Hostname: page-component-cd9895bd7-q99xh Total loading time: 0 Render date: 2024-12-28T18:00:31.210Z Has data issue: false hasContentIssue false
  • English
  • Français

Adsorbed Water on Clay: A Review

Published online by Cambridge University Press:  01 January 2024

R. Torrence Martin
R. Torrence Martin*
Affiliation:
Soil Engineering Division, Department of Civil Engineering Massachusetts Institute of Technology, Cambridge, Massachusetts, 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.

Current knowledge of clay mineralogy and changing concepts of clay behavior have suggested a re-examination of the experimental data concerning adsorbed water. Data published between 1935 and 1959 have been studied and evaluated. In some instances this requires a reinterpretation of data that may lead to inferences or conclusions not intended by the original author. The intention of the re-evalution of data is to clarify understanding of the nature of adsorbed water and to suggest fruitful avenues for future research. While all literature on the subject has not been included, a concerted effort has been made to include representative data from all viewpoints and experimental methods. Data reviewed come under the following headings: X-ray and electron diffraction, density, dielectric and magnetic, thermodynamic, diffusion and fluid flow, freezing, and rigid water films.

Utilizing present knowledge of crystal and surface chemistry of clay leads to the following conclusions: (a) Positions of the oxygen atoms of the adsorbed water molecules have been established by X-ray diffraction of vermiculite. These positions preclude both the ice structure and the Hendricks-Jefferson net structure even after modification to accommodate the exchangeable ions, (b) Density of water sorbed on Na montmorillonite has a minimum value of about 0.97 g/cm3 at a water content of 0.7 g H2O/g clay (approximately the plastic limit). For water contents less than 0.7 the density rapidly rises to about 1.4, and for water contents greater than 0.7 the density gradually rises until at about 6.5 g H2O/g clay the density of the adsorbed water equals that of normal liquid water. (c) The differential entropy of water adsorbed on kaolinite has a minimum value approximately that of ice; however, (1) this minimum occurs at about 0.7 of a monolayer, and (2) the integral entropy is greater than that for normal liquid water up to at least two molecular layers. The apparently contradictory entropy of sorbed water on montmorillonitic clay has not been resolved but is believed to be at least partially associated with clay swelling. (d) Diffusion and fluid flow phenomena are shown to be extremely sensitive to clay fabric; therefore, it is the writer's opinion that diffusion and fluid flow data on loosely compacted clay are of little help in ascertaining the structure of the adsorbed water phase. (e) Adsorbed water is easily supercooled and an appreciable fraction of the adsorbed water remains unfrozen after ice has once formed.

The two major hypotheses indicate that the nature of the adsorbed water is. (1) a solidlike substance, o. (2) a two-dimensional fluid. In the writer’s opinion the only data that cannot be adequately explained by both of the hypotheses are the integral entropy data on kaolinite. The integral entropy data favor the two-dimensional fluid hypothesis; however, the paucity of data requires that this be a very tentative conclusion.

The major difficulty encountered in the re-examination of data for this review was that a rather poorly defined clay surface was employed by various investigators. If progress is to be made in unraveling the water-clay complex, it is deemed absolutely essential that experiments be carried out on very carefully defined and controlled clay surfaces. The nature of adsorbed water as interpreted from physico-chemical data on water-clay systems is no better than the purity of the clay surface regardless of the accuracy and precision of the measurements.

Type
Symposium on the Engineering Aspects of the Physico-Chemical Properties of Clays
Information
Clays and Clay Minerals (National Conference on Clays and Clay Minerals) , Volume 9 , February 1960 , pp. 28 - 70
Copyright
Copyright © The Clay Minerals Society 1960

References

Anderson, D.M. and Low, P. F. (1958) The density of water adsorbed by Li-, Na-, and K-bentonite: Soil Sci. Soc. Amer. Proc., v. 22, pp. 99–103.CrossRefGoogle Scholar
Auty, R. P. and Cole, R. H. (1952) Dielectric properties of ice: J. Chem. Phys., v. 20, pp. 1309 to 1314.CrossRefGoogle Scholar
Barshad, Isaac (1952) Temperature and heat of reaction calibration of the differential thermal analysis apparatus: Amer. Min., v. 37, pp. 667–694.Google Scholar
Barshad, Isaac (1960) Thermodynamics of water adsorption and desorption on montmorillonite: in Clays and Clay Minerals, Pergamon Press, New York, v. 8, pp. 84r–101.CrossRefGoogle Scholar
Bradley, W. F. (1959) Density of water sorbed on montmorillonite: Nature, v. 183, pp. 1614 to 1615.CrossRefGoogle Scholar
Bradley, W. F., Grim, R. E. and Clark, G. F. (1937) A study of the behavior of montmorillonite on wetting: Z. Krist., v. 97, pp. 216–222.Google Scholar
University, Cornell (1951) Fundamental Properties, Clay-Water Systems: Final report soil solidification research, Cornell University, Ithaca, New York, v. 2, 405 pp.Google Scholar
Deeg, E. and Huber, O. (1955) Dielectric constant of clays in decimeter wavelength as a function of water content: Ber. dtsch. heram. Ges., v. 32, pp. 261–272.Google Scholar
DeWit, C. T. and Arens, P. L. (1950) Moisture content and density of some clay minerals and some remarks on the hydration pattern of clay: Trans. 4th Int. Cong. Soil Sci., v. 2, pp. 59–62.Google Scholar
Dorscy, N. E. (1948) The freezing of supercooled water: Trans. Amer. Phil. Soc., v. 38, pp. 247–328.CrossRefGoogle Scholar
Forslind, E. (1948) Crystal structure and water adsorption of clay minerals: Svenska Forskningsinstitut fur Cement och Betong, Meddelande no. 11, 20 pp.Google Scholar
Foster, W. R., Savins, J. G. and Waite, J. M. (1955) Lattice expansion and rheological behavior relationships in water-montmorillonite systems: in Clays and Clay Minerals, Natl. Acad. Sci.-Natl. Res. Council, pub. 395, pp. 296–316.Google Scholar
Frank, H. S. and Wen, W. Y. (1957) Structure aspects of ion-solvent interaction in aqueous solutions: a suggested picture of water structure: Disc. Faraday Soc., no. 24, pp. 133–140.CrossRefGoogle Scholar
Glasstone, S., Laidler, K. J. and Eyring, H. (1941) The Theory of Rate Processes: McGraw-Hill Book Co., Inc., New York, 611 pp.Google Scholar
Goates, J. R. and Bennett, S. J. (1957) Thermodynamic properties of water adsorbed on soil minerals, II. Kaolinite: Soil Sci., v. 83, pp. 325–330.CrossRefGoogle Scholar
Grim, R. E. and Cuthbert, F. C. (1945) Some clay-water properties of certain clay minerals: J. Amer. Ceram. Soc., v. 28, pp. 90–95.CrossRefGoogle Scholar
Hauser, E. A. and Le Beau, D. S. (1938) Studies in colloidal clays, I: J. Phys. Chem., v. 42, pp. 1031–1049.CrossRefGoogle Scholar
Hendricks, S. B., Nelson, R. A. and Alexander, L. T. (1940) Hydration mechanisms of the clay mineral montmorillonite saturated with various cations: J. Amer. Chem. Soc., v. 62, pp. 1457–1464.CrossRefGoogle Scholar
Hendricks, S. B. and Jefferson, M. E. (1938) Structures of kaolin and talc-pyrophyllite hydrates and their bearing on water sorption of the clays: Amer. Min., v. 23, pp. 863–875.Google Scholar
Hill, T. L. (1950) Statistical mechanics of adsorption, IX, Adsorption thermodynamics and solution thermodynamics: J. Chem. Phys., v. 18, pp. 246–256.CrossRefGoogle Scholar
Hill, T. L. (1951) Thermodynamics of adsorption: Trans. Faraday Soc., v. 47, pp. 376–380.CrossRefGoogle Scholar
Hosier, C. L. and Hosier, C. R. (1955) An investigation of the freezing of water in capillaries: Trans. Amer. Geophys. Un., v. 36, pp. 126–132.Google Scholar
Husted, R. F. and Low, P. F. (1954) Ion diffusion in bentonite: Soil Sci., v. 77, pp. 343–353.CrossRefGoogle Scholar
I.C.T. (1926) International Critical Tables of Numerical data, Physics, Chemistry, and Technology: McGraw-Hill, New York, v. 5, 470 pp.Google Scholar
Keymeulen, J. v. and Dekeyser, Willy (1957) Dielectric loss of and defects in clay minerals: J. Chem. Phys., v. 27, pp. 172–175.CrossRefGoogle Scholar
Kolaian, J. H. (1960) Thermodynamic and freezing properties of water adsorbed by Wyoming bentonite: Ph. D. thesis, Purdue University.Google Scholar
Kurosaki, S. (1952) Dielectric properties of adsorbed water—IV. Adsorbed water on silica gel: J. Chem. Soc. Japan, Pure Chem. Sect., v. 73, pp. 606–610.Google Scholar
Lambe, T. W. (1953) The structure of inorganic soil: J. Soil Mech. and Foundation Div. of A.S.C.E., v. 79, pp. 315–1 to 315-49.Google Scholar
Lange, N. A. (1944) Handbook of Chemistry: Handbook Publishers, Sandusky, Ohio, 5th Ed., 1777 pp.Google Scholar
Lange, N. A. (1956) Handbook of Chemistry: Handbook Publishers, Inc., Sandusky, Ohio, 9th Ed., 1969 pp.Google Scholar
Leonards, G. A, (1958) Discussion of the structure of compacted clay: J. Soil Mech. and Foundation Div. of A.S.C.E., v. 84, pp. 1828–41 to 1828-46.Google Scholar
Low, P. F. (1955) The role of aluminum in the titration of bentonite: Soil Sci. Soc. Amer. Proc., v. 19, pp. 135–139.CrossRefGoogle Scholar
Low, P. F. (1958) The apparent mobilities of exchangeable alkali metal cations in bentonite- water systems: Soil Sci. Soc. Amer. Proc., v. 22, pp. 395–398.CrossRefGoogle Scholar
Low, P. F. (1960) Viscosity of water in clay systems: in Clays and Clay Minerals, Pergamon Press, New York, v. 8, pp. 170–182.CrossRefGoogle Scholar
Low, P. F. and Anderson, D. M. (1958a) The partial specific volume of water in bentonite suspension: Soil Sci. Soc. Amer. Proc., v. 22, pp. 22–24.CrossRefGoogle Scholar
Low, P. F. and Anderson, D. M. (1958b) Osmotic pressure equations for determining thermodynamic properties of soil water: Soil Sci., v. 86, pp. 251–253.CrossRefGoogle Scholar
MacEwan, D. M. C. (1948) Complex formation between montmorillonite, halloysite and certain organic liquids: Trans. Faraday Soc., v. 44, pp. 349–367.CrossRefGoogle Scholar
MacEwan, D.M. C. (1951) The montmorillonite minerals (montmorillonoids): in X-ray Identification and Crystal Structures of Clay Minerals. Mineralogical Society, London, pp. 86–137.Google Scholar
Macey, H. H. (1942) Clay-water relationship and the internal mechanism of drying: Trans. Brit. Ceram. Soc., v. 41, pp. 73–121.Google Scholar
Mackenzie, R. C. (1958) Density of water sorbed on montmorillonite: Nature, v. 181, p. 334.CrossRefGoogle Scholar
Martin, R. T. (1958) Water sorption on lithium kaolinite: in Clays and Clay Minerals, Natl. Acad. Sci. —Natl. Res. Council, pub. 566, pp. 23–38.Google Scholar
Martin, R. T. (1960) Water vapor sorption on kaolinite: entropy of adsorption: in Clays and Clay Minerals, Pergamon Press, New York, v. 8, pp. 102–114.CrossRefGoogle Scholar
Massachusetts Institute of Technology (1955) Soil stabilization research sponsored by industrial funds: Rpts. XII, XIII and XIV.Google Scholar
Massachusetts Institute of Technology (1956) Soil stabilization research sponsored by industrial funds: Rpts. XV and XVI.Google Scholar
Mathers, A. C., Weed, S. B. and Coleman, N. T. (1955) The effect of acid and beat treatment on montmorillonoids: in Clays and Clay Minerals, Natl. Acad. Sci.—Natl. Res. Council, pub. 395, pp. 403–412.Google Scholar
Mathieson, A. McL. and Walker, G. F. (1954) Crystal structure of magnesium-vermiculite: Amer. Min., v. 39, pp. 231–255.Google Scholar
Mcintosh, R., Rideal, E. K. and Snelgrove, J. A. (1951) The dielectric behaviour of vapours adsorbed on activated silica gel: Proc. Boy. Soc., v. 208A, pp. 292–310.Google Scholar
Méring, J. (1946) On the hydration of montmorillonite: Trans. Faraday Soc., v. 42B, pp. 205–219.CrossRefGoogle Scholar
Michaels, A. S. (1959) Discussion of physico-chemical properties of soils, soil water systems: J. Soil Mech. and Foundation Div. of A.S.C.E., ν. 85, pp. 91–102.CrossRefGoogle Scholar
Michaels, A. S. and Lin, C. S. (1954) The permeability of kaolinite: Ind. Eng. Chem., v. 46, pp. 1239–1246.CrossRefGoogle Scholar
Michaels, A. S. and Lin, C. S. (1955) Effects of counter-electroosmosis and sodium ion exchange on permeability of kaolinite: Ind. Eng. Chem., v. 47, pp. 1249–1253.CrossRefGoogle Scholar
Mitchell, J. K. (1956) Importance of structure to the engineering behavior of clay: D. Sc. Thesis, M.I.T.Google Scholar
Mooney, R. W. (1951) The adsorption of water vapor by the clay minerals, kaolinite and montmorillonite: Ph. D. Thesis, Cornell University.Google Scholar
Mooney, R. W., Keenan, A. G. and Wood, L. A. (1952) Adsorption of water vapor on montmorillonite, II: J. Amer. Chem. Soc., v. 74, pp. 1371–1374.CrossRefGoogle Scholar
Muir, J. (1954) Dielectric loss in water films adsorbed by some silicate clay minerals: Trans. Faraday Soc., v. 50, pp. 249–254.CrossRefGoogle Scholar
Nitzsch, W. V. (1940) Uber den Bau der Hydrathülle der anorganischen Bodenkolloide: Kolloid-Z., v. 93, pp. 110–115.CrossRefGoogle Scholar
Norrish, Keith (1954) The swelling of montmorillonite: Faraday Society Discussion no. 18, pp. 120–134.Google Scholar
Norrish, Keith and Quirk, J. P. (1954) Crystalline swelling of montmorillonite: Nature, Lond. v. 173, pp. 255–256.CrossRefGoogle Scholar
Ottar, B. (1955) Self diffusion and viscosity in liquids: Acta Chem. Scand., v. 9, pp. 344–345.CrossRefGoogle Scholar
Pacey, J. G. Jr. (1956) The structure of compacted soils: M. S. Thesis, M.I.T.Google Scholar
Pickett, A. G. and Lemcoe, M. M. (1959) An investigation of shear strength of the clay- water system by radio-frequency spectroscopy: J. Geophys. Bes., v. 64. pp. 1579–1586.CrossRefGoogle Scholar
Quirk, J. P. (1955) Significance of surface areas calculated from water vapor sorption isotherms by use of the BET equation: Soil. Sci., v. 80, pp. 423–430.CrossRefGoogle Scholar
Roberts, J. E. (1960) Unpublished data: M.I.T. Soil Engineering.Google Scholar
Robins, J. S. (1952) Some thermodynamic properties of soil moisture: Soil Sci., v. 74, pp. 127–140.CrossRefGoogle Scholar
Robinson, R. A. and Stokes, R. H. (1955) Electrolyte Solutions: Academic Press, Inc., New York, 512 pp.Google Scholar
Rosenqvist, I. Th. (1955) Investigations in the clay-electrolyte-water system: Norges Geo. Inst., pub. 9, 125 pp.Google Scholar
Rosenqvist, I. Th. (1959) Physico-chemical properties of soils. Soil endash water systems: J. Soil Mech. and Foundation Div. oj A.S.C.E., v. 85, pp. 31–53.CrossRefGoogle Scholar
Samuels, S. G. (1950) The effect of base exchange on the engineering properties of soils: Building Research Station Note C 176, Garston, Watford, Herts., England, 16 pp.Google Scholar
Schofield, R. K. and Dakshinamurti, C. (1948) Ionic diffusion and electrical conductivity in sands and clays: Faraday Society Discussion, no. 3, pp. 56–61.Google Scholar
von Engelhardt, W. and Tunn, W. L. M. (1955) The flow of fluids through sandstones: Heidelberger Beit, zur Min. und Petro., v. 2, pp. 12–25. Used in this review a translation by P. A. Witherspoon, 111. State Geol. Survey, Circular 194.Google Scholar
Waidelich, W. C. (1958) Influence of liquid and clay mineral type on consolidation of clay-liquid systems: Highway Res. Bd. Special Report no. 40, pp. 24–42.Google Scholar
Walker, G. F. (1956) The mechanism of dehydration of Mg-vermiculite: in Clays and Clay Minerals, Natl. Acad. Sci. —Natl. Res. Council, pub. 456, pp. 101–115.Google Scholar
Wang, J. H. (1951) Self diffusion and structure of liquid water, II. Measurement of self diffusion of liquid water with O18 as tracer: J. Amer. Chem. Soc., v. 73, pp. 4181–4183.CrossRefGoogle Scholar
Wang, J. H. (1954) Effect of ions on the self diffusion and structure of water in aqueous electrolytic solutions: J. Phys. Chem., v. 58, pp. 686–692.CrossRefGoogle Scholar
Worthing, A. G. and Geffner, J. (1943) Treatment of Experimental Data: John Wiley & Sons, Inc., New York, 342 pp.Google Scholar
Zimmerman, J. R., Holmes, B. G. and Lasater, J. A. (1956) A study of adsorbed water on silica gel by nuclear resonance techniques: J. Phys. Chem., v. 60, pp. 1157–1161.CrossRefGoogle Scholar
Zimmermann, J. R. and Lasater, J. A. (1958) Nuclear magnetic resonance relaxation studies of adsorbed water on silica gel, III: J. Phys. Chem., v. 62, pp. 1157–1163.CrossRefGoogle Scholar