Solute–Solvent Interactions in Hydrophilic Interaction Liquid Chromatography: Characterization of the Retention in a Silica Column by the Abraham Linear Free Energy Relationship Model

The Abraham linear free energy relationship model has been used to characterize a hydrophilic interaction liquid chromatography (HILIC) silica column with acetonitrile/water and methanol/water mobile phases. Analysis by the model for acetonitrile/water mobile phases points to solute volume and hydrogen bond basicity as the main properties affecting retention, whereas solute hydrogen bond acidity, dipolarity and polarizability practically do not affect it. Formation of a cavity is easier in acetonitrile-rich mobile phases than in the aqueous stationary phase, and hence increase of solute volume decreases retention. Conversely, hydrogen bond acidity is stronger in the aqueous stationary phase than in the acetonitrile-rich mobile phase and thus an increase of solute hydrogen bond basicity increases retention. Results are similar for methanol/water mobile phases with the difference that solute hydrogen bond acidity is significant too. Increase in hydrogen bond acidity of the solute decreases retention showing that methanol mobile phases must be better hydrogen bond acceptors than acetonitrile ones, and even than water-rich stationary phases. The results are like the ones obtained in zwitterionic HILIC columns bonded to silica or polymer supports for acetonitrile/water mobile phases, but different for solute hydrogen bond acidity for a polymer bonded zwitterionic column with methanol/water mobile phases, indicating that bonding support plays an important role in HILIC retention. Comparison to RPLC characterized systems confirms the complementarity of HILIC systems to RPLC ones because the main properties affecting retention are the same but with reversed coefficients. The least retained solutes in RPLC are the most retained in HILIC.