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Alcohol-Water Interactions on Montmorillonite Surfaces. I. Ethanol

Published online by Cambridge University Press:  01 July 2024

R. H. Dowdy*
Affiliation:
Department of Soil Science, Michigan State University, East Lansing, Michigan
M. M. Mortland
Affiliation:
Department of Soil Science, Michigan State University, East Lansing, Michigan
*
USDA, ABS, SWCRD, Soil Science Department, University of Minnesota, St. Paul, Minnesota.

Abstract

Infrared spectroscopic, X-ray diffraction and gravimetric techniques were used so study the vapor phase adsorption of ethanol on homoionic Cu-, Al-, Ca,, Na-, and NH4-montmorillonite films. Equilibration of these films with ethanol vapor at a relative pressure of unity reduced the water content to less than 0.7% (300°C). As dehydration proceeded, the infrared absorption bands of the residual water were observed. Apparent differences between different cation saturations are reconciled by a consideration of the different types of ion-dipole interactions involved. Adsorption isotherms and X-ray diffraction results substantiated the interpretations of the infrared data. Prolonged evacuation did not remove all of the adsorbed ethanol as shown by spectroscopic and gravimetric techniques. Cu-, Al- and Ca-montmorillonite retained 4.5, 7.9, and 4.5 molecules per ion, respectively, while Na- and NH4-clays retained less than one molecule per cation. Ethanol loss occurred rapidly at 40% relative humidity except in the Cu-system where 70 hr were required for complete replacement. These differences indicate that the adsorption and retention of alcohol by montmorillonite is affected by the saturating cation and that alcohol and water compete for the same adsorption sites. Ion-dipole type interactions should thus be considered in adsorption mechanisms of alcohol on montmorillonite.

Type
General
Copyright
Copyright © 1967, The Clay Minerals Society

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Footnotes

*

Published with the approval of the Director of the Michigan Agricultural Experiment Station as Journal Article Number 3936.

References

Bradley, W. F. (1945) Molecular associations between montmorillonite and some polyfunctional organic liquids: Jour. Amer. Chem. Soc. 67, 975–81.10.1021/ja01222a028CrossRefGoogle Scholar
Brindley, G. W. and Hoffman, R. W. (1962) Orientation and packing of aliphatic chain molecules on montmorillonite. Clay-organic studies VI: Clays and Clay Minerals, Proc. 9th Conf., Pergamon Press, New York, 546–56.Google Scholar
Brindley, G. W. and Ray, S. (1964) Complexes of Ca-montmorillonite with primary monohydric alcohols (Clay-organic studies VIII): Amer. Min, 49, 106–15.Google Scholar
Coburn, W. S. Jr. and Grunwald, E. (1958) Infrared measurements of the association of ethanol in carbon tetrachloride: Jour. Amer. Chem. Soc. 90, 1318–22.Google Scholar
Dowdy, R. H. (1966) Alcohol-Water Interactions on Montmorillonite Surfaces. Ph.D. Thesis, Michigan State University.Google Scholar
Dowdy, R. H. and Mortland, M. M. (1966) Alcohol-Water interactions on montmorillonite surfaces. II. Ethylene glycol (manuscript in preparation).Google Scholar
Drushel, H. U., Senn, W. L. Jr. and Ellerbe, J. S. (1963) Effect of structure on the methyl and methylene group absorptivities in aliphatic alcohols: Spectrochim. Acta 19, 1915–30.10.1016/0371-1951(63)80198-8CrossRefGoogle Scholar
Emerson, W. W. (1957) Organo-clay complexes; Nature 180, 48–9.CrossRefGoogle Scholar
Glaeser, Rachel (1954) Complexes organo-argileus et rôle des cations exchangeables: Thèse (Paris).Google Scholar
Haas, C. and Hornig, D. E. (1960) Inter- and intramolecular potentials and the spectrum of ice: Jour. Chem. Phys. 32, 1762–9.Google Scholar
Hoffmann, R. W. and Brindley, G. W. (1961) Adsorption of ethylene glycol and glycerol by montmorillonite: Amer. Min. 46, 450–2.Google Scholar
Hornig, D. F., White, H. F. and Reding, F. P. (1958) The infrared spectra of crystalline H3O, D2O, and HDO: Spectrochim. Acta 12, 338–49.CrossRefGoogle Scholar
Jackson, M. L. (1963) Aluminum bonding in soils: a unifying principle in soil science: Soil Sci. Soc. Amer. Proc. 27, 110.CrossRefGoogle Scholar
Krimm, S., Liang, C. Y. and Sutherland, G. V. B. M. (1956) Infrared spectra of high polymers. U. Polyvinyl alcohol: Jour. Poly. Sci. 22, 227–47.Google Scholar
MacEwan, D. M. C. (1948) Complexes of clays with organic compounds. I. Complex formation between montmorillonite and halloysite and certain organic liquids: Trans. Faraday Soc. 44, 349–67.CrossRefGoogle Scholar
Martin, R. T. (1962) Adsorbed water oil clay: a review: Clays and Clay Minerals, Proc. 9th Conf., Pergamon Press, New York, 2870.CrossRefGoogle Scholar
Mering, J. (1946) On the hydration of montmorillonite: Trans. Faraday Soc. 42B, 205–19.Google Scholar
Plyler, E. K. (1952) Infrared spectra of methanol, ethanol, and n-propanol: Jour. Res. Nat. Bur. Standard 48, 281–6.Google Scholar
Quirk, J. P. (1955) Significance of surface area calculated from water vapor sorption isotherms by use of the B.E.T. equation: Soil Sci. 80, 423–30.CrossRefGoogle Scholar
Rundle, R. E., Nakamoto, K. and Richardson, J. W. (1955) Concerning hydrogen positions in aquo—complexes—CuCl2 H2O: Jour. Chem. Phys. 23, 2450–1.Google Scholar
Russell, J. D. and Farmer, V. C. (1964) Infrared spectroscopic study of the dehydration of montmorillonite and saponite: Clay Min. Bull. 5, 443–64.10.1180/claymin.1964.005.32.04CrossRefGoogle Scholar