Manipulation of separation selectivity for alkali metals and ammonium in ion-exchange capillary electrochromatography using a suspension of cation exchange particles in the electrolyte as a pseudostationary phase

Abstract

The viability of using ion-exchange particles as a pseudostationary phase in capillary electrochromatography for the separation of monovalent inorganic cations has been investigated. Using sulfonated polymeric particles (average diameter 225 nm) as the pseudostationary phase, the separation selectivity for alkali metals and ammonium was examined under a range of background electrolyte compositions and employing indirect absorbance detection. Addition of ion-exchange particles to the background electrolyte resulted in a reduction in the observed electrophoretic mobility of the analytes due to the establishment of ion-exchange interaction with the pseudostationary phase, with the decrease in mobilities following the ion-exchange interaction order for these analytes with a sulfonated stationary phase. Increasing the concentration of the particles resulted in a uniform reduction in the electrophoretic mobility of the analytes, similar to that observed in micellar electrokinetic chromatography. Conversely, increasing the concentration of the cationic indirect detection probe (which also acted as an ion-exchange competing cation) resulted in a decrease in the ion-exchange interaction with the particles and a reduction of the relative ion-exchange contribution to the overall separation mechanism. Plots of log[retention factor] versus log[electrolyte concentration] were linear, as is the case for ion-exchange chromatography, but the observed slopes were greater than predicted from ion-exchange theory. Indirect absorbance detection was found to give poor sensitivity due to light scattering effects caused by the particles of pseudostationary phase.