Mechanism of ion stacking in aqueous partition chromatographic processes

It has been reported that ion enrichment phenomena are observed in liquid chromatographic processes with an aqueous mobile phase on the columns packed with nonionic materials. However, the mechanism of the ion enrichment is not at all well understood. In this study, we investigated the retention and enrichment behaviors of simple inorganic anions on a C18-bonded silica column and a cross-linked hydroxylated methacrylic polymer gel column with pure aqueous mobile phases containing various electrolytes. We show that the stacking of ionic solutes can successfully be accounted for by the ion partition model, and it takes place due to the effect of the background coion in the eluent and/or sample solution on the distribution of the ions between the bulk water and the water incorporated in the packing material, which acts as the stationary phase. Using the ion exclusion effect of fixed anionic charges on a packing material as well as the ion stacking by partition, we developed a simple and versatile method for effective enrichment of anionic solutes in aqueous solutions. The enrichment factor and the elution time of the stacked ion zone can be predicted by the ion partition model.