Thermodynamic behaviour and the effect of temperature on the removal of dyes from aqueous solution using modified diatomite: A kinetic study

The effect of solution temperature and the determination of the thermodynamic parameters of adsorption of methylene blue (MB), Cibacron Reactive black C-NN (RB) and Cibacron Reactive golden yellow MI-2RN (RY) onto manganese-oxides-modified diatomite (MOMD), such as activation energy, E, enthalpy of activation, ΔH∗, entropy of activation, ΔS∗, and free energy of activation, ΔG∗, on the adsorption rates is important in understanding the adsorption mechanism. The rate and the transport/kinetic processes of dye adsorption onto the adsorbents were described by applying various kinetic adsorption models. This would lead to a better understanding of the mechanisms controlling the adsorption rate. The pseudo-second-order model was the best choice among all the kinetic models to describe the adsorption behaviour of RB onto MOMD, suggesting that the adsorption mechanism might be a chemisorption process. The activation energies, E, for RB, RY and MB were −6.74, 56.65 and 99.80 kJ/mol, respectively. The negative value of the activation energy suggested that the rise in the solution temperature did not favour RB adsorption onto MOMD. Moreover, the activation energy of the diffusion process, E′, for RB, RY and MB increased as MB > RY ≫ RB. It means that the RB molecules are much faster moving and a lower energy is needed to diffuse into MOMD than RY and MB molecules. E′, the activation energy for adsorption into pores, of RY is higher than E, indicating that the rate-limiting step of RY adsorption onto MOMD might be diffusion controlled, while the activation energy of the diffusion process, E′, of MB is slightly lower than E, suggesting that the rate-limiting step is a combination of chemical and diffusion adsorption.