Thermodynamic studies of Congo red dye adsorption: avoiding erroneous conclusions from the use of isotherm models

Abstract

The importance of adsorption in water purification and the need to guard against erroneous conclusions often associated with the use of equilibrium adsorption model studies in adsorption systems informed this work. Water purification by adsorption of Congo red (CR) from synthetic aqueous solution to acid treated corncob charcoal (ATCC) was carried out at three different pH values (8.0, 10.5, and 12.0) and at temperatures 10–40 °C. The maximum adsorption capacity of ATCC for CR was 85.8 mg/g at pH 12. The resulting data from the batch adsorption studies were plotted at different temperatures and were fitted to linear form of three isotherm models; Freundlich, Langmuir, and Temkin. Though all three models fitted the experimental data linearly, only Langmuir model was able to account for the observed thermodynamic behavior of the adsorbent–adsorbate systems under the pH conditions. The standard enthalpy values for the adsorption of CR on ATCC at pH 8.0, 10.5, and 12.0 were −5.010 ± 0.312, −7.024 ± 0.440, and −71.426 ± 3.130 kJ mol−1, respectively. The corresponding entropies at pH 8.0, 10.5, and 12.0 were 98.7 ± 1.0, 87.8 ± 1.5, and 129.0 ± 10.5 J mol−1 K−1, respectively. The effect of pH on the thermodynamic quantities were rationalized on the basis of the type of interaction between the CR and the adsorbent. To determine the most suitable model, it was important to juxtapose the observed dependence of adsorption affinity on temperature with the thermodynamic information of the adsorption studies.