Column selectivity in reversed-phase liquid chromatography: III. The physico-chemical basis of selectivity

Abstract

Reversed-phase liquid chromatography (RP-LC) retention data for 23 additional solutes have been acquired to further test and evaluate a general relationship from part I: (1) log α= log (k/k ref )= η′ H (i) + σ′ S (ii) + β′ A (iii) + α′ B (iv) + κ′ C (v) The physico-chemical origin of terms i– v above is examined here by comparing values of (a) the solute parameters of Eq. (1) ( η′, σ′, etc.) vs. solute molecular structure, and (b) the column parameters ( H, S, etc.) vs. column properties (ligand length and concentration, pore diameter, end-capping). We conclude that terms i– v correspond, respectively, to hydrophobic ( i), steric ( ii), hydrogen bonding ( iii, iv) and ionic ( v) interactions between solute and stationary phase. While steric interaction (term ii) is superficially similar to what previously has been defined as “shape selectivity”, the role of the solute and column in determining steric selectivity (term ii) appears more complex than previously proposed for “shape selectivity”. Similarly, what has previously been called hydrogen bonding between donor solutes and an acceptor group in the stationary phase (term iv) is very likely an oversimplification.