RES³T - Rossendorf Expert System for Surface and Sorption Thermodynamics

The adsorption of cadmium onto kaolinite and Muloorina illite in the presence of citric acid has been measured as a function of pH and cadmium concentration at 25 °C. When citric acid is present in the systems cadmium adsorption is slightly enhanced below pH 5, but significantly suppressed between pH 5 and 8, for both substrates. At higher citric acid concentrations very little cadmium adsorbs onto kaolinite from pH 5 to 8. Above pH 8 adsorption of Cd(II) onto illite is enhanced in the presence of citric acid, especially at lower concentrations, but this does not occur for kaolinite. Adsorption and potentiometric titration data were fitted by simple extended constant-capacitance surface complexation models for the two substrates. Enhancement of adsorption at lower pH values was ascribed to the ternary reaction

[X⁻--K⁺]⁰ + Cd²⁺ + L³⁻ + 2H⁺ ↔ [X⁻--(CdLH₂)⁺]⁰ + K⁺

involving outer-sphere complexation with permanently charged X⁻ sites on the “silica” faces of both clay minerals. The models suggested that suppression of adsorption in the intermediate pH range was due to the formation of a strong CdL⁻ solution complex which adsorbed neither on the permanently charged sites nor on the surface hydroxyl groups at the edges of the clay crystals. At higher pH values the dominant solution complex, CdLOH²⁻, apparently adsorbed as an outer-sphere complex at surface hydroxyl groups on illite,

SOH + 2Cd²⁺ + L³⁻ ↔ [SOCd⁺--CdOHL²⁻]⁻ + 2H⁺

but not on kaolinite. This difference in behavior results from the presence of =FeOH groups on the illite surface which can form surface complexes with CdLOH²⁻, while the =AlOH groups on the kaolinite surface cannot.