The influence of pH on the adsorption of lead by Na-clinoptilolite: Kinetic and equilibrium studies

Abstract

The objectives of this study were, firstly, to establish the mechanism by which modified clinoptilolite (in Na form) adsorbs lead ions and, secondly, to assess the extent of influence of pH on the adsorption capacity. To this end, the experimental data have been fitted by adsorption isotherms, thermodynamic and kinetic models. Based on the standard errors obtained during experiments, it was determined that the accuracy of prediction of the isotherm models considered for adsorption decreases in the order: Dubinin-Raduschkevich (4.63%, average normalised standard deviation error); Langmuir (7.90%); and Freundlich (15.98%). For the kinetic models, the accuracy of prediction decreases in the order: intra-particle Weber-Morris (with an average normalised standard deviation error of 5.53%); heterogeneous diffusion (5.67%); pseudo-second orderkinetic model (10.47%); diffusion through the particle surface (41.73%); and the pseudo-first kinetic model (47.51%). The mechanism of adsorption of lead ions by Na-clinoptilolite was found to occur in a monolayer and heterogeneous surface. The pH of contact solutions played an important role owing to competition by hydrogen ions. As the pH of the solution decreased, the maximum monolayer adsorption capacity established theoretically, based on the Langmuir isotherm, also decreased. Thus, if, for instance, the pH decreases from 4 to 1, the maximum adsorption capacity decreases from 0.3569 to 0.1604 mol·kg-1. At high pH of the contact solution, the adsorption process occurs by ion exchange and at low pH; i.e., it is physical. The variation of the Gibbs free energy demonstrates that adsorption occurs spontaneously. The process was also observed to occur at a higher rate at low acidity. Diffusion through the internal structure of macro- and micropores is the stage taking place with the lowest speed during the adsorption process and plays an important role in the mechanism of adsorption. The intra-particle diffusion coefficient depends on pH, which can modify the shape and concentrations of the hydrated metal complexes in solutions, thus affecting the  adsorption process. The decrease of pH from 4 to 1 resulted in a decrease of the intra-particle diffusion coefficient from 4.06·10-11 to 1.96·10-11 m2·min-1. The film diffusion coefficients were found to be 10 times larger than the intra-particle coefficients, suggesting that diffusion to the external surface cannot be the rate-limiting step in the adsorption mechanism.