Theoretical and experimental studies on the adsorption of aromatic compounds onto cellulose

The adsorption of several aromatic compounds over microcrystalline cellulose was studied by molecular modeling and experimentally using gas chromatography. Experimental adsorption enthalpies were obtained from an equation based on Clausius-Clapeyron formalism and the temperature dependence of retention volume at infinite dilution. Four different cellulose surfaces (three crystalline (110, 100, and 010) and one amorphous) were modeled. Overall strong agreement was observed between the experimental and theoretical work with 84% of the adsorbate-cellulose systems having differences between measured and predicted values of less than 20%. Based on both calculated and experimental data, a morphology for the microcrystalline cellulose as a weighted combination of the four surfaces was proposed: 39% (110), 28% (100), 10% (010), and 23% amorphous. By adopting this distribution, differences between experimental and weighted average predicted adsorption energies were 10% or less for 14 out of 17 compounds; a maximum of 15% was observed for guaiacol. Experimental results for monosubstituted aromatic compounds revealed that adsorption enthalpies are related to the hydrophilic/hydrophobic character of the substituent groups: 3.5 kJ mol(-1) for a methyl group, 15.7 kJ mol(-1) for a double bond, 21.0 kJ mol(-1) for a methoxyl group, 22.8 kJ mol(-1) for a carbonyl group, and 27.6 kJ mol(-1) for a hydroxyl group. These tendencies were confirmed by modeling, except for the aldehyde carbonyl group, where an overestimation of 10.8 kJ mol(-1) was observed. Analysis of experimental and predicted adsorption enthalpies of multisubstituted aromatic compounds suggests that the efficiency of their interaction with cellulose depends on a compromise between the roughness of the cellulose surface and their conformational adaptability.