Thermodynamic behavior of supercritical fluid mixtures

Abstract

The recent surge of interest in supercritical extraction has brought the unusual properties of supercritical mixtures into the focus of attention. We discuss some of the properties of binary mixtures in a range around the gas-liquid critical line from the point of view of supercritical solubility. The general thermodynamic relationships that govern the enhancement of supercritical solubility are readily derived by a mathematical method introduced by Ehrenfest. The enhancement is governed by a strong divergence centered at a critical end point. We give the classical and nonclassical power-law behavior of the solubility along the experimental paths of constant temperature or pressure. The factor multiplying the strong divergence contains the partial molar volume or enthalpy of the solute in the supercritical phase. These partials are quite anomalous, especially if the mole fraction of the solute is small. They diverge at the solvent's critical point. We cite experimental evidence of these divergences, especially the results of recent experiments in dilute near-critical salt solutions. The anomalies found in these salt solutions are common to all dilute near-critical mixtures with a nonvolatile second component. We show that on experimentally convenient paths the solubility in a binary liquid mixture near its consolute points is not strongly enhanced. Finally, we sketch a nonclassical model based on the decorated lattice gas that can be used to describe supercritical solubility enhancement at low solubility, with the pure solvent used as a reference.