Adsorption kinetics of pentachloroethane by iron-bearing smectites

The oxidation state of structural Fe greatly alters surface chemistry, which may have a large influence on clay-organic interactions. The effect of structural-iron oxidation state on chlorinated hydrocarbons at the clay-water interface was examined. Pentachloroethane (5CA) was reacted with oxidized, reduced, and reoxidized forms of three different smectites: montmorillonite, ferruginous smectite, and nontronite in aqueous suspension under controlled-atmosphere conditions. Pentachloroethane was found to adsorb at different rates for the three smectites. A series of 5CA-adsorption rate constants in the presence of these clays showed a strong correlation with the Fe(II) content of the clay (r2 = 0.98). The clay surface behaves as a Brønsted base and promotes 5CA dehydrochlorination. The adsorption kinetics at the clay-water interface were described by the formation of a precursor complex prior to 5CA dehydrochlorination.