Effect of the ionic strength of salts on retention and overloading behavior of ionizable compounds in reversed-phase liquid chromatography II.: Symmetry-C18

In a companion paper, we describe the influence of the concentration and the nature of salts dissolved in the mobile phase (methanol: water, 40:60, nu/nu) on the adsorption behavior of propranolol (R'-NH2+-R, Cl-) on XTerra-C-18. The same experiments were repeated on a Symmetry-C-18 column to compare the adsorption mechanisms of this ionic compound on these two very different RPLC systems. Frontal analysis (FA) measurements were first carried out to determine the best isotherm model accounting for the adsorption behavior of propranolol hydrochloride on Symmetry with a mobile phase without salt (and only 25% methanol to compensate for the low retention in the absence of salt). The adsorption data were best modeled by the bi-Moreau model. Large concentration band profiles of propranolol were recorded with mobile phases having increasing KCl concentrations (0, 0.002, 0.005, 0.01, 0.05, 0.1 and 0.2 M) and the best values of the isotherm coefficients were determined by the inverse method (IM) of chromatography. The general effect of a dissociated salt in the mobile phase was the same as the one observed earlier with XTerra-C-18. Increasing the salt concentration increases the two saturation capacities of the adsorbent and the adsorption constant on the low-energy sites. The adsorption constant on the high-energy sites decreases and the adsorbate-adsorbate interactions tend to vanish with increasing salt concentration of the mobile phase. The saturation capacities decrease with increasing radius of the monovalent cation (Na+, K+, Cs+, etc.). Using sulfate as a bivalent anion (Na2SO4) affects markedly the adsorption equilibrium: the saturation capacities are drastically reduced, the high-energy sites nearly disappear while the adsorption constant and the adsorbate-adsorbate interactions on the low-energy sites increase strongly. The complexity of the thermodynamics in solution might explain the different influences of these salts on the adsorption behavior. (C) 2004 Elsevier B.V. All rights reserved.