Selection of comparison criteria and experimental conditions to evaluate the kinetic performance of monolithic and packed-bed columns

The present study concerns the problem of finding appropriate experimental conditions and comparison criteria to assess the kinetic performance of LC supports with different sizes or morphologies. A general procedure, based on evaluating each support for its own optimal mobile-phase composition, is proposed. The practical elaboration of the procedure is illustrated using the specific case of a capillary LC separation of a series of polycyclic aromatic test compounds employing silica-monolith capillary columns and capillary columns packed with 6-μm porous particles. To compare the systems for their ability to yield the fastest critical-pair separation, plate-height measurements are transformed into an effective plate number kinetic plot, i.e., a plot of the extrapolated retention time divided by the square of the extrapolated effective plate number (tR/Neff2) versus Neff. This type of data representation provides a direct and universal basis to compare the kinetic performance of different LC supports and it corrects for differences in retention strength arising from different phase ratios.