Abstract: | The influence of the nature of quaternary ammonium compounds on retention in high-performance liquid chromatography on dynamically modified silica was investigated. Adsorption isotherms were determined on bare silica (LiChrosorb Si 60) for four alkyltrimethylammonium bromides and two symmetrical tetraalkylammonium bromides, each containing 15–21 carbon atoms. It was found that only the long-chain quaternary ammonium ions are adsorbed on to the silica surface in appreciable amounts and that the affinity increasing number of carbon atoms in the alkyl chain. The maximum amount that can be adsorbed per gram of silica is of the same order of magnitude for each of the four long-chain quaternary ammonium compounds. This amount, however, is reached at lower concentrations in the eluent the longer is the alkyl chain.The retention of five test compounds was determined over the whole concentration range investigated for each of the modiflying agents. The surfactant concentration that causes maximum retention for four of five test compounds coincides with its critical micellar concentration. The retention mechanisms and the influence of the type of the modifying agent on selectivity are discussed, and compared with published results on related experiments on chemically bonded stationary phases. |