Solvation parameters. Part 5: Physicochemical interpretation of experimental solvent values for stationary phases of gas–liquid chromatography

It has been demonstrated for a long time that in the particular case of gas–liquid chromatography (GLC), a linear free energy relationship (LFER) of five terms can be established, each term including a parameter of solute and a parameter of solvent. The nature of some of these parameters has been quite clearly identified, even if not always well predicted from the molecular structure. First of all, the five solute parameters: two involved in the hydrogen bonding and three in the Van der Waals forces; secondly, the two solvent parameters involved in hydrogen bonding. It was remaining an uncertainty concerning the nature of the solvent parameters named D, W and E, respectively associated with the solute parameters of dispersion, orientation and induction/polarizability. This uncertainty has been solved using experimental chromatographic data of McReynolds (56 phases) and of the Kováts group (11 phases). The parameter W appears as of polar nature strictly speaking. The parameters D and E can be expressed by two opposite bilinear functions of 1/V (inverse of molecular volume) and PSA/V (ratio of the polar surface area over the molecular volume). These results are in agreement with previous studies limited to alkanes by the Kováts group.