Effects of pore flow on the separation efficiency in capillary electrochromatography with porous particles.

The effect of pore flow on the separation efficiency of capillary electrochromatography (CEC) has been studied using columns packed with particles with different pore sizes. A previously developed model was used to predict the (relative) pore flow velocity in these columns under various experimental conditions. Equations are derived describing the effect of pore flow on peak broadening in CEC. The theory has been compared with practice in the reversed-phase CEC separation of various polyaromatic hydrocarbons. It is shown, by theory and experimentally, that the mass-transfer resistance contribution to peak dispersion can be effectively eliminated when using porous particles with a high (> or =50 nm) average pore diameter. Moreover, at high pore-to-interstitial flow ratios the flow inhomogeneity contribution (the A term in the plate height equation) is also shown to decrease. Under optimal conditions, a reduced plate height of 0.3 for the nonretained compound could be obtained. It is argued that fully perfusive porous particles can be a more efficient separation medium in CEC than nonporous particles.