title: Evaluation of the kinetic performance of new prototype 2.1mm×100mm narrow-bore columns packed with 1.6μm superficially porous particles.
abstract: The mass transfer mechanism in three prototype narrow-bore columns (2.1mm×100mm format) packed with 1.6μm 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 1.6μm core-shell particles since these columns provide intrinsic efficiencies higher than 400,000 plates per meter.
authors.affiliation: Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA.
authors.forename: Fabrice
authors.initials: F
authors.lastname: Gritti
authors.affiliation: Waters Corporation, Milford, MA 01757, USA.
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Shiner
authors.affiliation: Waters Corporation, Milford, MA 01757, USA.
authors.forename: Jacob N
authors.initials: JN
authors.lastname: Fairchild
authors.affiliation: Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA. Electronic address: guiochon@utk.edu.
authors.forename: Georges
authors.initials: G
authors.lastname: Guiochon
mesh_terms: D002851:Chromatography, High Pressure Liquid / Q000295:instrumentation / Q000379:methods*; D004058:Diffusion; D007700:Kinetics; D016062:Porosity
keywords: Core–shell particles; Eddy dispersion; Extra-column band broadening; Longitudinal diffusion; Mass transfer mechanism; Solid–liquid mass transfer resistance