On physical meaning of van't Hoff equation and its applicability in chromatography.

The van't Hoff equation is a widely used tool to study adsorption thermodynamics in chromatography. Recent experimental data and some theoretical arguments questioned the accuracy of thermodynamic characteristics determined by using this equation. The present report addresses these concerns and shows that if certain requirements are satisfied, the van't Hoff analysis provide reliable results. These requirements include isothermality of the column not perturbed by the percolation of the mobile phase, mass transfer kinetics allowing sufficient proximity to equilibrium, pressure below 200 bar for low molecular weight compounds and below 50 bar for macromolecules, and knowledge of the phase ratio at all experimental temperatures to allow accurate conversion of the retention factor to the equilibrium constant. Physical meaning of adsorption enthalpy and entropy obtained by means of the van't Hoff analysis particularly in the case of heterogeneous adsorbents is discussed and recommendations on how to perform experiments to obtain reliable results are given.