Evaluation of the kinetic performance of new prototype 2.1 mm × 100 mm narrow-bore columns packed with 1.6 μm superficially porous particles

• The kinetic performance of new 1.6 μm prototype core–shell particles is presented.
• Narrow-bore columns packed with them can provide over 400,000 plates per meter.
• Ultra-low dispersive vHPLC systems are necessary to achieve most of this efficiency level.
• The system variance was measured with a zero dead volume union connector.
• The system variance is underestimated by 20–30% when using ZDV union connectors.

The mass transfer mechanism in three prototype narrow-bore columns (2.1 mm × 100 mm format) packed with 1.6 μm superficially porous particles was investigated using different instruments. The heights equivalent to a theoretical plate of three small molecules were measured using a mixture of acetonitrile and water as the eluent. The values reported include the contributions of longitudinal diffusion, eddy dispersion, and the solid–liquid mass transfer resistance. The bulk diffusion coefficients of the analytes were measured using the capillary method, calibrated with thiourea in pure water. The reduced longitudinal diffusion coefficient was determined from the results of a series of peak parking experiments. The solid–liquid mass transfer resistance coefficient and the intra-particle diffusivities of the analytes in the porous region of the particles were estimated from Garnett–Torquato's model of effective diffusion in dense beds packed with core–shell particles. The eddy dispersion term, mostly due to trans-column and border effects, was obtained by subtracting the longitudinal diffusion and the solid–liquid mass transfer resistance terms from the total HETP obtained from the first and second central peak moments calculated by numerical integration (Simpson's approach) after baseline correction and systematic left and right cuts of the peak profiles. The results show that the eddy dispersion controls at least 66% of the overall column HETP for small molecules beyond the optimum velocity. This work illustrates how important it is to use ultra-low dispersive very high pressure liquid chromatography (vHPLC) systems to properly measure and to practically use the high efficiencies of narrow-bore columns packed with 1.6 μm core–shell particles since these columns provide intrinsic efficiencies higher than 400,000 plates per meter.