title: A computational study of the porosity effects in silica monolithic columns.
abstract: We report on a theoretical study of the influence of the through-pore porosity on the main chromatographic performance parameters (reduced theoretical plate height, flow resistance, and separation impedance) of silica monoliths. To investigate this problem devoid of any structural uncertainties, computer-generated structural mimics of the pore geometry of silica monolithic columns have been studied. The band broadening in these synthetic monoliths was determined using a commercial Computational Fluid Dynamics (CFD) software package. Three widely differing external porosities (epsilon = 0.38, epsilon = 0.60, and epsilon = 0.86) are considered and are compared on the basis of an identical intra-skeleton diffusivity (Ds = 5 x 10(-10)m2/s), internal porosity (epsilon(int) = 0.5), and for the same phase retention factor (k' = 1.25). Since the data are obtained for perfectly ordered structures, the calculated plate heights and separation impedances constitute the ultimate performance ever to be expected from a monolithic column. It is found that, if silica monoliths could be made perfectly homogeneous, domain size-based reduced plate heights as small as h(min) approximately 0.8 (roughly independent of the porosity) and separation impedances as small as Emin approximately 130 (epsilon = 0.60) and Emin approximately 40 (epsilon = 0.86) should be achievable with pure water as the working fluid. The data also show that, although the domain size is a much better reduction basis than the skeleton size, the former is still not capable of bringing the van Deemter curves of different porosity columns into perfect agreement in the C term dominated velocity range. It is found that, in this range, large porosity monoliths can be expected to yield smaller domain size-based reduced plate heights than small porosity monoliths.
authors.affiliation: Vrije Universiteit Brussel, Department of Chemical Engineering (CHIS-TW), Pleinlaan 2, B-1050 Brussels, Belgium. pgzil@vub.ac.be
authors.forename: Piotr
authors.initials: P
authors.lastname: Gzil
authors.forename: Nico
authors.initials: N
authors.lastname: Vervoort
authors.forename: Gino V
authors.initials: GV
authors.lastname: Baron
authors.forename: Gert
authors.initials: G
authors.lastname: Desmet
mesh_terms: D002845:Chromatography / Q000379:methods*; D004058:Diffusion; D007700:Kinetics; D008958:Models, Molecular; D008962:Models, Theoretical; D016062:Porosity; D012822:Silicon Dioxide / Q000737:chemistry*; D012984:Software
chemical_list: D012822:Silicon Dioxide