Hostname: page-component-78c5997874-fbnjt Total loading time: 0 Render date: 2024-11-20T00:23:08.312Z Has data issue: false hasContentIssue false
  • English
  • Français

Equilibrium Theory of the Kaolinite-Water System at Low Moisture Contents, with Some Remarks Concerning Adsorption Hysteresis

Published online by Cambridge University Press:  01 July 2024

Garrison Sposito  and
K. L. Babcock
Garrison Sposito*
Affiliation:
Department of Soils and Plant Nutrition, University of California, Berkeley, California
K. L. Babcock
Affiliation:
Department of Soils and Plant Nutrition, University of California, Berkeley, California
*
*Present address: Department of Chemistry-Physics, Sonoma State College, Rohnert Park, California, USA
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

A microscopic theory of the kaolinite-water system is presented, based upon the assumption that the clay-water interaction may be envisioned as partly hydration of the exchangeable cations and partly adsorption by the oxygen and hydroxyl surfaces. The theory treats exchangeable cation hydration quantum-mechanically as an ion-dipole phenomenon and considers water adsorption by the mineral surface as a problem in hydrogen bonding. A statistical mechanical model incorporating the quantum-theoretical results is then invoked to find the contribution of each component interaction to the initial portion of the adsorption isotherm for homoionic kaolinite. Good agreement between the theoretical calculations and available experimental data is achieved for water vapor adsorption by Li-, Na-, K-, and Mg-kaolinite, without the use of ad hoc empirical parameters. The concordance, in turn, is used to suggest that the basis for adsorption hysteresis in kaolinite-water vapor systems is the irreversible transition: mineral surface water → cation hydration water.

Type
Research Article
Information
Clays and Clay Minerals , Volume 14 , February 1966 , pp. 133 - 147
Copyright
Copyright © Clay Minerals Society 1966

References

Ahrens, L. H. (1952) The use of ionization potentials. Part 1. Ionic radii of the elements, Geochim. et Cosmochim. Acta 2, 155–69.CrossRefGoogle Scholar
Auty, R. P. and Cole, R. H. (1952) Dielectric properties of ice and solid D2O, Jour. Chem. Phys. 20, 1309–14.Google Scholar
Everett, D. H. (1954) A general approach to hysteresis. Part 3. A formal treatment of the independent domain model of hysteresis, Trans. Faraday Soc. 50, 1077–96.Google Scholar
Everett, D. H. and Whitton, W. I. (1952) A general approach to hysteresis, Trans. Faraday Soc. 48, 749–57.CrossRefGoogle Scholar
Fox, J. J. and Martin, A. E. (1940) Investigations of infrared spectra (2.5-7.5 μ). Absorption of water, Proc. Royal Soc. (London), 174a, 234–62.Google Scholar
Herzberq, G. (1945) Molecular Spectra and Molecular Structure. II. D. Van Nostrand, New York.Google Scholar
Hill, T. L. (1960) An Introduction to Statistical Thermodynamics, Addison-Wesley, Reading, Massachusetts.Google Scholar
Jurinak, J. J. (1963) Multilayer adsorption of water by kaolinite, Proe. Soil Sci. Soc. Amer. 27, 269–72.Google Scholar
Keenan, A. G., Mooney, R. W. and Wood, L. A. (1951) The relation between exchangeable ions and water adsorption on kaolinite, Jour. Phys. Chem. 55, 1462–74.CrossRefGoogle Scholar
Kohl, R. A., Cary, J. W. and Taylor, S. A. (1964) On the interaction of water with a Li kaolinite surface, Jour. Colloid Sci. 19, 699–707.CrossRefGoogle Scholar
Ledoux, R. L. and White, J. L. (1963) Infrared study of the OH groups in expanded kaolinite, Science 143, 244–6.Google Scholar
Longuet-Escard, J., Mering, J. and Brindley, G. W. (1960) Etude des profiles des bandes de diffraction dans la Montmorillonite—Influence de l'hydration et de la nature des cations échangeables, Proc. Intern. Geol. Congress (Copenhagen) 24, 17–27.Google Scholar
Martin, R. T. (1959) Water-vapor sorption on kaolinite: Hysteresis, Clays and Clay Minerals, Proc. 6th Conf., Pergamon Press, New York, 259–78.Google Scholar
Martin, R. T. (1962) Adsorbed water on clay: A review, Clays and Clay Minerals, Proc. 9th Conf., Pergamon Press, New York, 28–70.CrossRefGoogle Scholar
Ockman, N. (1958) The infrared and Raman spectra of ice, Advances in Phys. 7, 199–220.CrossRefGoogle Scholar
Pauling, L. (1960) The Nature of the Chemical Bond, Cornell University Press, Ithaca, New York, 3rd ed.Google Scholar
Rowlinson, J. S. (1949) The second virial coefficients of polar gases, Trans. Faraday Soc. 45, 974–84.CrossRefGoogle Scholar
Sposito, G. (1965) On the General Theory of the Clay-Water Interaction, Unpublished Ph.D. thesis, University of California, Berkeley, California.Google Scholar