Reversed-phase high-performance liquid chromatography behavior of chaotropic counteranions

The retention behavior of inorganic liophilic anions in reversed-phase HPLC columns was studied. Usually, the addition of these ions to the mobile phase influences the retention of protonated basic analytes similar to the effect of amphiphilic ions (ion-pairing agents). The nature of this influence is the subject of this paper. HPLC retention of perchlorate (ClO4−), tetrafluoroborate (BF4−), and hexafluorophosphate (PF6−) ions was studied on six columns with different bonded phases including alkyl, phenyl and perfluorophenyl phases. The effect of the mobile phase ionic strength on the retention of liophilic ions was investigated. The influence of the type of organic modifier, acetonitrile and methanol, on the retention of inorganic ions was also studied and interpreted on the basis of adsorption from solutions. Semi-empirical expression is suggested for the description of the retention profile of studied liophilic ions versus the eluent composition. Significant retention of these ions is observed in acetonitrile–water eluents. Multilayer-type adsorption of the acetonitrile on the reversed-phase surface and its strong dispersive (or π–π) interactions with liophilic ions are responsible for significant retention of these ions. This accumulation of liophilic ions in the adsorbed layer on the surface of reversed-phase material introduces an electrostatic component in the retention of protonated basic analytes.