Cosolvent interactions in supercritical fluid solutions

Abstract The addition of cosolvents to supercritical fluid (SCF) solvents can have large effects on solubilities, giving engineers the ability to tailor loadings and selectivities of solutes for difficult separations. It is necessary to have a better understanding of the special intermolecular interactions that occur in SCF solutions to predict the effects of cosolvents. We use a SCF chromatographic technique to acquire a database of cosolvent effects for a variety of cosolvents and solutes; examination of the cosolvent effects shows evidence of hydrogen bonding, charge transfer complex formation, and dipole‐dipole coupling between solute and cosolvent molecules. SCF solvents, carbon dioxide, ethane, and fluoroform, are compared, and then the use of the chromatograph to measure solubilities is discussed.