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Adsorption Kinetics of Pentachloroethane by Iron-Bearing Smectites

Published online by Cambridge University Press:  28 February 2024

Javiera Cervini-Silva
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801 USA
Jun Wu
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801 USA
Joseph W. Stucki
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801 USA
Richard A. Larson
Affiliation:
Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, Illinois 61801 USA

Abstract

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.

Type
Research Article
Copyright
Copyright © 2000, The Clay Minerals Society

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References

Barriuso, E. Laird, D.A. Koskinen, W.C. and Dowdy, R.H., 1994 Atrazine desorption from smectites. Soil Science Society of America Journal 58 1632 38 10.2136/sssaj1994.03615995005800060008x.CrossRefGoogle Scholar
Gates, W.P. Wilkinson, H.T. and Stucki, J.W., 1993 Swelling properties of microbially reduced ferruginous smectite. Clays and Clay Minerals 41 360364 10.1346/CCMN.1993.0410312.CrossRefGoogle Scholar
Jeffers, P.M. Ward, L.M. Woytowitch, L.M. and Wolfe, N.L., 1989 Homogeneous hydrolysis rate constants for selected chlorinated methanes, ethanes, ethenes, and propanes. Environmental Science and Technology 23 965969 10.1021/es00066a006.CrossRefGoogle Scholar
Komadel, P. and Stucki, J.W., 1988 Quantitative assay of minerals for Fe2+ and Fe3+ using 1,10-phenanthroline: III. A rapid photochemical method. Clays and Clay Minerals 36 379384 10.1346/CCMN.1988.0360415.CrossRefGoogle Scholar
Larson, R.A. and Weber, E.J., 1994 Reaction Mechanisms in Environmental Organic Chemistry. Michigan Lewis Publishers, Chelsea.Google Scholar
Lear, P.R. and Stucki, J.W., 1989 Effects of iron oxidation state on the specific surface area of nontronite. Clays and Clay Minerals 37 547552 10.1346/CCMN.1989.0370607.CrossRefGoogle Scholar
Low, P.R., 1980 The swelling of clay. II. Montmorillonites. Soil Science Society of America Journal 44 667676 10.2136/sssaj1980.03615995004400040001x.CrossRefGoogle Scholar
Lowry, T.H. and Richardson, K.S., 1987 Mechanism and Theory in Organic Chemistry. New York Harper Collins Publishers.Google Scholar
Manceau, A. Lanson, B. Drits, V.A. Chateigner, D. Gates, W.P. Wu, J. Huo, D. and Stucki, J.W., 2000 Oxidation-reduction mechanism of iron in dioctahedral smectites. 1. Structural chemistry of oxidized reference nontronites. American Mineralogist. 85 133152 10.2138/am-2000-0114.CrossRefGoogle Scholar
Pilling, M.J. and Seakins, P.W., 1995 Reaction Kinetics. New York Oxford University Press.Google Scholar
Roberts, A.L. and Gschwend, P.M., 1991 Mechanism of pen-tachloroethane dehydrochlorination to tetrachloroethylene. Environmental Science and Technology 25 7686 10.1021/es00013a006.CrossRefGoogle Scholar
Stone, A.T. Morgan, J.J. and Stumm, W., 1991 Kinetics of chemical transformation in the environment Aquatic Chemical Kinetics New York John Wiley & Sons 141.Google Scholar
Stucki, J.W., Stucki, J.W. Goodman, B.A. and Schwertmann, U., 1988 Structural Fe in smectites Iron in Soils and Clay Minerals Dordrecht D. Reidel Publishing Company 625675 10.1007/978-94-009-4007-9_17.CrossRefGoogle Scholar
Stucki, J.W., Auerswald, K. and Stanjek, H., 1997 Redox processes in smectites: Soil environmental significance Advances in GeoEcology, Volume 30 Amsterdam Catena-Verlag 395406.Google Scholar
Stucki, J.W. and Tessier, D., 1991 Effects of iron oxidation state on the texture and structural order of Na-nontronite gels. Clays and Clay Minerals 39 137143 10.1346/CCMN.1991.0390204.CrossRefGoogle Scholar
Stucki, J.W. Golden, D.C. and Roth, C.B., 1984 Effects of reduction and reoxidation of structural iron on the surface charge and dissolution of dioctahedral smectites. Clays and Clay Minerals 32 350356 10.1346/CCMN.1984.0320502.CrossRefGoogle Scholar
Stumm, W., 1992 Chemistry of the Solid-Water Interface. New York John Wiley & Sons.Google Scholar
Stumm, W. Wieland, E. and Stumm, W., 1991 Dissolution of oxide and silicate minerals: Rates depend on surface speciation Aquatic Chemical Kinetics New York John Wiley & Sons 367400.Google Scholar
Thornton, E.K. Thornton, E.R., Gandour, R. and Schowen, R.L., 1978 Scope and limitations of the concept of the transition state Transition States of Biochemical Processes New York Plenum Press 153.Google Scholar
Wilkins, R.G., 1991 Kinetics and Mechanisms of Reactions of Transition Metal Complexes. Weinheim VCH Publishers 10.1002/3527600825.CrossRefGoogle Scholar
Xu, C., 1998 Pesticide adsorption and degradation properties as influenced by iron oxidation state in clay minerals Urbana, Illinois Ph.D. thesis, University of Illinois.Google Scholar
Yan, L. and Stucki, J.W., 1999 Effects of structural Fe oxidation state on the coupling of interlayer water and structural Si-O stretching vibrations in montmorillonite. Lang-muir 15 46484657 10.1021/la9809022.CrossRefGoogle Scholar
Yan, L. Low, P.E. and Roth, C.B., 1996 Enthalpy changes accompanying the collapse of montmorillonite layers and the penetration of electrolyte into interlayer space. Journal of Colloid and Interface Science 182 417424 10.1006/jcis.1996.0482.CrossRefGoogle Scholar
Yan, L. Roth, C.B. and Low, P.E., 1996 Changes in the Si-O vibration of smectites layers accompanying the sorption of interlayer water. Langmuir 12 44214429 10.1021/la960119e.CrossRefGoogle Scholar
Yan, L. Low, P.E. and Roth, C.B., 1996 Swelling pressure of montmorillonite layers versus H-O-H bending frequency of the interlayer water. Clays and Clay Minerals 44 749765 10.1346/CCMN.1996.0440605.CrossRefGoogle Scholar
Zhang, Z.Z. Low, P.E. Cushman, J.H. and Roth, C.B., 1990 Adsorption and heat of adsorption of organic compounds on montmorillonite from aqueous solutions. Soil Science Society of America Proceedings 38 2935.Google Scholar