Inverse supercritical fluid chromatography (ISFC) is used to measure p
artition coefficients of five polar and nonpolar organic solids betwee
n supercritical CO2 and cross-linked poly-(dimethylsiloxane) (PDMS) sw
ollen with CO2. Polymer-solute interaction energies, which are determi
ned from the partition coefficients, correlate with the heats of vapor
ization of the pure solutes. These interaction energies can be determi
ned at ambient temperature for solutes that are too nonvolatile to stu
dy by inverse gas chromatography. Binary and ternary phase equilibria
are modeled with lattice fluid theory including a term to account for
the degree of polymer crosslinking. Experimental results indicate that
solute adsorption on the support phase, which can be severe in packed
columns, is negligible with the use of capillary columns.