Djamel E Cherrak

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.

Evidence of a wall friction effect in the consolidation of beds of packing materials in chromatographic columns

Abstract Experimental observations demonstrate the intensity of the friction between the bed of a packed chromatographic column and its wall. The wall supports the bed but, in the process, causes the strong radial heterogeneity of the bed which has been previously reported and is now well documented. Friction against the wall is not entirely harmful, however. Without wall friction, the bed would contract with increasing head pressure. the bed in a typical analytical column would be a few mm longer in the absence of mobile phase flow than under standard operation conditions. Experiments demonstrate the existence of bed friction against the column wall in an axial compression column. They show that the friction coefficient depends on the nature of the solvent, the axial compression stress applied to the bed, and the bed length.

Adsorption Behavior and Prediction of the Band Profiles of the Enantiomers of 3-Chloro-1-Phenyl-1-Propanol. Influence of the Mass Transfer Kinetics.

The single-component and competitive adsorption isotherms of the enantiomers of 3-chloro-1-phenyl-1-propanol were measured by frontal analysis. The stationary phase was a cellulose tribenzoate coated on silica, the mobile phase an n-hexane-ethyl acetate (95:5) solution. The adsorption data measured fitted well to the Langmuir isotherm model. The band profiles of single components and of their mixtures were calculated using the equilibrium-dispersive model. These profiles were found to match quite satisfactorily the experimental band profiles. However, the agreement between calculated and experimental band profiles was significantly improved when a more complex model taking into account the mass transfer kinetics was used. The mass transfer rate coefficients, k(f), for both single components were determined by using the transport-dispersive model of chromatography. The coefficients obtained were used to predict the band profiles of mixtures of the two enantiomers to good agreement.

Study on the accuracy of the elution by characteristic point method for the determination of single component isotherms

The accuracy of the method of elution by characteristic point (ECP) used to determine single component isotherms was studied numerically. Overloaded elution peaks were calculated using the equilibrium-dispersive model of nonlinear chromatography while varying the four parameters, i.e., the number of theoretical plates, the dimensionless Langmuir equilibrium constant, the retention and the loading factor, involved in the fundamental equations of the problem. Single component isotherms were estimated by analyzing the diffuse profile of the elution peaks by the ECP method. Similar results were obtained with the transport-dispersive model. The comparison of these calculated isotherms with the initial Langmuir isotherms provided detailed information on the influence of the mass transfer resistances on the accuracy of the isotherms afforded by the ECP method. The systematic error made on the isotherms depends on the experimental conditions, described by the four parameters. It is expected that this error could be eliminated by correcting the influence of nonequilibrium in the column on the basis of results of the nondimensional calculations. The concentration range of the objective isotherm which can be determined by the ECP method can also be predicted by numerical calculations. The usefulness of the correction strategy and the prediction of the concentration range were experimentally demonstrated.

Prediction of the band profiles of the mixtures of the 1-indanol enantiomers from data acquired with the single racemic mixture

Abstract The adsorption isotherm data of R- and S-1-indanol and of their racemic mixture on cellulose tribenzoate were measured by frontal analysis. These data were then fitted to the Langmuir, the Bilangmuir, the Toth, and the Langmuir–Freundlich isotherm models. The single component data fitted well to both the Bilangmuir and the Toth models. Combined with the lumped pore diffusion model (POR) of chromatography, these isotherms were used to calculate overloaded elution profiles of the pure enantiomers. The calculated and the experimental profiles agree excellently in all cases if the former are derived from the Bilangmuir model. The competitive experimental data also gave excellent agreement with the Bilangmuir model. The simultaneous fit of all the data, for the single components and the racemic mixture, gave again superior agreement with the bilangmuir model. The overloaded elution profiles of samples of the racemic mixture calculated with the Bilangmuir isotherm model combined with the POR model of chromatography gave results in very good agreement with the experimental band profiles of large samples of the racemic mixture. This confirms that in numerous cases the whole set of competitive isotherms of two enantiomers can be derived from the experimental data obtained only with the racemic mixture.

Study of the adsorption behavior of the enantiomers of 1-phenyl-1-propanol on a cellulose-based chiral stationary phase.

Using single-step frontal analysis, we measured single-component and competitive adsorption isotherm data for the two enantiomers of 1-phenyl-1-propanol (PP). These experimental data were fitted to several competitive bi-Langmuir models (with 8, 6, 5 and 4 parameters) and to the competitive Langmuir model. The latter model accounted well for the behavior of both PP enantiomers on Chiracel OB (cellulose tribenzoate coated on silica gel). The parameters obtained were used in numerical calculations to predict the band profiles of the two single components and of their mixtures under overloaded conditions. The equilibrium-dispersive model provides satisfactory results, with minor differences between the calculated and the experimental profiles. These differences became negligible when a more complex kinetic model was used, with a concentration-dependent rate coefficient.

Phenomenological study of the bed–wall friction in axially compressed packed chromatographic columns

The properties of column beds prepared with slurries of Kromasil C8 in 12 different solvents, using the same axial compression skid, were investigated. The extent of the consolidation of the column beds, their permeabilities, and the friction shear stress of these beds against the column wall were determined, as well as the column efficiencies (for an unretained tracer). The results of this study illustrate the influence of the wall effect on the consolidation. The permeability of columns consolidated under a constant compression stress was found to increase with increasing bed length. The bed-wall friction shear stress increases rapidly with increasing bed length and varies widely with the nature of the solvent used. No correlation was found between this shear stress and any physico-chemical property of the solvent. The best efficiency was observed for a column consolidated from a slurry in ethanol.