Predicting freezing points of ternary salt solutions with the multisolute osmotic virial equation.

Previously, the multisolute osmotic virial equation with the combining rules of Elliott et al. has been shown to make accurate predictions for multisolute solutions with only single-solute osmotic virial coefficients as inputs. The original combining rules take the form of an arithmetic average for the second-order mixed coefficients and a geometric average for the third-order mixed coefficients. Recently, we derived generalized combining rules from a first principles solution theory, where all mixed coefficients could be expressed as arithmetic averages of suitable binary coefficients. In this work, we empirically extended the new model to account for electrolyte effects, including solute dissociation, and demonstrated its usefulness for calculating the properties of multielectrolyte solutions. First, the osmotic virial coefficients of 31 common salts in water were tabulated based on the available freezing point depression (FPD) data. This was achieved by polynomial fitting, where the degree of the polynomial was determined using a special criterion that accounts for the confidence intervals of the coefficients. Then, the multisolute model was used to predict the FPD of 11 ternary electrolyte solutions. Furthermore, models with the new combining rules and the original combining rules of Elliott et al. were compared using both mole fraction and molality as concentration units. We find that the mole-fraction-based model with the new combining rules performs the best and that the results agree well with independent experimental measurements with an all-system root-mean-square error of 0.24 osmoles/kg (0.45 °C) and close to zero mean bias for the entire dataset (371 data points).