Surface Heterogeneity of Trimethylphenylammonium-Smectite as Revealed by Adsorption of Aromatic Hydrocarbons from Water

Abstract

AbstractAdsorption studies of aromatic hydrocarbons of various molecular sizes on organo-clays in aqueous solution were carried out for characterizing the surface heterogeneity of organo-clays. Benzene, toluene, p-xylene, ethylbenzene and n-propylbenzene adsorption by a smectite with 5 different exchange degrees of trimethylphenylammonium (TMPA) cations for Ca2+ was measured. The Langmuir isotherm equation did not adequately describe the experimental data, especially for small molecules, whereas the Dubinin-Radushkevich (DR) equation combined with a gamma-type adsorption energy distribution function described all experimental data well, suggesting the surface and structural heterogeneity of TMPA-smectites. The calculated adsorption energy distributions indicated that the apparent heterogeneity depends on the molecular size of adsorbates. Small adsorbate molecules such as benzene explore a highly heterogeneous surface of TMPA-smectites while large molecules such as n-propylbenzene detect a relatively homogeneous surface. The surface fractal dimension was dependent on the extent of TMPA exchange for Ca2+. When TMPA content is less than 75% of the cation exchange capacity (CEC) of the smectite, the heterogeneity decreases as TMPA content increases; it increases with TMPA content thereafter. These results are related to the size distribution of micropores in TMPA-smectites, which are defined by the 2 semi-infinite aluminosilicate sheets and the interlayer cations. The micropore size distributions and, hence, heterogeneity are created in part by the inhomogeneity of the charge density of clay surfaces and the tendency for cation segregation in these systems.