Energetic and Entropic Features of Cu(II) Sorption Equilibria on Fibrous Clay Minerals

Abstract

Sorption equilibria of copper(II) ions onto palygorskite and sepiolite clay minerals were studied as a function of temperature. The experimental data were fitted to the Langmuir, Freundlich, Temkin, and R-D models to obtain the isothermal constants. van’t Hoff, Gibbs, Clausius–Clapeyron, and modified Arrhenius equations were also employed to evaluate the thermodynamic parameters involved in Cu sorption. The results showed that fibrous clay minerals exhibit enhanced Cu(II) sorption capacities at higher temperatures. Enthalpy changes (ΔH°) were found to be positive, confirming that the process of Cu(II) sorption on both palygorskite and sepiolite was endothermic. Positive values were also obtained for the entropy changes (ΔS°), which suggests increased randomness at the solid-solution interface during the sorption of Cu(II) ions on both fibrous clay minerals investigated. The free energy changes (ΔG°) were negative for all the different temperatures and initial Cu(II) concentrations tested, indicating that sorption on the minerals is spontaneous and favorable. It was, therefore, concluded that sorption of Cu(II) ions on fibrous clay minerals is entropically driven. The values of isosteric heat of sorption (∆H x ) decreased with increasing sorption density, which shows that the clay surface is heterogeneous in terms of the active sites available for Cu(II) retention. The values of activation energy (E a ) and sticking probability (S * ) generally lied within the ranges associated with physisorption for palygorskite and chemisorptions for sepiolite. In conclusion, the thermodynamic parameters investigated revealed the higher tendency and capacity of sepiolite, compared to palygorskite, for the feasible, spontaneous, and endothermic retention of Cu(II). However, the intensity of Cu(II) interactions with the fibrous clay minerals was found to depend to a large extent on the temperature and the initial Cu loading of the systems.