The influence of temperature on the adsorption of mellitic acid onto goethite

The adsorption of mellitic acid (benzene-1,2,3,4,5,6-hexacarboxylic acid) onto goethite was investigated at five temperatures between 10 and 70 °C. Mellitic acid adsorption increased with increasing temperature below pH 7.5, but at higher pH the effect of increasing temperature was to reduce the amount adsorbed. Potentiometric titrations were conducted and adsorption isotherms were measured over the same temperature range, and the data obtained were used in conjunction with adsorption edge data to develop an Extended Constant Capacitance Surface Complexation Model of mellitic acid adsorption. A single set of reactions was used to model the adsorption for the three different experiment types at the five temperatures studied. The adsorption reactions proposed for mellitate ion (L 6−) adsorption at the goethite surface (SOH) involved the formation of two outer-sphere complexes: SOH + L 6 − + 3H + ⇌ [ ( SOH 2 ) + ( LH 2 ) 4 − ] 3 − , 2SOH + L 6 − + 2H + ⇌ [ ( SOH 2 ) 2 2 + ( L ) 6 − ] 4 − . This mechanism is consistent with recent ATR-FTIR spectroscopic measurements of the mellitate-goethite system. Thermodynamic parameters calculated from the temperature dependence of the equilibrium constants for these reactions indicate that the adsorption of mellitic acid onto goethite is accompanied by a large entropy increase. Adsorption of mellitic acid onto goethite at temperatures between 10 and 70 °C. Below pH 7 adsorption is greater at lower temperature; above pH 7 uptake is greater at higher temperature.