Enhanced radial dispersion in open tubular column chromatography

Abstract

AbstractRadial diffusion of solutes in the mobile phase limits the practical linear velocities that can be used to increase speed of analysis in conventional open tubular column chromatography. Several methods have been devised to enhance radial dispersion that do not depend only on molecular radial diffusion. In this review, the methods of enhancing dispersion found in the chromatographic literature are discussed. These methods include the use of deformed columns, and spinning band and static mixer columns. These techniques have been found to be of little value in analytical chromatography. Electroosmotic flow has been used to generate a plug‐like flow profile in LC and generates one to two orders of magnitude lower plate height than produced at laminar flow conditions. Turbulent and secondary flow have been used to enhance radial diffusion in open tubular columns for gas, liquid, and supercritical fluid chromatography. These techniques are described from their theoretical and practical aspects.Turbulent flow has been investigated as a means for enhancing radial dispersion in open tubular column chromatography for several years. At low linear velocities (Reynolds numbers < 2000), the Golay equation accurately predicts that increasing velocities generate higher plate heights. However, turbulent flow experimental results have shown that unretained solutes have decreasing plate heights with increasing velocity after a critical velocity is achieved. Up to this time, turbulent flow chromatography has not been shown to be useful for retained solutes, and applications in analytical separations are absent in the literature.Secondary flow has also been studied by several investigators for the enhancement of radial dispersion. A circular, radial flow profile can be generated by centrifugal forces in tightly coiled columns, and after a critical velocity is achieved, columns coiled to appropriate aspect ratios yield lower plate heights than straight columns for unretained solutes as the velocity is increased. Although retained solutes yield higher plate heights in coiled rather than conventional straight columns in some cases due to the resistance to mass transfer at the interphase region, higher speeds of analysis are obtained. Secondary flow chromatography has been successfully applied in gas and supercritical fluid chromatography for the rapid separation of alkanes having low retention. Nevertheless, applications using secondary flow in chromatographic separations are limited.