The influence of chlorine substitution on the adsorption of chlorophenols on HDTMA-modified halloysite in aqueous solutions

This article focuses on discussing the adsorption process of phenol and its chloro-derivatives on the HDTMA-modified halloysite. Optimized chemical structures of phenol, 2-, 3-, 4-chlorophenol, 2,4-dichloro-, and 2,4,6-trichlorophenol were obtained with computational calculation (the Scigress program). Charge distributions and the hypothetical structure of the system HDTMA-modified halloysite are among their key features. The above-mentioned calculations are applied in order to explain adsorption mechanism details of chlorophenols on the HDTMA-modified halloysite in aqueous solutions. The results of electron density distribution and solvent accessible surface area calculations for phenol and chlorophenols molecules illustrate the impact of chlorine substitution position in a phenol molecule, both on the mechanism and the kinetics of their adsorption in aqueous solutions. Experimental adsorption data were sufficiently represented using the Langmuir multi-center adsorption model for all adsorbates. In addition, the relations between adsorption isotherm parameters and the adsorbate properties were discussed. This study also targets at explaining the role of meta position as a chlorine substituent for mono-chloro derivatives. Given the above findings, two possible mechanisms were utilized as regards chlorophenol adsorption on the HDTMA-modified halloysite, i.e., electrostatic and partition interactions when the chlorophenols exist in a molecular form.