Kinetic, Isotherm, and Thermodynamic Modeling of Methylene Blue Adsorption Using Natural Rice Husk: A Sustainable Approach

Abstract

The discharge of synthetic dyes in industrial wastewaters poses a serious environmental threat as they are difficult to degrade naturally and are harmful to aquatic organisms. This study aimed to evaluate the feasibility of using clean untreated rice husk (CRH) as a sustainable and low-cost adsorbent for the removal of methylene blue (MB) from synthetic wastewater. This approach effectively avoids the energy-intensive grinding process by directly using whole unprocessed rice husk, highlighting its potential as a sustainable and cost-effective alternative to activated carbon. A series of batch adsorption experiments were conducted to evaluate the effects of key operating parameters such as initial dye concentration, contact time, pH, ionic strength, and temperature on the adsorption performance. Adsorption kinetics, isotherm models, and thermodynamic analysis were applied to elucidate the adsorption mechanism and behavior. The results showed that the maximum adsorption capacity of CRH for MB was 5.72 mg/g. The adsorption capacity was stable and efficient between pH 4 and 10, and reached the highest value at pH 12. The presence of sodium ions (Na+) and calcium ions (Ca2+) inhibited the adsorption efficiency, with calcium ions having a more significant effect. Kinetic analysis confirmed that the adsorption process mainly followed a pseudo-second-order model, suggesting the involvement of a chemisorption mechanism; notably, in the presence of ions, the Elovich model provided better predictions of the data. Thermodynamic evaluation showed that the adsorption was endothermic (ΔH° > 0) and spontaneous (ΔG° < 0), accompanied by an increase in the disorder of the solid–liquid interface (ΔS° > 0). The calculated activation energy (Ea) was 17.42 kJ/mol, further supporting the involvement of chemisorption. The equilibrium adsorption data were well matched to the Langmuir model at high concentrations (monolayer adsorption), while they were accurately described by the Freundlich model at lower concentrations (surface heterogeneity). The dimensionless separation factor (RL) confirmed that the adsorption process was favorable at all initial MB concentrations. The results of this study provide insights into the application of agricultural waste in environmental remediation and highlight the potential of untreated whole rice husk as a sustainable and economically viable alternative to activated carbon, which can help promote resource recovery and pollution control.