Hostname: page-component-848d4c4894-xm8r8 Total loading time: 0 Render date: 2024-07-05T01:57:24.611Z Has data issue: false hasContentIssue false

Characterization of Montmorillonite Saturated with Short-Chain Amine Cations: 1. Interpretation of Basal Spacing Measurements

Published online by Cambridge University Press:  01 January 2024

Sidney Diamond
Affiliation:
Physical Research Division, Bureau of Public Roads, Washington, D.C., USA
Earl B. Kinter
Affiliation:
Physical Research Division, Bureau of Public Roads, Washington, D.C., USA

Abstract

Basal spacing measurements were made for a montmorillonite saturated with a series of small aliphatic primary, secondary, and tertiary amine and quaternary ammonium cations, using wet, oven-dry, and glycerol-treated specimens. The spacings ranged from about 12 to 14Å, depending on the cation, indicating that in each case a monolayer of cations is interleaved between adjacent montmorillonite layers. The observed spacings are consistent with the concept that the cations are oriented with their minimum thickness in the c-axis direction, but it is possible that the smallest cations have a long axis in this direction and are partially embedded in the clay surfaces.

Montmorillonite saturated with cations containing up to four carbon atoms retained some sensitivity to water, as indicated by a slight contraction of the lattice on oven drying and rapid re-expansion on exposure to the humidity of the laboratory atmosphere.

For cations having a layer thickness less than glycerol, limited lattice expansion occurred on glycerol treatment, usually to a spacing sufficient to accommodate a single layer of glycerol molecules. Apparently the cations function as pillars separating the montmorillonite layers, and the glycerol molecules may expand the lattice as necessary to enter the spaces between the pillars. However, exceptions occurred with methylamine-saturated montmorillonite, in which both one- and two-layer complexes of glycerol were present simultaneously in the same specimen, and with trimethylamine-saturated clay, in which two different one-layer complexes were present. It is suggested that the glycerol in one-layer montmorillonite complexes may exist in two orientations, one leading to a layer thickness of about 4.1 Å, the other to a thickness of about 4.6 Å.

Type
Symposium on Clay-Organic Complexes
Copyright
Copyright © Clay Minerals Society 1961

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Barrer, R. M. and MacLeod, D. M. (1955) Activation of montmorillonite by ion-exchange and sorption complexes of tetra-alkyl ammonium montmorillonite: Trans. Faraday Soc., v. 51, pp. 12901300.CrossRefGoogle Scholar
Barrer, R. M. and Reay, J. S. S. (1957) Sorption and intercalation by methyl ammonium montmorillonites: Trans. Faraday Soc., v. 53, pp. 1253–71.CrossRefGoogle Scholar
Beavers, A. H. and Larson, B. L. (1953) Electrophoresis of clays by the schlieren moving boundary procedure: Soil Science Soc. Amer. Proc., v. 17, pp. 2226.CrossRefGoogle Scholar
Bradley, W. F. (1945) Molecular associations between montmorillonite and some poly- functional organic liquids: J. Amer. Chem. Soc., v. 67, pp. 975981.CrossRefGoogle Scholar
Brindley, G. W. and Hoffman, R. W. (1962) Orientation and packing of aliphatic chain molecules on montmorillonite: in Clays and Clay Minerals, v, 9, Pergamon Press, New York, pp. 546556.CrossRefGoogle Scholar
Greene-Kelly, R. (1955) Sorption of aromatic organic compounds by montmorillonite. Part I—Orientation studies: Trans. Faraday Soc., v. 51, pp. 412424.CrossRefGoogle Scholar
Greene-Kelly, B. (1956) The swelling of organophilic montmorillonites in liquids: J. Colloid. Science, v. 11, pp. 7779.CrossRefGoogle Scholar
Jordan, John W. (1949) Organophilic Bentonites I.—Swelling in organic liquids: J. Phys. and Colloid Chem., v. 53, pp. 294306.CrossRefGoogle Scholar
Kinter, E. B. and Diamond, S. (1955) A new method for preparation and treatment of oriented-aggregate specimens of soil clays for X-ray diffraction analysis: Soil Science, v. 81, pp. 111120.CrossRefGoogle Scholar
Kinter, E. B. and Diamond, S. (1958) Gravimetric determination of monolayer glycerol complexes of clay minerals: in Clays and Clay Minerals, Nat. Acad. Sci.-Nat. Res. Council, pub. 566, pp. 318333.Google Scholar
Kinter, E. B. and Diamond, S. (1960) Pretreatment of soils and clays for measuring external surface area by glycerol retention: in Clays and Clay Minerals, 7th Conf., Pergamon Press, New York, pp. 125134.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., v. 44, pp. 349367.CrossRefGoogle Scholar
Pauling, Linus (1940) The Nature of the Chemical Bond: 2nd edition, Cornell University Press, Ithaca, 450 pp.Google Scholar
Rowland, Richards A. and Weiss, E. J. (1962) Bentonite-methylamine complexes: This volume.Google Scholar