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The choice of analogue ion of the mobile phase additive is shown to significantly affect the analysis of quaternary ammonium compounds (QACs) in ion-pair reversed-phase high-performance liquid chromatography. A series of bromide-containing and dodecyl-sulfate-containing mobile phase additives are investigated using two QAC probe analytes. In all instances, the quaternary-ammonium-containing mobile phase additives perform better than the corresponding sodium-containing additives for effective QAC elution. These results indicate that the structure of the analogue ion, not just its formal charge, is important in the reversed-phase ion-pair chromatography of these compounds. The relative elution order of the QAC probe analytes is also influenced by the counter ions of the mobile phase additives, with bromide and dodecyl sulfate offering opposite elution orders.

The Role of Analogue Ions in the Ion-Pair Reversed-Phase Chromatography of Quaternary Ammonium Compounds