Effect of electrolytes on the retention behavior of some benzenesulfonates in electrochemically modulated liquid chromatography

The effects of electrolytes on the retention behavior of some benzenesulfonates in electrochemically modulated liquid chromatography were studied. Both cations and anions were found to have considerable effects on retention. As cation size increases, retention decreases, while anions show more complicated effects were anionic size and charge distribution contribute to the overall behavior of anions. Large anions with a delocalized negative charge on the whole species result in lower retention times, and vice versa. Also, electrolyte concentration plays an important role in the retention behavior observed. Initially, as electrolyte concentration was increased retention increased due to electrostatic interactions of cations with the negatively charged stationary phase. However, retention starts to slightly decrease or increase after some specific electrolyte concentration depending on the nature of the electrolytic species. Finally, an interesting behavior of double peak appearance of a single solute was observed at low electrolyte concentrations and was attributed to the presence of other active sites on the carbon stationary phase.