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The kinetics of dehydration in Ca-montmorillonite: an in situ X-ray diffraction study

Published online by Cambridge University Press:  05 July 2018

Helen J. Bray ,
Simon A. T. Redfern  and
Simon M. Clark
Helen J. Bray
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK
Simon A. T. Redfern
Affiliation:
Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge, CB2 3EQ, UK
Simon M. Clark
Affiliation:
CLRC, Daresbury Laboratory, Daresbury, Warrington, WA4 4AD, UK
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Abstract

The thermal dehydration of naturally occurring Ca-montmorillonite has been studied by in situ X-ray diffraction at temperatures between 60–120°C. The time-temperature-dependence of the position of the basal (001) reflection reveals that interlayer water loss on isothermal dehydration occurs in two stages. After an initial rapid decrease in interlayer spacing (on shock heating to an isothermal soak temperature) the reaction proceeds towards equilibrium more slowly. Furthermore, the width of the (001) reflection changes with time, reflecting transformation-dependent changes in homogeneity perpendicular to (001) with a maximum in peak width at the point where the rate of the reaction appears to change. This suggests that, as the interlayer spacing collapses, a local change is induced in the structure, affecting the means of movement of the water from the interlayer.

Keywords

montmorillonitedehydrationsynchrotron radiationsmectitekinetics
Type
Research Article
Information
Mineralogical Magazine , Volume 62 , Issue 5 , October 1998 , pp. 647 - 656
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1998

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References

Allison, E.B. (1954) Determination of specific heats and heats of reaction of clay minerals by thermal analysis. Silicates Ind., 19, 363–73.Google Scholar
Barshad, I. (1949) The nature of lattice expansion and its relation to the hydration in montmorillonite and vermiculite. Amer. Mineral., 34, 675–84.Google Scholar
Barnes, P., Turillas, X., Jupe, A.C., Colston, S.L., David, O., Cernik, R.J., Livesey, P., Hall, C., Bates, D. and Dennis, R. (1996) Applied crystallography solution to problems in solid-state chemistry case examples with ceramics, cements and zeolites. J. Chem. Soc. Faraday. Trans., 92, 2187–96.CrossRefGoogle Scholar
Bellotto, M., Gualtieri, A., Artoli, G. and Clark, S.M. (1995) Kinetic study of the kaolinite-mullite reaction sequence. Part I. Kaolinite dehydroxylation. Phys. Chem. Minerals, 22, 207–14.CrossRefGoogle Scholar
Boek, E.S., Coveney, P.V. and Skipper, N.T. (1995) Monte Carlo molecular studies of hydrated Li-, Na- and K- smectites: understanding the role of potassium as a clay swelling inhibitor. J. Amer. Chem. Soc., 117, 12608–17.CrossRefGoogle Scholar
Bridgeman, C.H., Buckingham, A.D., Skipper, N.T. and Payne, M.C. (1996) Ab-initio total energy study of uncharged 2:1 clays and their interaction with water. Mol. Phys., 89, 879–88.CrossRefGoogle Scholar
Brindley, G.W., Sharp, J.H., Patterson, J.H. and Narahari, B.N. (1967) Kinetics and mechanism of dehydroxylation processesses. 1. Temperature and vapor pressure dependence of dehydroxylation of kaolinite. Amer. Mineral., 52, 201–11.Google Scholar
Calvet, R. and Prost, R. (1971) Cation migration into empty octahedral sites and surface properties of clays. Clays Clay Minerals, 19, 175–86.CrossRefGoogle Scholar
Chang, F.R.C., Skipper, N.T. and Sposito, G. (1995) Computer simulation of interlayer molecular structure in Sodium montmorillonite hydrates. Langmuir, 11, 2734–41.CrossRefGoogle Scholar
Clarke, S.M. (1996) A new energy-dispersive powder diffraction facility at the SRS. Nucl. Inst. Meth. Phys. Res. A, 381, 161–8.CrossRefGoogle Scholar
Craido, J.M., Ortega, A., Real, C. and Torres de Torres, E. (1984) Re-examination of the kinetics of the thermal dehydroxylation of kaolinite. Clay Minerals, 19, 653–61.CrossRefGoogle Scholar
Farmer, V.C. and Russell, J.D. (1967) IR absorption spectrometry in clay studies. Clays Clay Minerals, 15, 121–42.CrossRefGoogle Scholar
Girgis, B.S., El-Barawy, K.A. and Feli, N.S. (1986) Dehydration kinetics of some smectites: a thermogravimetric study. Thermochimica Acta, 98, 181–9.Google Scholar
Greene-Kelly, R. (1955) Dehydration of montmorillonite minerals. Clay Minerals Bull., 5, 604–15.Google Scholar
Guindy, N.M., El-Akkad, T.M., Flex, N.S., El-Massry, S.R. and Nashed, S. (1985) Thermal dehydration of mono- and di-valent montmorillonite cationic derivatives. Thermochimica Acta, 85, 211–4.CrossRefGoogle Scholar
Hall, P.L., Astill, D.M. and McConnell, J.D.C. (1986) Thermodynamic and structural aspects of the dehydration of smectites in sedimentary rocks. Clay Minerals, 21, 633–48.CrossRefGoogle Scholar
Hancock, J.D. and Sharp, J.H. (1972) Method of comparing solid-state kinetic data and its application to the decomposition of kaolinite, brucite and BaCO3 . J. Amer. Ceram. Soc., 55, 74–7.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. Mineral., 23, 863–75.Google Scholar
Hofman, H. and Klemen, R. (1950) Verlust der Austauschfahigheit von Lithiuimionen an Bentonit durch Erhitzung. Zeits. Anorg. Chem., 262, 95–9.CrossRefGoogle Scholar
Huang, W.L., Bassett, W.A. and Wu, T.C. (1994) Dehydration and hydration of montmorillonite at elevated temperatures and pressures monitored using synchrotron radiation. Amer. Mineral., 79, 683–91.Google Scholar
Karaboni, S., Smit, B., Urah, J. and van Oort, E. (1996) The swelling of clays: molecular simulations of the hydration of montmorillonite. Science, 271, 1102–4.CrossRefGoogle Scholar
Kittrick, J.A. (1969a) Interlayer forces in montmorillonite and vermiculite. Soil. Sci. Soc. Amer. Proc., 33, 217–22.CrossRefGoogle Scholar
Kittrick, J.A. (1969b) Quantitative evaluation of the strong-force model for expansion and contraction of vermiculite. Soil. Sci. Soc. Amer. Proc., 33, 222–5.CrossRefGoogle Scholar
Koster van Gross, A F. and Guggenheim, S. (1984) The effect of pressure on the dehydration reaction of interlayer water in Na-montmorillonite (Swy-1). Amer. Mineral., 69, 872–9.Google Scholar
Koster van Groos, A.F. and Guggenheim, S. (1986) Dehydration of K-exchanged montmorillonite at elevated temperatures and pressures. Clays Clay Minerals, 34, 281–6.CrossRefGoogle Scholar
Koster van Groos, A.F. and Guggenheim, S. (1989) Dehydroxylation of Ca- and Mg-exchanged montmorillonite. Amer. Mineral., 74, 627–36.Google Scholar
Laird, D.A. (1996) Model for the crystalline swelling of 2:1 layer phyllosilicates. Clays Clay Minerals, 44, 553–9.CrossRefGoogle Scholar
Laird, D.A. Shang, C. and Thompson, M.L. (1995) Hysteresis in crystalline swelling of smectites. J. Coll. Interface Sci., 171, 240–5.CrossRefGoogle Scholar
Low, P.F. (1979) Nature and properties of water in montmorillonite-water systems. Soil. Sci. Amer. J., 45, 651–8.CrossRefGoogle Scholar
Magara, K. (1964) Reevaluation of montmorillonite dehydration as cause of abnormal pressure and hydrocarbon migration. Amer. Assoc. Petroleom. Geol. Bull., 59, 202–9.Google Scholar
Miletich, R., Zemann, J. and Nowak, M. (1997) Reversible hydration in synthetic mixite BiCu6(OH)6(AsO4)3.nH2O (n3): hydration kinetics and crystal chemistry. Phys. Chem. Minerals, 24, 411–22.CrossRefGoogle Scholar
Moore, D.M. and Hower, J. (1986) Ordered interstratication of dehydrated and hydrated Na- smectite. Clays Clay Minerals, 34, 379–84.CrossRefGoogle Scholar
Murray, P. and White, J. (1955) Kinetics of thermal dehydration characteristics of the clay minerals. Trans. Brit. Ceram. Soc., 54, 137–50.Google Scholar
Norrish, K. (1954) The swelling of montmorillonite. Discuss. Faraday Soc., 18, 120–34.CrossRefGoogle Scholar
Parker, J.C. (1986) Hydrostatics of water in porous media. In Soil Physical Chemistry(Sparks, D.L., ed.). Boca Raton, FL: CRC Press. 209–96.Google Scholar
Ransom, B. and Helgeson, H.C. (1995) A chemical and thermodynamic model of dioctahedral 2:1 layer clay minerals in diagenetic processes: dehydration of dioctahedral aluminous smectite as a function of temperature and depth in sedimentary basins. Amer. J. Sci., 295, 245–81.CrossRefGoogle Scholar
Redfern, S.A.T. (1987) The kinetics of dehydroxylation of kaolinite. Clay Minerals, 22, 447–56.CrossRefGoogle Scholar
Ruan, H.D. and Gilkes, R.J. (1996) Kinetics of thermal dehydroxylation of aluminous goethite. J. Therm. Anal., 46, 1223–38.CrossRefGoogle Scholar
Salje, E.K.H. (1986) Phase Transitions in Ferroelastic and Co-elastic Crystals. Cambridge University Press, Cambridge 202–11.Google Scholar
Salje, E.K.H. and Wruck, B. (1988) Kinetic rate laws as derived f rom order parameter theory. II Interpretation of experimental data by Laplacetransformation, the relaxation spectra and the kinetic gradient coupling between two order parameters. Phys. Chem. Minerals, 16, 140–7.CrossRefGoogle Scholar
Skipper, N.T., Refson, K. and McConnell, J.D.C. (1989) Computer calculation of water-clay interactions using atomic pair potentials. Clay Minerals, 24, 411–25.CrossRefGoogle Scholar
Skipper, N.T., Refson, K. and McConnell, J.D.C. (1991) Computer simulation of interlayer water in 2:1 clays. J. Chem. Phys. 91, 7434–45.CrossRefGoogle Scholar
Skipper, N.T., Chang, F.RC. and Sposito, G. (1995a) Monte Carlo simulation of interlayer molecularstructure in swelling clay minerals. 1. Methodology. Clays Clay Minerals, 43, 285–93.CrossRefGoogle Scholar
Skipper, N.T., Sposito, G. and Chang, F.R.C. (1995b) Monte Carlo simulations of interlayer molecularstructure in swelling clay-minerals. 2. Monolayer hydrates. Clays Clay Minerals, 43, 294–303.CrossRefGoogle Scholar
Steiger, R.P. (1982) Fundamentals and use of potassium/polymer drilling fluids to minimize drilling and completion problems associated with hydratable clays. J. Petrol. Tech., 24, 1661–70.CrossRefGoogle Scholar
Tettenhorst, R. (1962) Cation migration in montmorillonite. Amer. Mineral., 47, 769–73.Google Scholar
van Olphen, H. (1965) Thermodynamics of interlayer adsoprtion of water in clays. J. Coll. Sci., 20, 822–37.CrossRefGoogle Scholar
Wu, T.C., Bassett, W.A., Koster van Groos, A.F. and Guggenheim, S. (1997) Montmorillonite under high H2O pressures: stability of hydrate phases, rehydration hysteresis and the effect of interlayer cation. Amer. Mineral., 82, 69–78.CrossRefGoogle Scholar