Industrial & Engineering Chemistry Research, Vol.33, No.7, 1792-1802, 1994
Mass-Transfer Phenomena on the Surface of Adsorbents in Reversed-Phase Chromatography
Characteristics of mass-transfer phenomena on the surface of adsorbents in reversed-phase chromatography were studied by the chromatographic method and moment analysis. Enthalpy-entropy compensation occurs for surface diffusion in various systems of reversed-phase chromatography. The mechanism of surface diffusion seems to be essentially identical regardless of adsorption conditions. The linear free-energy relation holds in reversed-phase liquid chromatographic systems. Analyzing the slope of the linear relations, it is concluded that the activation energy of surface diffusion is essentially smaller than the isosteric heat of adsorption in liquid-phase adsorption as well as in gaseous systems though the heat of adsorption is experimentally determined to be smaller than the activation energy. Surface diffusion coefficients were correlated to physical properties of adsorbates. Concentration dependence of surface diffusion coefficient was explained by the chemical potential driving force model. An estimation method of the surface diffusion coefficient at each given temperature and amount adsorbed in reversed-phase liquid chromatography was proposed.
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