New model of surface diffusion in reversed-phase liquid chromatography.

A new model of surface diffusion in reversed-phase liquid chromatography (RPLC) was derived by assuming a correlation between surface and molecular diffusion. Analysis of surface diffusion data under different conditions of sample compounds, mobile and stationary phases, and temperature in RPLC systems validates this assumption and shows that surface diffusion should be regarded as a molecular diffusion restricted by the adsorptive interactions between the adsorbate molecule and the stationary phase surface. A surface-restricted molecular diffusion model was proposed as a first approximation for the mechanism of surface diffusion. The model is formulated according to the absolute rate theory. The activation energy of surface diffusion (Es) was quantitatively interpreted assuming that Es consists of the contributions of two processes, a hole-making and a jumping one. The former contribution is nearly equal to the activation energy of molecular diffusion and is correlated with the evaporative energy of the mobile phase solvent. The latter contribution is a fraction of the isosteric heat of adsorption. An appropriate explanation based on this new model of surface diffusion is provided for two contradictory results related to the relationship between retention equilibrium and surface diffusion in RPLC and to the surface diffusion coefficient for weakly retained sample compounds.

[1]  G. Guiochon,et al.  The role of the temperature in reversed-phase high-performance liquid chromatography using pyrocarbon-containing adsorbents , 1978 .

[2]  K. J. Sladek,et al.  Diffusion on Surfaces. II. Correlation of Diffusivities of Physically and Chemically Adsorbed Species , 1974 .

[3]  H. Issaq,et al.  High-performance liquid chromatography separations of nitrosamines. IV: Effect of temperature on the separation of nitrosamino conformers , 1989 .

[4]  K. Miyabe,et al.  Adsorption Characteristics in Reversed-Phase Liquid Chromatography Using Methanol/Water and Acetonitrile/Water Mobile Phases , 1997 .

[5]  R. E. Treybal.  Mass-Transfer Operations , 1955 .

[6]  G. Guiochon,et al.  Determination of the lumped mass transfer rate coefficient by frontal analysis. , 2000, Journal of chromatography. A.

[7]  G. Guiochon,et al.  Influence of column radial heterogeneity on peak fronting in linear chromatography. , 1999, Journal of chromatography. A.

[8]  G. Guiochon,et al.  Estimation of the column radial heterogeneity from an analysis of the characteristics of tailing peaks in linear chromatography , 1999 .

[9]  Miroslav Kubín,et al.  Beitrag zur theorie der chromatographie II. Einfluss der diffusion ausserhalb und der adsorption innerhalb des sorbens-korns , 1965 .

[10]  G. Guiochon,et al.  Introduction to reversed-phase high-performance liquid chromatography , 1977 .

[11]  J. Knox,et al.  The performance of packings in high-speed liquid chromatography , 1973 .

[12]  Georges Guiochon,et al.  Analysis of Surface Diffusion Phenomena in Reversed-Phase Liquid Chromatography , 1999 .

[13]  K. J. Sladek,et al.  Diffusion on Surfaces. I. Effect of Concentration on the Diffusivity of Physically Adsorbed Gases , 1974 .

[14]  G. Guiochon,et al.  Retention and mass transfer characteristics in reversed-phase liquid chromatography using a tetrahydrofuran-water solution as the mobile phase. , 2001, Journal of chromatography. A.

[15]  J. Smith,et al.  Intraparticle mass transport in liquid-filled pores , 1974 .

[16]  M. Jaroniec.  Partition and displacement models in reversed-phase liquid chromatography with mixed eluents , 1993 .

[17]  Motoyuki Suzuki,et al.  Concentration dependence of surface diffusion coefficient of propionic acid in activated carbon particles , 1982 .

[18]  Motoyuki Suzuki,et al.  Chromatography of liquid‐phase adsorption on octadecylsilyl‐silica gel , 1992 .

[19]  G. Guiochon,et al.  Comparison of some packings for reversed-phase high-performance liquid—solid chromatography: II. Some theoretical considerations , 1978 .

[20]  G. Guiochon,et al.  Peak tailing and column radial heterogeneity in linear chromatography , 1999 .

[21]  E. Grushka.  Chromatographic peak shapes. Their origin and dependence on the experimental parameters , 1972 .

[22]  James M. Miller.  Dynamics of Chromatography , 1966 .

[23]  M. Muraki,et al.  RATE OF LIQUID-PHASE ADSORPTION ON ACTIVATED CARBON IN THE STIRRED TANK , 1982 .

[24]  K. Miyabe,et al.  Effect of acetonitrile/water mobile-phase composition on adsorption characteristics of reversed-phase liquid chromatography. , 1997, Analytical chemistry.

[25]  G. Guiochon,et al.  Influence of the modification conditions of alkyl bonded ligands on the characteristics of reversed-phase liquid chromatography. , 2000, Journal of chromatography. A.

[26]  D. Ruthven,et al.  Measurement of intracrystalline diffusivities in NaX zeolite by liquid chromatography , 1988 .

[27]  M. Hearn.  [9] Reversed-phase high-performance liquid chromatography , 1984 .

[28]  G. Guiochon,et al.  Correlation between Surface Diffusion and Molecular Diffusion in Reversed-Phase Liquid Chromatography , 2001 .

[29]  H. Issaq,et al.  Enthalpy and entropy effects for homologous solutes in HPLC with alkali chain bonded phases , 1989 .

[30]  E. Grushka,et al.  Computer characterization of chromatographic peaks by plate height and higher central moments , 1969 .

[31]  K. Hidajat,et al.  Evaluation of Equilibrium and Kinetic Parameters of Smaller Molecular Size Amino Acids on KX Zeolite Crystals via Liquid Chromatographic Techniques , 1989 .

[32]  R. Majors,et al.  Studies of Siloxane Phases Bonded to Silica Gel for Use in High Performance Liquid Chromatography , 1974 .

[33]  C. Horváth,et al.  Liquid Chromatography with Hydrocarbonaceous Bonded Phases; Theory and Practice of Reversed Phase Chromatography , 1977 .

[34]  K. Miyabe,et al.  Adsorption Characteristics in Reversed-Phase Liquid Chromatography Using Ethanol/Water Mixed Solvent , 1999 .

[35]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[36]  Samuel Glasstone,et al.  The Theory Of Rate Processes , 1941 .

[37]  K. Miyabe,et al.  Analysis of Surface Diffusion Phenomena in Liquid Phase Adsorption , 1997 .

[38]  G Guiochon,et al.  Analysis of the surface diffusion of alkylbenzenes and p-alkylphenols in reversed-phase liquid chromatography using the surface-restricted molecular diffusion model. , 2001, Analytical chemistry.

[39]  G. Guiochon,et al.  Thermodynamic Characteristics of Surface Diffusion in Reversed-Phase Liquid Chromatography , 1999 .

[40]  Lloyd R. Snyder,et al.  Practical HPLC method development , 1988 .

[41]  G. Guiochon,et al.  Extension of a Jovanovic-Freundlich isotherm model to multicomponent adsorption on heterogeneous surfaces. , 1998, Journal of chromatography. A.

[42]  S. Khattabi,et al.  Study on the accuracy of the elution by characteristic point method for the determination of single component isotherms. , 2000, Journal of chromatography. A.

[43]  Guiochon,et al.  Restricted diffusion model for surface diffusion in reversed-phase liquid chromatography , 2000, Analytical chemistry.

[44]  E. Kucera,et al.  Contribution to the theory of chromatography: linear non-equilibrium elution chromatography. , 1965, Journal of chromatography.