Hostname: page-component-55f67697df-4ks9w Total loading time: 0 Render date: 2025-05-23T03:41:53.554Z Has data issue: false hasContentIssue false
  • English
  • Français

Infrared Study of Water Sorption on Na-, Li-, Ca-, and Mg-Exchanged (SWy-1 and SAz-1) Montmorillonite

Published online by Cambridge University Press:  28 February 2024

Weizong Xu ,
Cliff T. Johnston ,
Paul Parker  and
Stephen F. Agnew
Weizong Xu
Affiliation:
Crop, Soil and Environmental Sciences, Agronomy Department, Purdue University, West Lafayette, Indiana 47907-1150, USA
Cliff T. Johnston
Affiliation:
Crop, Soil and Environmental Sciences, Agronomy Department, Purdue University, West Lafayette, Indiana 47907-1150, USA
Paul Parker
Affiliation:
Crop, Soil and Environmental Sciences, Agronomy Department, Purdue University, West Lafayette, Indiana 47907-1150, USA
Stephen F. Agnew
Affiliation:
CST4, MS J586, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
Get access Rights & Permissions [Opens in a new window]

Abstract

An environmental infrared microbalance (EIRM) cell was used to study H2O sorption on two montmorillonite samples as a function of water content and type of exchangeable cation. The vibrational spectra showed that H2O sorbed to the clay at low-water content was strongly influenced by the exchangeable cation and by the close proximity to the clay surface. At water contents <6 H20 molecules per exchangeable cation, the H-O-H bending mode of H2O (v2 mode) shifts to a lower frequency and is characterized by an increase in molar absorptivity. In contrast, the positions of the asymmetric and symmetric OH-stretching modes of sorbed water (v1 and v3 modes) shift to higher energies. These observations indicate that H2O molecules sorbed to the clay surface at low-water content are less hydrogen bonded than in bulk H2O. In addition, the vibrational-stretching and bending bands of the structural OH groups of the 2:1 layer are also strongly influenced by H2O content and type of exchangeable cation. By using the EIRM cell, the molar absorptivities of the structural OH-bending vibrations were measured as a function of H2O content. The position and molar absorptivity of the structural OH-bending bands at 920, 883, and 840 cm-1 are strongly influenced by H2O content and type of exchangeable cation. The molar absorptivity of the 920-cm-1 band, which is assigned to the AlAlOH group, decreased strongly at low-H2O content. This reduction in intensity is assigned to a dehydration-induced change in orientation of the structural OH groups resulting from the penetration of H2O molecules into siloxane ditrigonal cavities that are not associated with a net negative charge from isomorphous substitutions.

Keywords

Exchangeable CationFTIRHydrationHysteresisSmectiteSorptionWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 48 , Issue 1 , February 2000 , pp. 120 - 131
Copyright
Copyright © 2000, 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.)

Article purchase

Temporarily unavailable

References

Alba, M.D. Alvero, R. Becerro, A.I. Castro, M.A. and Trillo, J.M., 1998 Chemical behavior of lithium ions in reex-panded Li-montmorillonites. Journal of Physical Chemistry B 102 2207–2213 10.1021/jp9715641.CrossRefGoogle Scholar
Berend, I. Cases, J.M. François, M. Uriot, J.P. Michot, L. Masion, A. and Thomas, F., 1996 Mechanism of adsorption and desorption of water vapor by homoionic mont-morillonites: 2. The Li+ Na+, K+, Rb+ and Cs+-exchanged forms. Clays and Clay Minerals. 43 324–336 10.1346/CCMN.1995.0430307.CrossRefGoogle Scholar
Breen, C. Madejova, J. and Komadel, P., 1995 Characterisation of moderately acid-treated, size-fractionated mont-morillonites using IR and MAS NMR Spectroscopy and thermal analysis. Journal of Materials Chemistry 5 469–474 10.1039/JM9950500469.CrossRefGoogle Scholar
Calvet, R. and Prost, R., 1971 Cation migration into empty octahedral sites and surface properties of clays. Clays and Clay Minerals 19 175–186 10.1346/CCMN.1971.0190306.CrossRefGoogle Scholar
Cancela, G.D. Huertas, F.J. Taboada, E.R. Sanchez Rasero, F. and Laguna, A.H., 1997 Adsorption of water vapor by homoionic montmorillomtes. Heats of adsorption and desorption. Journal of Colloid and Interface Science 185 343–354 10.1006/jcis.1996.4572.CrossRefGoogle Scholar
Cases, J.M. Berend, I. Besson, G. François, M. Uriot, J.P. Thomas, F. and Poirier, J.E., 1992 Mechanism of adsorption and desorption of water vapor by homoionic mont-morillonite. 1. The sodium exchanged form. Langmuir 8 2730–2739 10.1021/la00047a025.CrossRefGoogle Scholar
Cases, J.M. Berend, I. Francois, M. Uriot, J.P. Michot, L.J. and Thomas, F., 1997 Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite. 3. The Mg2+, Ca2+, Sr2+ and Ba2+ exchanged forms. Clays and Clay Minerals 45 8–22 10.1346/CCMN.1997.0450102.CrossRefGoogle Scholar
Chang, F.R.C. Skipper, N.T. and Sposito, G., 1997 Monte Carlo and molecular dynamics simulations of interfacial structure in lithium-montmorillonite hydrates. Langmuir 13 2074–2082 10.1021/la9603176.CrossRefGoogle Scholar
Chiou, C.T. and Rutherford, D.W., 1997 Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays. Clays and Clay Minerals 45 867–880 10.1346/CCMN.1997.0450611.CrossRefGoogle Scholar
Farmer, V.C. and Farmer, V.C., 1974 The Layer Silicates The Infrared Spectra of Minerals London The Mineralogical Society 331–359 10.1180/mono-4.15.CrossRefGoogle Scholar
Farmer, V.C., Greenland, D.J. and Hayes, M.H.B., 1978 Water on particle surfaces Chemistry of Soil Constituents New York Wiley 405–448.Google Scholar
Johnston, C.T. Aohci, Y.O. and Sparks, D.L., 1996 Fourier transform infrared and Raman spectroscopy Methods of Soil Analysis Part 3 Chemical Methods Wisconsin Soil Science Society of America, Madison 269–321.Google Scholar
Johnston, C.T. and Stone, D.A., 1990 Influence of hydrazine on the vibrational modes of kaolinite. Clays and Clay Minerals 38 121–128 10.1346/CCMN.1990.0380202.CrossRefGoogle Scholar
Johnston, C.T. Tipton, T. Stone, D.A. Erickson, C. and Trabue, S.L., 1991 Chemisorption of p-dimethoxybenzene on Cu-montmorillonite. Langmuir 7 289–296 10.1021/la00050a015.CrossRefGoogle Scholar
Johnston, C.T. Sposito, G. and Erickson, C., 1992 Vibrational probe studies of water interactions with montmorillonite. Clays and Clay Minerals 40 722–730 10.1346/CCMN.1992.0400611.CrossRefGoogle Scholar
Johnston, C.T. Xu, W. Parker, P. Agnew, S.E., Yamagishi, A. Aramata, A. and Taniguchi, M., 1998 Characterization of active sites on mineral surfaces: An infrared study of water sorption on montmorillonte The Latest Frontiers of Clay Chemistry: Proceedings of the Sapporo Conference on the Chemistry of Clays and Clay Minerals Sapporo The Smectite Forum of Japan 47–69.Google Scholar
Karaborni, S. Smit, B. Heidug, W. Urai, J. and van Oort, E., 1996 The swelling of clays: Molecular simulations of the hydration of montmorillonite. Science 271 1102–1104 10.1126/science.271.5252.1102.CrossRefGoogle Scholar
Keren, R. and Shainberg, I., 1975 Water vapor isotherms and heat of immersion of Na/Ca-montmorillonite systems - I: Homoionic clay. Clays and Clay Minerals 23 193–200 10.1346/CCMN.1975.0230305.CrossRefGoogle Scholar
Kijne, J.W., 1969 On the interaction of water molecules and montmorillonite surfaces. Soil Science Society of America Proceedings 33 539–543 10.2136/sssaj1969.03615995003300040017x.CrossRefGoogle Scholar
Madejova, J. Bujdak, J. Gates, W.P. and Komadel, P., 1996 Preparation and infrared spectroscopic characterization of reduced-charge montmorillonite with various Li contents. Clay Minerals 31 233–241 10.1180/claymin.1996.031.2.09.CrossRefGoogle Scholar
Mooney, R.W. Keenan, A.G. and Wood, L.A., 1952 Adsorption of water vapor by montmorillonite. I. Heat of de-sorption and application of BET theory. Journal of the American Chemical Society 74 1367–1370 10.1021/ja01126a001.CrossRefGoogle 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. Journal of the American Chemical Society 74 1371–1374 10.1021/ja01126a002.CrossRefGoogle Scholar
Mortland, M.M. and Raman, K.V., 1968 Surface acidities of smectites in relation to hydration, exchangeable-cation and structure. Clays and Clay Minerals 16 393–398 10.1346/CCMN.1968.0160508.CrossRefGoogle Scholar
Pimentel, G.C. and McClellan, A.B., 1960 The Hydrogen Bond, 1st edition San Fransisco W.H. Freeman and Co..Google Scholar
Poinsignon, C. Cases, J.M. and Fripiat, J.J., 1978 Electrical-polarization of water molecules adsorbed by smectites. An infrared study. Journal of Physical Chemistry 82 1855–1860 10.1021/j100505a016.CrossRefGoogle Scholar
Russell, J.D. and Farmer, V.C., 1964 Infra-red spectroscopic study of the dehydration of montmorillonite and saponite. Clay Minerals Bulletin 5 443–464 10.1180/claymin.1964.005.32.04.CrossRefGoogle Scholar
Serratosa, J.M. Rausell-Colom, J.A. and Sanz, J., 1984 Charge-density and its distribution in phyllosilicates: Effect on the arrangement and reactivity of adsorbed species. Journal of Molecular Catalysis 27 223–234 10.1016/0304-5102(84)85082-8.CrossRefGoogle Scholar
Skipper, N.T. Refson, K. and McConnell, J.D.C., 1991 Computer simulation of interlayer water in 2:1 clays. Journal of Chemical Physics 94 7434–7445 10.1063/1.460175.CrossRefGoogle Scholar
Skipper, N.T. Chang, F.R.C. and Sposito, G., 1995 Monte-Carlo simulation of interlayer molecular structure in swelling clay minerals. 1. Methodology. Clays and Clay Minerals 43 285–293 10.1346/CCMN.1995.0430303.CrossRefGoogle Scholar
Skipper, N.T. Sposito, G. and Chang, F.R.C., 1995 Monte Carlo simulation of interlayer molecular structure in swelling clay minerals. 2. Monolayer hydrates. Clays and Clay Minerals 43 294–303 10.1346/CCMN.1995.0430304.CrossRefGoogle Scholar
Sposito, G. and Prost, R., 1982 Structure of water adsorbed on smectites. Chemistry Review 82 553–573 10.1021/cr00052a001.CrossRefGoogle Scholar
Sposito, G. Prost, R. and Gaultier, J.P., 1983 Infrared spectroscopic study of adsorbed water on reduced-charge Na/ Li montmorillonites. Clays and Clay Minerals 31 9–16 10.1346/CCMN.1983.0310102.CrossRefGoogle Scholar
Suqute, H. Calle, C.D.I. and Pezerat, H., 1975 Swelling and structural organization of saponite. Clays and Clay Minerals 23 1–9 10.1346/CCMN.1975.0230101.CrossRefGoogle Scholar
Tipton, T. Johnston, C.T. Trabue, S.L. Erickson, C. and Stone, D.A., 1993 Gravimetric/FTIR apparatus for the study of vapor sorption on clay films. Review of Scientific Instruments 64 1091–1092 10.1063/1.1144468.CrossRefGoogle Scholar
van Olphen, H. and Fripiat, J.J., 1979 Data Handbook for Clay Materials and Other Non-Metallic Minerals, 1st edition Oxford Pergamon Press.Google Scholar
Venyaminov, S.Y. and Prendergast, F.G., 1997 Water (H2O and D2O) molar absorptivity in the 1000–4000 cm-1 range and quantitative infrared spectroscopy of aqueous solutions. Analytical Biochemistry 248 234–245 10.1006/abio.1997.2136.CrossRefGoogle Scholar
Weaver, C.E. and Pollard, L.D., 1973 The Chemistry of Clay Minerals Amsterdam Elsevier Scientific Publishing Co..Google Scholar
Yan, L. Roth, C.B. and Low, P.E., 1996 Changes in the Si-O vibrations of smectite layers accompanying the sorption of interlayer water. Langmuir 12 4421–4429 10.1021/la960119e.CrossRefGoogle Scholar
Yan, L. Low, P.E. and Roth, C.B., 1996 Swelling pressure of montmorillonite layers versus H-O-H bending frequency of the interlayer water. Clays and Clay Minerals 44 749–756 10.1346/CCMN.1996.0440605.CrossRefGoogle Scholar
Yariv, S., 1992 The effect of tetrahedral substitution of Si by Al on the surface acidity of the oxygen plane of clay minerals. International Reviews in Physical Chemistry 11 345–375 10.1080/01442359209353275.CrossRefGoogle Scholar
Yariv, S., Schrader, M.E. and Loeb, G., 1992 Wettability of clay minerals Modern Approaches to Wettability: Theory and Applications. New York Plenum Press 279–326 10.1007/978-1-4899-1176-6_11.CrossRefGoogle Scholar