A theoretical explanation for the retention mechanism of ion exclusion chromatography

Abstract

AbstractIon Exclusion Chromatography is classically used for the separation of weak acid anions. Dilute strong acids (e.g. sulphuric or perchloric acid) or just water are used as eluents. To increase the exclusion effect, strong cation exchangers, characterized by high concentration of functional groups, are applied. The inner column volume of commercially available columns is increased by increasing their size in comparison to traditional ones (usually 300×7.8 mm ID). The description of the retention mechanism of this technique implicitly assumes that both mobile and stationary phases are typical aqueous solutions, and their dielectric constants are thus equal. This equality implies the equality of solute dissociation constants in both phases. Another implicit assumption is that the dead‐ and inner volumes of the column are constant, and independent of the mobile phase composition. The present paper shows that stationary and mobile phases are generally characterized by different physicochemical parameters. Thus, they cannot be considered as regular aqueous solutions. Additionally, we show that weak cation exchanger resins, which are characterized by a relatively small concentration of the functional groups, and weak acid based buffers can also be used in IEC. This would expand the possible applications of this method and enable, for example, the separation of strong acids (anions). The influence of ionic strength on the retention and dead‐ and inner column volumes is also discussed. Finally we also briefly describe the retention mechanism of Electrostatic Ion Chromatography.