Competitive sorption of anionic and cationic dyes onto cetylpyridinium-modified montmorillonite

Abstract

Single-and multi-solute competitive sorptions of anionic dyes; Eriochrome Black T (EBT), Orange II (OR) and Methyl Orange (MO) and cationic dyes; Thioflavin T (TT), Methylene Blue (MB) and Crystal Violet (CV) onto montmorillonite modified with a cationic surfactant, cetylpyridinium chloride (CP), were investigated. In single-solute sorption, the sorption affinity, as represented by Freundlich sorption coefficient (K F) and Langmuir sorption capacity (q mL ), was in the order of EBT > OR > MO for anionic dyes and in the order of TT > MB > CV for cationic dyes. The sorption affinity of the cationic dye was higher than that of the anionic dye mainly due to the difference in sorption mechanisms: ion exchange to the bare montmorillonite surface plus two dimensional surface adsorption onto the pseudo-organic medium formed by the conglomeration of the long-chain hydrocarbon tail groups of the CP cation on the montmorillonite for cationic dyes vs. two dimensional surface adsorption only for anionic dyes. Three-parameter models (dual-mode and Song models) fitted better than the two-parameter models (Freundlich, Langmuir and Dubinin-Radushkevich models) due to the number of parameters involved. The conventional Dubinin-Radushkevich (D-R) model often used to classify sorption mechanisms based on the mean free energy were not able to explain the higher sorption of cationic dyes than anionic dyes. Among the tested models, the Song model was the best in predicting single-solute sorption in terms of the coefficient of determination (R2) and the sum of squared errors (SSE) values. Although both dual-mode and Song models fitted well to the sorption data, the results of asymptotic behavior analyses showed that Song model was better than dual-mode model in predicting sorption behaviors and in explaining sorption mechanisms. Competition between the solutes in the bisolute and trisolute system reduced the sorbed amount of each solute compared with that in the single-solute system. Generally the ideal adsorbed solution theory (IAST) coupled to the single-solute sorption model predicted the bisolute and tri-solute competitive sorption data favorably except a few bisolute systems.