Issue 12, 2003

Moment analysis of retention equilibrium, mass transfer kinetics, and thermodynamic properties in reversed-phase liquid chromatography using phenyl bonded silica gel

Abstract

Information about retention equilibrium, mass transfer kinetics, and related thermodynamic properties of chromatography using phenyldimethylsilyl (Ph)-silica gel was derived by moment analysis of pulse response peak profiles. The results for the Ph-silica gel were compared with those for octadecyldimethylsilyl (C18)-silica gel. Some parameters characterizing the chromatographic behavior of the two stationary phases were correlated with the hydrophobic surface area of sample molecules. Surface diffusion had a predominant role for intraparticle diffusion. An enthalpy-entropy compensation was established for both the retention equilibrium and surface diffusion. A linear correlation was observed between the logarithm of surface diffusion coefficient (Ds) and that of retention equilibrium constant (Ka), suggesting the establishment of a linear free energy relationship. The ratio of Ds to molecular diffusivity (Dm) decreased with increasing Ka and was correlated by a single curved line. The value of Ds was of the same order of magnitude with Dm when Ka became negligible. These results suggest the presence of a sort of correlation between surface diffusion and molecular diffusion and the restriction of the molecular mobility by surface diffusion due to the retention strength.

Article information

Article type
Paper
Submitted
18 Jul 2003
Accepted
14 Oct 2003
First published
29 Oct 2003

Analyst, 2003,128, 1425-1433

Moment analysis of retention equilibrium, mass transfer kinetics, and thermodynamic properties in reversed-phase liquid chromatography using phenyl bonded silica gel

K. Miyabe, Y. Sakai, M. Sarashina and C. Yokokawa, Analyst, 2003, 128, 1425 DOI: 10.1039/B308293H

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