Partial molar properties from solute retention in supercritical fluid chromatography: thermodynamic framework, advantages, and limitations

Abstract

The changes in chromatographic retention of a solute with the operating parameters such as pressure, temperature and composition of the mobile-phase fluid may be employed to measure the infinite-dilution partial molar volume of the solute in the mobile-phase fluid, the infinite-dilution partial molar enthalpy of the solute in the mobile-phase fluid, and the change of the infinite-dilution fugacity coefficient of the solute in a binary mobile-phase fluid with composition of the fluid. The theoretical background, benefits and limitations of this technique are discussed with emphasis on supercritical fluid chromatography.