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Infrared Spectroscopic Analyses on the Nature of Water in Montmorillonite

Published online by Cambridge University Press:  28 February 2024

Janice L. Bishop ,
Carlé M. Pieters  and
John O. Edwards
Janice L. Bishop*
Affiliation:
Department of Chemistry, Brown University, Providence, Rhode Island 02912 Department of Geological Sciences, Brown University, Providence, Rhode Island 02912
Carlé M. Pieters
Affiliation:
Department of Geological Sciences, Brown University, Providence, Rhode Island 02912
John O. Edwards
Affiliation:
Department of Chemistry, Brown University, Providence, Rhode Island 02912
*
*Address correspondence to: Janice Bishop, DLR, Forchungszentrum Berlin Institute fuer Planetenerkundung Rudower Chaussee 5, 12484 Berlin, Germany
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Abstract

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Interlayer cations and moisture content greatly influence the molecular vibrations of H2O in montmorillonite as shown through reflectance spectroscopy in the infrared. The absorptions due to H2O have been studied in montmorillonites exchanged with H, Na, Ca, Mg and Fe3+ interlayer cations under variable moisture environments. Band assignments have been made for absorptions in the 3 µm region due to structural OH vibrations, symmetric and asymmetric H2O stretching vibrations and the H2O bending overtone. Changes in the energies of the absorptions due to H2O stretching vibrations were observed as the samples were dehydrated by reducing the atmospheric pressure. Absorptions near 3620 cm−1 and 3550 cm−1 have been assigned to water bound directly to cations (inner sphere) and surface-bonded H2O and absorptions near 3450 cm−1 and 3350 cm−1 have been assigned to additional adsorbed water molecules. Band assignments have been made for combination bands in the near-infrared as well. Absorptions near 1.41 μm and 1.91 μm are assigned to bound H2O combination bands, while the shoulders near 1.46μm and 1.97 μm are assigned to combinations of additional H2O molecules adsorbed in the interlayer regions and along grain surfaces.

Keywords

MontmorilloniteSpectroscopyWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 42 , Issue 6 , December 1994 , pp. 702 - 716
Copyright
Copyright © 1994, Clay Minerals Society

References

Adams, J. B., 1975. Interpretation of visible and near-infrared diffuse reflectance spectra of pyroxenes and other rockforming minerals. In Infrared Spectra of Lunar and Terrestrial Minerals. Karr, C., ed. New York: Academic Press, 91–116.CrossRefGoogle Scholar
Banin, A., and Rishpon, J.. 1979 . Smectite clays in Mars soil: Evidence for their presence and role in Viking biology experimental results. J. Molec. Evolut. 14: 133–152.CrossRefGoogle ScholarPubMed
Bertie, J. E., Ahmed, M. K., and Eysel, H. H.. 1989 . Infrared intensities of liquids. 5. Optical and dielectric constants, integrated intensities, and dipole moment derivatives of H2O and D2O at 22° C. J. Phys. Chem. 93: 2210–2218.CrossRefGoogle Scholar
Bishop, J. L., 1994. Spectroscopic analyses of chemically altered montmorillonites and applications to the soils on Mars. Ph.D. Thesis. Department of Chemistry, Brown University, Providence, Rhode Island.Google Scholar
Bishop, J. L., 1988. The effects of water, octahedral cation substitution and exchangeable cation composition on the shortwave infrared reflectance spectrum of montmorillonite. M.S. report, School of Earth Science, Stanford University, Stanford, California.Google Scholar
Bishop, J. L., Pieters, C. M., and Burns, R. G.. 1993 . Reflectance and Mössbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials. Geochim. Cosmochim. Acta 57: 4583–4595.CrossRefGoogle ScholarPubMed
Bishop, J. L., Pieters, C. M., Burns, R. G., Edwards, J. O., Mancinelli, R. L., and Froeschl, H.. 1994 . Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials. Icarus (in press).CrossRefGoogle Scholar
Bishop, J. L., and Pieters, C. M.. 1994 . Low temperature and low atmospheric pressure infrared reflectance spectroscopy of Mars soil analog materials. J. Geophys. Res. (in press).CrossRefGoogle Scholar
Bruckenthal, E. A., 1987. The dehydration of phyllosilicates and palagonites. Reflectance spectroscopy and differential scanning calorimetry. M.S. Thesis. Univ. Hawaii, Honolulu, Hawaii.Google Scholar
Buijs, K., and Choppin, G. R.. 1963 . Near-infrared studies of the structure of water. I. Pure water. J. Chem. Phys. 39: 2035–2041.CrossRefGoogle Scholar
Cariati, F., Erre, L., Gessa, C., Micera, G., and Piu, P.. 1981 . Water molecules and hydroxyl groups in montmorillonites as studied by near infrared spectroscopy. Clays & Clay Miner. 29: 157–159.CrossRefGoogle Scholar
Cariati, F., Erre, L., Gessa, C., Micera, G., and Piu, P.. 1983a . Polarization of water molecules in phyllosilicates in relation to exchange cations as studied by near infrared spectroscopy. Clays & Clay Miner. 31: 155–157.CrossRefGoogle Scholar
Cariati, F., Erre, L., Gessa, C., Micera, G., and Piu, P.. 1983b . Effects of charge on the near-infrared spectra of water molecules in smectites and vermiculites. Clays & Clay Miner. 31: 447–449.CrossRefGoogle Scholar
Clark, R. N., King, T. V., Klejwa, M., Swayze, G. A., and Vergo, N.. 1990 . High spectral resolution reflectance spectroscopy of minerals. J. Geophys. Res. 95: 12653–12680.CrossRefGoogle Scholar
Coyne, L. M., Bishop, J. L., Scattergood, T., Banin, A., Carle, G., and Orenberg, J.. Near infrared correlation spectroscopy: Quantifying iron and surface water in a series of variably cation-exchanged montmorillonite clays. In Spectroscopy of Minerals and Their Surfaces. Coyne, L. M., 1990a et al. eds. Am. Chem. Soc. 407–429.Google Scholar
Coyne, L. M., Bishop, J. L., Howard, L., and Scattergood, T.. 1990b . Recent spectroscopic findings concerning clay-water interactions at low humidity: Possible applications to models of Martian surface reactivity. 4th Symposium on Chemical Evolution and the Origin of Life. July 24–27, NASA-Ames Research Center, Moffett Field, California.Google Scholar
Eischens, R. P., and Pliskin, W. A.. 1958 . The infrared spectra of adsorbed molecules. Adv. Catalysis 10: 2–56.Google Scholar
Eisenberg, D., and Kauzmann, W.. 1969 . The Structure and Properties of Water. New York: Oxford University Press, 296 pp.Google Scholar
Farmer, V. C., and Russell, J. D.. 1971 . Interlayer complexes in layer silicates: The structure of water in lamellar ionic solutions. Trans. Faraday Soc. 67: 2737–2749.CrossRefGoogle Scholar
Farmer, V. C., 1974 ed. . The Infrared Spectra of Minerals. London: Mineralogical Society, 539 pp.CrossRefGoogle Scholar
Farmer, V. C., 1978. Water on particle surfaces. Chapter 6 In Chemistry of Soil Constituents. Greenland, D., and Hayes, M., eds. New York: Wiley, 405–448.Google Scholar
Fripiat, J. J., Chaussidon, J., and Touillaux, R.. 1960 . Study of dehydration of montmorillonite and vermiculite by infrared spectroscopy. J. Phys. Chem. 64: 1234–1241.CrossRefGoogle Scholar
Grim, R. E., and Kulbicki, G.. 1961 . Montmorillonite: High temperature reactions and classification. Am. Mineral. 46: 1329–1369.Google Scholar
Hall, P. L., and Astill, D. M.. 1989 . Adsorption of water by homoionic exchange forms of Wyoming montmorillonite (SWy-1). Clays & Clay Miner. 37: 355–363.CrossRefGoogle Scholar
Herzberg, G., 1945. Molecular Spectra and Molecular Structure. II. Infrared and Raman Spectra of Polyatomic Molecules. New York: Van Nostrand Company, 632 pp.Google Scholar
Huheey, J. E., Keiter, E. A., and Keiter, R. L.. 1993 . Inorganic Chemistry, 4th ed. New York: Harper Collins College Pub. 964 pp.Google Scholar
Hunt, G. R., and Salisbury, J. W.. 1970 . Visible and near-infrared spectra of minerals and rocks, I. Silicate minerals. Mod. Geol. 1: 283–300.Google Scholar
Johnston, C. T., Sposito, G., and Erickson, C.. 1992 . Vibrational probe studies of water interactions with montmorillonite. Clays & Clay Miner. 40: 722–730.CrossRefGoogle Scholar
Kiselev, A. V., and Lygin, V. I.. 1962 . Use of infra-red spectroscopy to investigate adsorption of surface chemical compounds. Russian Chemical Reviews 31: 175–195.CrossRefGoogle Scholar
Low, P. F., 1979. Nature and properties of water in montmorillonite-water systems. Soil Sci. Soc. Am. J. 43: 651–658.CrossRefGoogle Scholar
Low, P. F., 1981. The swelling of clay: III. Dissociation of exchangeable cations. Soil Sci. Soc. Amer. J. 45: 1074–1078.CrossRefGoogle Scholar
Lyon, R. J. P., and Green, A. A.. Reflectance and emittance of terrain in the mid-infrared (6–25 μm) region. In Infrared Spectra of Lunar and Terrestrial Minerals. Karr, C., 1975 ed. New York: Academic Press, 165–195.CrossRefGoogle Scholar
Luck, W. A. P., 1974 ed. . Structure of water and aqueous solutions. (Proceedings of the Int'l Symposium, Marburg, 1973), Verlag Chemie, Weinheim, Germany, 590 pp.Google Scholar
Mortland, M., Fripiat, J., Chaussidon, J., and Uytterhoeven, J.. 1963 . Interaction between ammonia and the expanding lattices of montmorillonite and vermiculite. J. Phys. Chem. 67: 248–258.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: 51–60.CrossRefGoogle Scholar
Mustard, J. F., and Pieters, C. M.. 1989 . Photometric phase functions of common geologic minerals and applications to quantitative analysis of mineral reflectance spectra. J. Geophys. Res. 94: 13619–13634.CrossRefGoogle Scholar
Pieters, C. M., 1983. Strength of mineral absorption features in the transmitted component of near-infrared reflected light: First results from RELAB. J. Geophys. Res. 88: 9534–9544.CrossRefGoogle Scholar
Poinsignon, C., Cases, J. M., and Fripiat, J. J.. 1978 . Electrical polarization of water molecules adsorbed by smectites. An infrared study. J. Phys. Chem. 82: 1855–1860.CrossRefGoogle Scholar
Post, J. L., and Noble, P. N.. 1994 . The near-infrared combination band frequencies of dioctahedral smectites, micas, and illites. Clays & Clay Miner. 41: 639–644.CrossRefGoogle Scholar
Prost, R., 1975. Étude de l'hydration des argiles: Interactions eau-minéral et mécanisme de la retention de l'eau. II. Étude d'une smectite. Ann. Agron. 26: 463–535.Google Scholar
Prost, R., 1976. Interactions between adsorbed water molecules and the structure of clay minerals: Hydration mechanism of smectites. Proc. Int. Clay Conf., 1975, 351–359.Google Scholar
Prost, R., and Chaussidon, J.. 1969 . The infrared spectrum of water adsorbed on hectorite. Clay Miner. 8: 143–149.CrossRefGoogle Scholar
Russell, J. D., and Farmer, V. C.. 1964 . Infra-red spectroscopic study of the dehydration of montmorillonite and saponite. Clay Min. Bull. 5: 443–464.CrossRefGoogle Scholar
Schultz, J. W., 1957. On the Raman spectra of water and concentrated aqueous solutions of alkali halides. Ph.D. thesis, Brown University, Department of Chemistry.Google Scholar
Sposito, G., Prost, R., and Gaultier, J.-P.. 1983 . Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li-montmorillonites. Clays & Clay Miner. 31: 9–16.CrossRefGoogle Scholar
Sposito, G., and Prost, R., 1982. Structure of water adsorbed on smectites. Chem. Rev. 82: 553–573.CrossRefGoogle Scholar
van Olphen, H., and Fripiat, J. J., 1979 eds. . Data Handbook for Clay Materials and Other Non-Metallic Minerals. New York: Pergamon Press, 346 pp.Google Scholar