Determination of the porosities of monolithic columns by inverse size-exclusion chromatography.

Retention data of polystyrene samples of narrow molecular size distribution and known average molecular mass were measured on several monolithic columns (Chromolith Performance, Merck) and one conventional packed column (Luna C18, Phenomenex) by size-exclusion chromatography. These data were used to determine the external, the internal, and the total porosities of these columns. These data provided also information on the pore-size distribution of the adsorbent medium. The external and the total porosities of these columns are much higher than those of conventional packed columns. The results illustrate the profound changes brought by monolithic columns to the balance of the hydrodynamic and the mass transfer kinetic properties of chromatographic columns. Classical methods of comparison between column performance must be re-evaluated.

Adsorption equilibria of butyl- and amylbenzene on monolithic silica-based columns.

The adsorption isotherms of butyl- and amylbenzene on silica monolithic columns were measured by frontal analysis. The external, internal and total porosities of these columns were determined by inverse size-exclusion chromatography. The adsorption isotherms are concave upward in the entire concentration range investigated. They were fitted to the anti-Langmuir model, an unusual model in liquid-solid and liquid-liquid phase equilibria. Band profiles under overloaded conditions were recorded. They were in good agreement with the profiles calculated using th,e lumped pore diffusion model of chromatography and these adsorption isotherms.

Behavior of packing materials in axially compressed chromatographic columns.

The behavior of a packing material (Luna C18 from Phenomenex, Torrance, CA, USA) was studied during the consolidation of a column bed under axial compression stress. The kinetics of this consolidation, the permeability and efficiency of the columns obtained, and the reproducibility of these column properties were measured under different conditions. The consolidation process and the column properties are considerably affected by the friction between the packing material in the bed and the column wall. Clear evidence of this wall effect was demonstrated. The apparent permeability of columns consolidated under the same axial stress increases with increasing column length. The apparent modulus of elasticity of the beds increases with increasing column length. The shear resistance between the packed bed and the column wall was measured for columns of different lengths. It increases rapidly with increasing bed length. The column efficiency for thiourea (unretained) and phenyloctane (retention factor, k' approximately 1) was much poorer after recompression than after the first compression. It depended little on the compression stress. The effect of the column length was small.