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Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801 USA
E-mail of corresponding author: jstucki{at}uiuc.edu
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.
Key Words: CMS Clay SWa-1 CMS Clay NG-1 Dehydrochlorination Iron(II) Iron(III) Montmorillonite Nontronite Oxidation Pentachloroethane Reduction Reactions Tetrachloroethene
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