期刊
JOURNAL OF CHROMATOGRAPHY A
卷 1218, 期 1, 页码 32-45出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/j.chroma.2010.10.087
关键词
B-term; Longitudinal diffusion; Peak parking; Effective Medium Theory; Modelling; Permeability
Using the permeability analogue of the diffusion and partitioning processes occurring in a chromatographic column, the different Effective Medium Theory (EMT) models that exist in literature for the electrical and thermal conductivity have been transformed into expressions that accurately predict the B-term band broadening in chromatographic columns. The expressions are written in such a form that they hold for both fully porous and porous-shell particles, and both spherical and cylindrical particles are considered. Mutually comparing the established EMT-expressions, it has been found that the most basic variant, i.e., the Maxwell-based expression, is already accurate to within 5% for the typical conditions encountered in liquid phase chromatography, independently of the exact microscopic morphology of the packing. For most typical values of the intra-particle diffusion rate and the species retention factors, it is even accurate to within 1%. If even higher accuracies are needed, more elaborate EMT-expressions are available. The modelling accuracy of all explicit EMT-expressions is much better than the residence time weighted (RTW) B-term expressions that have been used up to now in the field of chromatography, where the error is typically on the order of 10% and more. The EMT-models have also been used to establish expressions for the obstruction and tortuosity factor in packings of non-porous particles. The EMT has also been applied to the meso-porous zone only, yielding an expression for the intra-particle diffusion coefficient that can be used without having to specify any obstruction factor. It has also been shown that the EMT also provides a very simple but exact expression to represent the way in which the solid core obstructs the effective intra-particle diffusion in the case of porous-shell particles. This obstruction factor is given by gamma(part) = 2/(2 + rho(3)) for spherical particles and gamma(part) = 1/(1 + rho(3)) for cylinders. Back-transforming the obtained expressions, a set of simple explicit expressions has been obtained that allow to directly obtain the intra-particle diffusion coefficient (D-part) from peak parking or B-term constant measurements. Using these expressions, it could be demonstrated that the traditionally employed RTW-model yields D-part-values that display an erroneous retention factor dependency, even in cases where the RTW-model appears to be able to closely fit the peak parking measurements. (C) 2010 Elsevier B.V. All rights reserved.
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