Role of mixing thermodynamic properties on the Soret effect

We demonstrate that the modified Kempers model, a recently developed theoretical model for the Soret effect in oxide melts, is applicable for predicting the composition dependence of the Soret coefficient in three binary molecular liquids with negative enthalpies of mixing. We compared the theoretical and experimental values for water/ethanol, water/methanol, water/ethylene glycol, water/acetone, and benzene/n-heptane mixtures. In water/ethanol, water/methanol, and water/ethylene glycol, which have negative enthalpies of mixing across the entire mole fraction range, the modified Kempers model successfully predicts the sign change of the Soret coefficient with high accuracy, whereas, in water/acetone and benzene/n-heptane, which have composition ranges with positive enthalpies of mixing, it cannot predict the sign change of the Soret coefficient. These results suggest that the model is applicable in composition ranges with negative enthalpies of mixing and provides a framework for predicting and understanding the Soret effect from the equilibrium thermodynamic properties of mixing, such as the partial molar volume, partial molar enthalpy of mixing, and chemical potential.