Measurement of the eddy dispersion term in chromatographic columns: III. Application to new prototypes of 4.6 mm I.D. monolithic columns

We investigated the mass transfer mechanism in four research prototypes of silica monolithic columns of the second generation provided by their manufacturer (Merck KGaA, Darmstadt, Germany). The heights equivalent to a theoretical plate (HETP) of these columns were measured. The different contributions to the total HETP (longitudinal diffusion term B/uS, skeleton/eluent mass transfer resistance term CuS, and eddy diffusion term A) were determined experimentally for a non-retained (uracil) and for a retained (naphthalene) compound. We used the peak parking method to determine the longitudinal diffusion term, a recently developed accurate model of effective diffusion in silica monolithic structures to determine the skeleton/eluent mass transfer resistance term, and an accurate method of measurement of the total column HETP to determine the eddy diffusion term. The results show that the minimum plate heights of these monolithic column prototypes range between 6 and 7 μm for retained analytes, three times lower than those observed for monolithic columns of the first generation. A detailed analysis of the eddy diffusion term demonstrates that the improvement observed in the column efficiency is explained in part by the 40% reduction of the domain size (which provides thinner half-height peak width) but mostly by a two-fold decrease of the radial velocity bias across the silica rods (which provides more symmetrical peaks). Yet, the rods in these columns exhibit a residual radial heterogeneity leading to a minimum HETP of only 10 μm for non-retained compounds.