Hostname: page-component-848d4c4894-nr4z6 Total loading time: 0 Render date: 2024-06-01T23:44:12.424Z Has data issue: false hasContentIssue false

Changes in the Properties of a Montmorillonite-Water System during the Adsorption and Desorption of Water: Hysteresis

Published online by Cambridge University Press:  02 April 2024

M. H. Fu
Affiliation:
Department of Agronomy, Purdue University, West Lafayette, Indiana 47907
Z. Z. Zhang
Affiliation:
Department of Agronomy, Purdue University, West Lafayette, Indiana 47907
P. F. Low
Affiliation:
Department of Agronomy, Purdue University, West Lafayette, Indiana 47907

Abstract

Samples of Na-saturated, Upton montmorillonite were prepared with different contents of water (H2O or D2O) by: (1) adsorption of water from the vapor phase at a specific value of p/p°, the relative humidity, (2) adsorption of water from the vapor phase at p/p° = 1.0 followed by desorption of the water into the vapor phase at a specific p/p° < 1.0, and (3) adsorption of water from the liquid phase followed by desorption of the water into the vapor phase at a specific p/p° < 1.0. Water adsorbed initially from the vapor phase was called V-adsorbed water, and water adsorbed initially from the liquid phase was called L-adsorbed water. The water contents of these samples were determined by gravimetric analysis, the c-axis spacings by X-ray powder diffraction, the O-D stretching frequencies by IR spectroscopy, and the heats of immersion by differential microcalorimetry. No difference was found between V-adsorbed and L-adsorbed water; however, if the final water content was established by adsorption, the system was in a different state than if the final water content was established by desorption. In particular, hysteresis was observed in the following properties: the relative humidity of the adsorbed water, the O-D stretching frequency in this water, and the degree of order in the stacking of the clay layers. The only property that did not exhibit hysteresis was the heat of immersion. Apparently, hysteresis occurred because the orderliness of the system was not reversible, and, thus, any property that depended on orderliness was hysteretic.

Type
Research Article
Copyright
Copyright © 1990, The Clay Minerals Society

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.)

Footnotes

1

Journal Paper No. 12,056, Purdue University Agricultural Experiment Station.

References

Brindley, G. W., Brindley, G. W. and Brown, G., 1980 Order-disorder in clay mineral structures Crystal Structures ofClay Minerals and their X-ray Identification London Mineralogical Society 125195.CrossRefGoogle Scholar
Everett, D. H. and Flood, E. A., 1967 Adsorption hysteresis The Solid-Gas Interface New York Marcel Dekker 10551113.Google Scholar
Farmer, V. C. and Russell, J. D., 1971 Interlayer complexes in layer silicates Trans. Faraday Soc. 67 27372749.CrossRefGoogle Scholar
Fu, M. H., 1985 Investigation of the properties of D2O adsorbed on montmorillonite from the vapor and liquid states: M.Sc. thesis Indiana Purdue University, West Lafayette.Google Scholar
Glaeser, R. and Méring, J., 1968 Domaines d’hydration homogene des smectites CR. Acad. Sci. Paris 267 463466.Google Scholar
Herzberg, G. H., 1950 Molecular Spectra and Molecular Structure. I. Spectra of Diatomic Molecules: Yon New York Nostrand 66145.Google Scholar
Jura, G. and Hill, T. L., 1952 Thermodynamic functions of adsorbed molecules from heat of immersion J. Amer. Chem. Soc. 74 15981599.CrossRefGoogle Scholar
Lahav, N. and Bresler, E., 1973 Exchangeable cation-structural parameter relationships in montmorillonite Clays & Clay Minerals 21 249255.CrossRefGoogle Scholar
Leonard, R. A., Weed, S. B. and Bailey, S. W., 1967 Influence of exchange ions on the 6-dimensions of dioctahedral vermiculite Clays and Clay Minerals, Proc. 15thNatl. Confi, Pittsburgh, Pennsylvania, 1966 New York Pergamon Press 149161.Google Scholar
Low, P. F., 1979 Nature and properties of water in mont-morillonite-water systems Soil Sci. Soc. Amer. J. 43 651658.CrossRefGoogle Scholar
Low, P. F., 1980 The swelling of clay: II. Montmorillonites Soil Sci. Soc. Amer. J. 44 667676.CrossRefGoogle Scholar
Margheim, J. F., 1977 Interrelations of 6-dimension, water content and rheology of Na-smectite: Ph.D. thesis Indiana Purdue University, West Lafayette.Google Scholar
Méring, J., Brindley, G. W. and Bailey, G. W., 1967 X-ray diffraction band profiles of montmorillonite-influence of hydration and the exchangeable cations Clays and Clay Minerals, Proc. 15th Natl. Conf., Pittsburgh, Pennsylvania, 1966 New York Pergamon Press 5160.Google Scholar
Mooney, R. W., Keenan, A. G. and Wood, L. A., 1952 Adsorption of water vapor by montmorillonite. II. Effect of exchangeable ions and lattice swelling as measured by X-ray diffraction J. Amer. Chem. Soc. 74 13711374.CrossRefGoogle Scholar
Mulla, D. J. and Low, P. F., 1983 The molar absorptivity of interparticle water in clay-water systems J. Colloid Interface Sci. 95 5160.CrossRefGoogle Scholar
Norrish, K., 1954 The swelling of montmorillonite Trans. Faraday Soc. Discussion 18 120134.CrossRefGoogle Scholar
Odom, J. W. and Low, P. F., 1978 Relation between swelling, surface area and b dimension of Na-montmorillonites Clays & Clay Minerals 26 345351.CrossRefGoogle Scholar
Odom, J. W. and Low, P. F., 1983 A kinetic method for determining desorption isotherms of water on clays Soil Sci. Soc. Amer. J. 47 10391041.CrossRefGoogle Scholar
Oliphant, J. L. and Low, P. F., 1982 The relative partial specific enthalpy of water in montmorillonite-water systems and its relation to the swelling of these systems J. Colloid Interface Sci. 89 366373.CrossRefGoogle Scholar
Pimentel, G. C. and McClellan, A. L., 1960 The Hydrogen Bond San Francisco W. H. Freeman.Google Scholar
Radoslovich, E. W. and Norrish, K., 1962 The cell dimensions and symmetry of layer-lattice silicates. I. Some structural considerations Amer. Mineral. 47 599616.Google Scholar
Ravina, I. and Low, P. F., 1977 Change of è-dimension with swelling of montmorillonite Clays & Clay Minerals 25 201204.CrossRefGoogle Scholar
Reynolds, R. C., Brindley, G. W. and Brown, G., 1980 Interstratified clay minerals Crystal Structures of Clay Minerals and Their X-ray Identification London Mineralogical Society 249303.CrossRefGoogle Scholar
Rios, E. G. and Vivaldi, J. L. M., 1950 Hydration of layer lattice silicates with exchangeable cations Trans. 4th Intern. Congr. Soil Sci., Amsterdam, Vol. 2 Groningen, The Netherlands Hoitsema Bros. 6771.Google Scholar
Salle de Chou, J., Low, P. F. and Roth, C. B., 1980 Absorption of infrared radiation by D2O and HDO mixed with montmorillonite Clays & Clay Minerals 28 111118.CrossRefGoogle Scholar
Sposito, G. and Prost, R., 1982 Structure of water adsorbed on smectites Chem. Rev. 82 553573.CrossRefGoogle Scholar
Sposito, G., Prost, R. and Gaultier, J. P., 1983 Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li-montmorillonites Clays & Clay Minerals 31 916.CrossRefGoogle Scholar
Sun, Y., Lin, H. and Low, P. F., 1986 The nonspecific interaction of water with the surfaces of clay minerals J. Colloid Interface Sci. 112 556564.CrossRefGoogle Scholar
Suquet, H., de la Calle, C. and Pezerat, H., 1975 Swelling and structural organization of saponite Clays & Clay Minerals 23 19.CrossRefGoogle Scholar
Swartzendruber, D. and Olson, T. C., 1963 Rate of change as determined graphically with an equilateral glass prism Soil Sci. Soc. Amer. Proc. 27 108110.CrossRefGoogle Scholar
Viani, B. E., Low, P. F. and Roth, C. B., 1983 Direct measurement of the relation between interlayer force and interlayer distance in the swelling of montmorillonite J. Colloid Interface Sci. 96 229244.CrossRefGoogle Scholar
Vinogradov, S. N. and Linnell, R. H., 1971 Hydrogen Bonding New York Van Nostrand Reinhold 4781.Google Scholar
Zhang, Z. Z., 1985 Thermodynamic properties of the montmorillonite-water system as affected by the mode of water adsorption: M.Sc. thesis Indiana Purdue University, West Lafayette.Google Scholar
Zhang, Z. Z. and Low, P. F., 1989 Relation between the heat of immersion and the initial water content of Li-, Na-, and K-montmorillonite J. Colloid Interface Sci. 133 461472.CrossRefGoogle Scholar