Radial heterogeneity of some analytical columns used in high-performance liquid chromatography

An on-column electrochemical microdetector was used to determine accurately the radial distribution of the mobile phase velocity and of the column efficiency at the exit of three common analytical columns, namely a 100 mm × 4.6 mm C18 bonded silica-based monolithic column, a 150 mm × 4.6 mm column packed with 2.7 μm porous shell particles of C18 bonded silica (HALO), and a 150 mm × 4.6 mm column packed with 3 μm fully porous C18 bonded silica particles (LUNA). The results obtained demonstrate that all three columns are not radially homogeneous. In all three cases, the efficiency was found to be lower in the wall region of the column than in its core region (the central core with a radius of 1/3 the column inner radius). The decrease in local efficiency from the core to the wall regions was lower in the case of the monolith (ca. 25%) than in that of the two particle-packed columns (ca. 35–50%). The mobile phase velocity was found to be ca. 1.5% higher in the wall than in the core region of the monolithic column while, in contrast, it was ca. 2.5–4.0% lower in the wall region for the two particle-packed columns.