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Restricted diffusion model for surface diffusion in reversed-phase liquid chromatography
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DOI：10.1021/ac9909913.png)
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摘要
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The analysis of experimental results in reversed-phase liquid chromatography (RPLC) allows further discussion of the restricted diffusion model of surface diffusion formulated on the basis of the absolute rate theory. Chromatographic data were acquired on different RPLC systems with two series of homologous compounds, several stationary phases having different alkyl ligand densities and ligands of various lengths, and methanol/ water mobile phases of different compositions, The enthalpy-entropy compensation observed and the linear free energy relationships found for surface diffusion suggest that the surface diffusion mechanism remains probably the same in all RPLC conditions studied, Whereas the isosteric heat of adsorption approaches zero with decreasing retention, the activation energy of surface diffusion tends toward a finite limit and the surface diffusion coefficient tends toward a value near the corresponding molecular diffusivity. These results support the validity of the restricted diffusion model. The influence of different factors on the validity of this model (i.e., the activation energy and the frequency factor of surface diffusion, and the surface tortuosity) was also considered.
Keyword:
OCTADECYLSILYL-SILICA GEL
DILUTE AQUEOUS-SOLUTIONS
LATERAL DIFFUSION
ACTIVATED CARBON
HOMOLOGOUS SERIES
FILLED PORES
ADSORPTION
COEFFICIENT
METHANOL/WATER
INTERFACE
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6.7
论文数:
4.7W
被引数:
15.9W
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Effect of acetonitrile/water mobile-phase composition on adsorption characteristics of reversed-phase liquid chromatography.png)
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ANALYTICAL CHEMISTRYIF6.7
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