts the salting out effect in all cases except for the solutions of acetic acid. The calculated activity and mean activity coefficients of fatty acids and fatty acid sodium salts, respectively, show deviation of the systems from ideal solution. The computed mean activity coefficients of the fatty acid salts in binary systems are in better agreement with experimentally derived values for the organic salts with longer aliphatic chain (C8–C10). The deviation of the solutions from ideality could lead to biased estimations of cloud condensation nuclei number concentrations if not considered in Köhler calculations and cloud microphysics.