Development of retention mechanism for the separation of carboxylic acids and inorganic anions in cryptand-based ion chromatography.

The ion-exchange and complex forming equilibria were quantitatively described and demonstrated in order to understand major factors in the control of selectivity in the analytical separation of carboxylic acids and inorganic anions in cryptand based ion chromatography. A complex retention model has been developed for the separation on a non-conventional IC column. Changes in retention are treated both theoretically and experimentally. Retention mechanism is employed on a macrocycle-based (cryptand n-decyl-[2.2.2]) ion-exchange chromatographic phase to improve the selectivity for a mixture of model analytes. We introduced an alternative internal gradient method by mixed eluent (i.e. eluents formed by combination of two alkali hydroxide with different molar ratio). The effect of binary mixed eluent (Li/Na, Li/K) on the retention behavior and peak shape of carboxylic acids are also discussed in view of the proposed theory. It was shown that the effects of binary aqueous mobile phases, held isocratically behave very similar to the step gradient mode. The "internal gradient" separation system has advantages over traditional step gradient mode. Twenty-six anions of widely varying chemical character (mono-, di-, tri-valent inorganic anions, mono-, di-, tri-valent aliphatic carboxylic acids, aromatic- and haloacetic carboxylic acids) were investigated on the cryptand-based (D222) stationary phase using different methods by LiOH, NaOH and KOH eluent. The predicted vs measured retention data are in rather good agreement. High degree of linearity was obtained for inorganic anions, multivalent carboxylic acids, and for aromatic and haloacetic acids R = 0.992, 0.969, and 0.980, respectively.