Abstract
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.
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Ahrens, L. H. (1952) The use of ionization potentials. Part 1. Ionic radii of the elements, Geochim. et Cosmochim. Acta 2, 155–69.
Auty, R. P., and Cole, R. H. (1952) Dielectric properties of ice and solid D2O, Jour. Chem. Phys. 20, 1309–14.
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.
Everett, D. H., and Whitton, W. I. (1952) A general approach to hysteresis, Trans. Faraday Soc. 48, 749–57.
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.
Herzberg, G. (1945) Molecular Spectra and Molecular Structure. II. D. Van Nostrand, New York.
Hill, T. L. (1960) An Introduction to Statistical Thermodynamics, Addison-Wesley, Reading, Massachusetts.
Jurinak, J. J. (1963) Multilayer adsorption of water by kaolinite, Proc. Soil Sci. Soc. Amer. 27, 269–72.
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.
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.
Ledoux, R. L., and White, J. L. (1963) Infrared study of the OH groups in expanded kaolinite, Science 143, 244–6.
Longuet-Escard, J., Mering, J., and Brindley, G. W. (1960) Étude 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.
Martin, R. T. (1959) Water-vapor sorption on kaolinite: Hysteresis, Clays and Clay Minerals, Proc. 6th Conf., Pergamon Press, New York, 259–78.
Martin, R. T. (1962) Adsorbed water on clay: A review, Clays and Clay Minerals, Proc. 9th Conf., Pergamon Press, New York, 28–70.
Ookman, N. (1958) The infrared and Raman spectra of ice, Advances in Phys. 7, 199–220.
Pauling, L. (1960) The Nature of the Chemical Bond, Cornell University Press, Ithaca, New York, 3rd ed.
Rowlinson, J. S. (1949) The second virial coefficients of polar gases, Trans. Faraday Soc. 45, 974–84.
Sposito, G. (1965) On the General Theory of the Clay-Water Interaction, Unpublished Ph.D. thesis, University of California, Berkeley, California.
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Sposito, G., Babcock, K.L. Equilibrium Theory of the Kaolinite-Water System at Low Moisture Contents, with Some Remarks Concerning Adsorption Hysteresis. Clays Clay Miner. 14, 133–147 (1966). https://doi.org/10.1346/CCMN.1966.0140112
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DOI: https://doi.org/10.1346/CCMN.1966.0140112