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Building on recent simulation work, it is demonstrated usingmolecular-dynamics (MD) simulations of two-component liquid mixtures that thechemical contribution to the Soret effect in two-component non-ideal fluidmixtures arises due to differences in how the partial pressures of thecomponents respond to temperature and density gradients. Further insight isobtained by reviewing the connection between activity and deviations fromRaoult's law in the measurement of the vapor pressure of a liquid mixture. Anew parameter gamma, defined in a manner similar to the activity coefficient,is used to characterize differences deviations from ``ideal'' behavior. It isthen shown that the difference gamma2-gamma1 is predictive of the sign of theSoret coefficient and is correlated to its magnitude. We hence connect theSoret effect to the relative volatility of the components of a liquid mixture,with the more volatile component enriched in the low-density, high-temperatureregion, and the less volatile component enriched in the high-density,low-temperature region. Because gamma is closely connected to the activitycoefficient, this suggests the possibility that measurement of partial vaporpressures might be used to indirectly determine the Soret coefficient. It isproposed that the insight obtained here is quite general and should beapplicable to a wide range of materials systems. An attempt is made tounderstand how these results might apply to other materials systems includinginterstitials in solids and multicomponent solids with interdiffusion occurringvia a vacancy mechanism.

Connection between partial pressure, volatility, and the Soret effect elucidated using simulations of non-ideal liquid mixtures