Detailed study of the mass transfer kinetics of Tröger's base on cellulose triacetate

Rearden, Preshious; Sajonz, Peter; Guiochon, Georges

doi:10.1016/s0021-9673(98)00253-2

Cited by 27 publications

(27 citation statements)

References 13 publications

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“…10,11 In other previous publications, a concentration dependence was also confirmed for intraparticle diffusivity, 12 for tracer diffusivity, 13 for axial dispersion, 14 for effective diffusivity, 15 and for mutual diffusion coefficients. 16 Concentration dependences of the diffusivities and the mass transfer rate coefficients, km or km,L, seem to be a general conclusion.…”

supporting

confidence: 63%

“…dependence of both km,L of BSA 17,18 and km of Tröger's base 19 reported previously [8][9][10][11] and derived new information concerning the mass transfer characteristics of the four transport processes described above. In the case of anion exchange separation of BSA, 17,18 it was shown that surface diffusion played a predominant contribution in the kinetic properties of mass transfer and that the linear concentration dependence of km,L probably resulted from that of the surface diffusion coefficient (Ds).…”

supporting

confidence: 60%

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Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Miyabe

Guiochon

2000

ANAL. SCI.

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Molecular imprinting is a most attractive method of preparation of dedicated stationary phases for chromatography. Its use for enantioseparations is attracting considerable interest. 1,2 Imprinted materials can provide a very high selectivity for the objective compound, i.e., the imprinted molecule. [1][2][3][4][5] Although analytical applications are rapidly developing, the situation on the preparative front is less rosy. 1 Columns packed with imprinted stationary phases exhibit a poor efficiency and elution peaks are often unsymmetrical, especially for the more retained enantiomer. Sellergren et al. 1,2 suggested that the nonlinear behavior of the adsorption isotherm was the main cause of the broad and unsymmetrical bands observed for L-phenylalanine anilide (PA) on an L-PA imprinted chiral stationary phase. Although the possibility of a slow mass transfer kinetics was also pointed out, no detailed study supported this assumption. Yet, information on the mass transfer characteristics of imprinted stationary phases is necessary to clarify strategies for the improvement of these materials.Most kinetic studies in chromatography assume that four mass transfer processes are involved in a column, (1) axial dispersion, (2) fluid-to-particle mass transfer, (3) intraparticle diffusion, and (4) adsorption/desorption. 6 The contributions of these four processes to peak spreading are evaluated separately. Axial dispersion and the fluid-to-particle mass transfer resistance are inherent to flow processes through packed beds. They are well understood, relatively easy to control, and their contributions are often small. By contrast, intraparticle diffusion and adsorption/desorption give often larger contributions to the mass transfer resistance in the column. Their properties are intrinsic to each packing material and they are still often poorly understood. In order to evaluate the actual performance of packing materials, the characteristics of the mass transfer kinetics inside stationary phase particles must be clarified.Sajonz et al. 7 measured the adsorption equilibrium isotherm and the mass transfer kinetics of L-and D-PA on a polymeric stationary phase imprinted with L-PA, using a staircase frontal analysis method. The isotherm was well represented by either the Bi-Langmuir or the Freundlich models, but not by the simple Langmuir isotherm. The equilibrium data suggested that the distribution of the adsorption energy on the surface of the imprinted stationary phase is heterogeneous and showed that this phase has a high selectivity for the imprinted L-enantiomer. The lumped mass transfer rate coefficient (km,L) was calculated from each single breakthrough curve by applying the transport model of chromatography. 6 The values of km,L increased with increasing concentration of the enantiomers. The extent of the positive concentration dependence of km,L was larger for L-PA than for D-PA. It is expected that a more detailed analysis of the overall mass transfer rate parameter, km,L, could provide new, useful information and all...

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supporting

confidence: 63%

supporting

confidence: 60%

Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Miyabe

Guiochon

2000

ANAL. SCI.

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“…(14a) to account for all the contributions leading to band broadening of the mass transfer processes. Also, it should be noted that in the literature, this mass balance equation is usually written as [11,13] …”

Section: The Ed and The Transport Modelsmentioning

confidence: 99%

“…With proper care, this concept can be extended to the case of nonlinear chromatography [5,11]. For the ED model, the plate height is given by [13,14] …”

Section: The Plate Heightmentioning

confidence: 99%

“…First, because the concentration range studied is divided into many small steps by SCM, it is usually reasonable to assume constant mass transfer coefficients in each step. Second, the isotherm lying in each step is always found to be approximately linear, which also ensures the use of the plate height equations that are derived from linear chromatography [11]. In this paper, we also extended the multiplate (MP) model to SCM which was previously used for SSM [24 -27].…”

Section: Introductionmentioning

confidence: 99%

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Investigation of the concentration dependence of mass transfer coefficients in reversed-phase liquid chromatography

Wang

Zhang

2006

J. Sep. Sci.

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In order to investigate the concentration dependence of mass transfer coefficients in RPLC, experimental breakthrough curves obtained by staircase frontal analysis (FA) were fitted to the simplified models such as multiplate (MP) model, equilibrium dispersive (ED) model, and transport model, and the sophisticated models such as lumped pore diffusion (POR) model and general rate (GR) model. The MP model was used to obtain the initial guesses of the parameters of the ED and the transport models. Then the best values were obtained by minimizing the differences between theoretical and experimental values with a nonlinear fitting procedure. The values of the parameters of the POR and the GR models can be calculated by using the expressions derived from the plate height equations, which was further validated by using the fitting method. It was found that the mass transfer coefficients would depend on the solute concentration. This can be ascribed to the surface diffusivity, which correlates with the concentration and is lumped into the mass transfer coefficients for both simplified and sophisticated models.

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Modeling chromatographic chiral separations under nonlinear competitive conditions

et al. 2000

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The chromatographic separation of Troger's base enantiomers with ethanol as eluent on microcrystalline triacetate cellulose (CTA) was studied Binary competitive adsorption equilibrium data measured were interpreted using ideal adsorbed solution and real adsorbed solution (RAS) theory. Both models were used to simulate a set of column breakthrough experiments. The competitive behavior of the two enantiomers is quantitatively discussed and the reliability of the two models is assessed The results show that the RAS model can describe with good accuracy the complex competitive adsorption behavior exhibited by the CTA/Troger's base model system. This conclusion is expected to apply to the adsorption of the other enantiomeric mixtures on chiral stationary phases

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Detailed study of the mass transfer kinetics of Tröger's base on cellulose triacetate

Cited by 27 publications

References 13 publications

Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Investigation of the concentration dependence of mass transfer coefficients in reversed-phase liquid chromatography

Modeling chromatographic chiral separations under nonlinear competitive conditions

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