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Effect of Clay Charge on Swelling: A Clay-Modified Electrode Study

Published online by Cambridge University Press:  28 February 2024

Alanah Fitch ,
Jia Du ,
Huamin Gan  and
J. W. Stucki
Alanah Fitch
Affiliation:
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Rd., Chicago, Illinois 60626
Jia Du
Affiliation:
Department of Chemistry, Loyola University of Chicago, 6525 N. Sheridan Rd., Chicago, Illinois 60626
Huamin Gan
Affiliation:
Department of Agronomy, University of Illinois, Champaign-Urbana, Urbana, Illinois 61801-4798
J. W. Stucki
Affiliation:
Department of Agronomy, University of Illinois, Champaign-Urbana, Urbana, Illinois 61801-4798
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Abstract

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The uniformity of clay films affects the transport of an anionic electroactive probe through the film. When cations other than Na+ are present in the initial swelling of the film (such as native K+ and Ca2+), or when the native clay is highly charged, internal dislocations of the film, caused by variable stacking domains, enhance the diffusive transport of Fe(CN)63− across the film. This effect is investigated using clay-modified electrodes in which the clays are of variable exchange forms (Na+, Ca2+, or K+) and variable charge. The charge on the clay is determined both by the native form of the clay and by reduction of structural Fe3+. The results suggest that swelling of clays increases in a linear fashion with CEC, at least for minimally charged clays.

Keywords

Charged claysDiffusive transportIron reduction
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 5 , October 1995 , pp. 607 - 614
Copyright
Copyright © 1995, The Clay Minerals Society

References

Adamson, A. W., 1982. Physical Chemistry of Surface. Chichester: Wiley, 295 pp.Google Scholar
Bard, A. J., and Faulkner, L. R., 1980. Electrochemical Methods. N. Y.: Wiley and Sons, 218 pp.Google Scholar
Baver, L. D., Gardner, W. H., and Gardner, W. R. 1972. Soil Physics. N. Y.: Wiley and Sons, 238–245.Google Scholar
Fitch, A., and Du, J. 1992. Diffusion layer in well-ordered clay-modified electrodes. J. Electroanal. Chem. 319: 409–414.Google Scholar
Fitch, A., and Fausto, C. L. 1988. Insulating properties of clay films towards Fe(CN)63– as affected by electrolyte concentration. J. Electroanal. Chem. 257: 299–303.Google Scholar
Guven, N., 1974. Electron-optical investigations on mont-morillonites I. Cheto, Camp Berteaux, and Wyoming mont-morillonites. Clays & Clay Miner. 22: 155–165.Google Scholar
Huheey, J. E., 1978. Inorganic Chemistry, 2nd ed. 1978, N.Y.: Harper and Row, 71 pp.Google Scholar
Khaled, E. F., and Stucki, J. W. 1991. Iron oxidation state effects on cation fixation in smectites. Soil Sci. Soc. Am. J. 55: 550–554.Google Scholar
Komadel, P., Lear, P. R., and Stucki, J. W., 1990. Reduction and reoxidation of nontronite: Extent of reduction and reaction rates. Clays & Clay Miner. 38: 203–208.Google Scholar
Lear, P. R., and Stucki, J. W. 1985. Role of structural hydrogen in the reduction and re-oxidation of iron and nontronite. Clays & Clay Miner. 33: 539–545.Google Scholar
Lear, P. R., and Stucki, J. W. 1989. Effects of iron oxidation state on the specific surface area of nontronite. Clays & Clay Miner. 37: 547–552.Google Scholar
Lee, S. A., and Fitch, A. 1990. Conductivity of clay-modified electrodes. Alkali metal cation hydration and film preparation effects. J. Phys. Chem. 94: 409–414.Google Scholar
Low, P. F., 1980. The swelling of clays: II Montmorillonites. Soil Sci. Soc. Am. J. 44: 667–676.Google Scholar
Meredith, R. W., and Tobias, C. W. 1962. Conduction in heterogeneous systems. In Advances in Electrochemistry and Electrochemical Engineering #2. Tobias, C. W., ed. John Wiley and Sons, 218–252.Google Scholar
Millington, R. J., and Quirk, J. P. 1961. Permeability of porous solids. Trans. Farad. Soc. 57: 1200–1204.Google Scholar
Norrish, K., 1954. The swelling of montmorillonites. Disc-Farad. Soc. 18: 120–134.Google Scholar
Nye, P. H., and Tinker, P. B. 1977. Solute Movement in the Soil-Root System. Berkeley: U. Calif. Press, 69–91.Google Scholar
Oesterling, T. D., and Olson, C. L. 1967. Chronoamperometry at tubular mercury-film electrodes. Anal. Chem. 39: 1546–1549.CrossRefGoogle Scholar
Parker, J. L., 1986. Hydrostatics of water in porous media. In Soil Physical Chem. Sparks, D. L., ed. Boca Raton, Fl.: CRC Press, 209–297.Google Scholar
Schreemeyer, L. F., Spengler, S. E., and Murphy, D. W. 1985. Ion selectivity in nickel hexacyanoferrate films on electrode surfaces. Inorg. Chem. 24: 3044–3046.CrossRefGoogle Scholar
Shen, S., Stucki, J. W., and Boast, C. W. 1992. Effects of structural iron reduction on the hydraulic conductivity of Na-smectite. Clays & Clay Miner. 40: 381–386.Google Scholar
Slade, P. G., Quirk, J. P., and Norrish, K. 1991. Crystalline swelling of smectite samples in concentrated NaCl in relation to layer charge. Clays & Clay Miner. 39: 234–238.Google Scholar
Sposito, G., 1984. The Surface Chemistry of Soils. Oxford: Oxford University, 31–32.Google Scholar
Stucki, J. W., Low, P. F., Roth, C. B., and Golden, D. C. 1984. Effect of oxidation state of octahedral iron on clay swelling. Clays & Clay Miner. 32: 357–362.Google Scholar
Subramanian, P., and Fitch, A. 1992. Diffusional transport of solutes through clay: Use of clay-modified electrodes. Em. Sci. Tech. 26: 1775–1779.Google Scholar
Suquet, H., De La Calle, C., and Pezerat, H. 1975. Swelling and structural organization of saponite. Clays & Clay Miner. 23: 1–9.Google Scholar
Van Olphen, H., 1979. The Data Handbook for Clay Materials and Other Non-Metallic Minerals. N.Y.: Pergamon.Google Scholar
Wu, J., Low, P. F., and Roth, C. B. 1989. Effects of octahedral iron reduction and swelling pressure on interlayer distances in Na-nontronite. Clays & Clay Miner. 37: 211–218.Google Scholar