Clustering in supercritical fluid mixtures

Abstract

AbstractThe local compositions of supercritical fluid carbon dioxide and a cosolvent about a solute at infinite dilution have been estimated for the first time using spectroscopic measurements. The solute was phenol blue, the bulk concentrations of the cosolvents n‐octane, acetone, ethanol, and methanol ranged from 0 to 100 mol%, and the pressure ranged from 80 to 300 bar. In each case, the clusters of solvent about the solute are enriched in cosolvent. Solubility data have been measured for phenol blue in CO2 with and without the cosolvent acetone, and regressed using an augmented van der Waals‐density‐dependent local composition model to determine the relevant binary interaction energies. The local compositions calculated from the model agree with those that were esimated spectroscopically. The model was used to predict solubilities of solids in supercritical fluid CO2 with various cosolvents.