Clays and Clay Minerals

, Volume 47, Issue 5, pp 672–677 | Cite as

Complex Formation of Cation-Exchanged Montmorillonites with Propylene Carbonate: Osmotic Swelling in Aqueous Electrolyte Solutions

  • Masanobu Onikata
  • Mrrsuji Kondo
  • Naoki Hayashi
  • Shoji Yamanaka


Montmorillonites saturated with Li+, Na+, K+, NH4+, Mg2+, Ca2+, Ba2+, or Ni2+ ions can form complexes with propylene carbonate (PC) by intercalation; the d(001) of montmorillonite expands to 19 Å. In the infrared absorption spectra of these complexes, the C=0 stretching band of the intercalated PC molecules shifts to lower frequencies, and the amount of the shift increased with the increase of the polarizing power of the interlayer cations. Water molecules were strongly bound to the cations. The PC molecules interacted with the cations by way of H2O molecules. With the removal of H2O, the PC molecules directly coordinate to the cations and the PC molecules show a much larger red-shift in the C=O frequency. The PC-montmorillonite complexes exhibited osmotic swelling, even in aqueous electrolyte solutions. This finding is interpreted in terms of the formation of thick electric double-layers consisting of PC and H2O between the 2:1 layers.

Key Words

Infra-Red Spectroscopy Intercalation Complex Montmorillonite Osmotic Swelling Propylene Carbonate 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. Calamai, L., Pantani, O., Pusino, A., Gessa, C., and Fusi, P. (1997) Interaction of rimsulfuron with smectites. Clays and Clay Minerals, 45, 23–27.CrossRefGoogle Scholar
  2. Dowdy, R.H. and Mortland, M.M. (1967) Alcohol-water interactions on montmorillonite surfaces. I. Ethanol. Clays and Clay Minerals, 15, 259–271.CrossRefGoogle Scholar
  3. Fusi, P., Ristori, G.G., and Franci, M. (1986) Interactions of carbaryl with homoionic montmorillonite. Applied Clay Science, 1, 375–383.CrossRefGoogle Scholar
  4. Fusi, P., Franci, M., and Bosetto, M. (1988) Interaction of fiuazifop-butyl and fluazifop with smectites. Applied Clay Science, 3, 63–73.CrossRefGoogle Scholar
  5. Glaeser, R. (1948) On the mechanism of formation of montmorillonite-acetone complexes. Clay Minerals Bulletin, 1, 88–90.Google Scholar
  6. Gutmann, V. (1976) Empirical parameters for donor and acceptor properties of solvents. Electrochimica Acta, 21, 661–670.CrossRefGoogle Scholar
  7. Israelachvili, J.N. (1991) Intermolecular and Surface Forces, 2nd edition. Academic Press, London, 450 pp.Google Scholar
  8. Kondo, M. (1996) US Patent 5,573,583.Google Scholar
  9. Konta, J. (1995) Clay and man: Clay raw materials in the service of man. Applied Clay Science, 10, 275–335.CrossRefGoogle Scholar
  10. MacEwan, D.M.C. and Wilson, M.J. (1980) Interlayer and intercalation complexes of clay minerals. In Crystal Structures of Clay Minerals and Their X-ray Identification, G.W. Brindley and G. Brown, eds. Mineralogical Society, London, 197–248.Google Scholar
  11. Mortland, M.M. (1970) Clay-organic complexes and interactions. In Advances in Agronomy, Volume 22, N.C. Brady, ed. Academic Press, New York, 75–117.CrossRefGoogle Scholar
  12. Norrish, K. and Quirk, J.P. (1954) Crystalline swelling of montmorillonite. Use of electrolytes to control swelling. Nature, 173, 255–256.CrossRefGoogle Scholar
  13. Olejnik, S., Posner, A.M., and Quirk, J.P. (1974) Swelling of montmorillonite in polar organic liquids. Clays and Clay Minerals, 22, 361–365.CrossRefGoogle Scholar
  14. Onikata, M., Kondo, M., and Kamon, M. (1996) Development and characterization of a multiswellable bentonite. In Environmental Geotechnics, M. Kamon ed., A.A. Balkema Publishers, Rotterdam, 587–590.Google Scholar
  15. Parfitt, R.L. and Mortland, M.M. (1968) Ketone adsorption on montmorillonite. Soil Science Society America Proceedings, 32, 355–363.CrossRefGoogle Scholar
  16. Pusino, A., Liu, W., and Gessa, C. (1993) Dimepiperate adsorption and hydrolysis on Al3+-, Fe3+-, Ca2+-, and Na+-montmorillonite. Clays and Clay Minerals, 41, 335–340.CrossRefGoogle Scholar
  17. Tensmeyer, L.G., Hoffmann, R.W., and Brindley, G.W. (1960) Infrared studies of some complexes between ketones and calcium montmorillonite. Clay-organic studies. Part III. Journal of Physical Chemistry, 64, 1655–1662.CrossRefGoogle Scholar
  18. Theng, B.K.G. (1974) The Chemistry of Clay-Organic Reactions. Adam Hilger, London, 343 pp.Google Scholar
  19. Yamanaka, S., Kanamaru, F., and Koizumi, M. (1974) Role of interlayer cations in the formation of acrylonitrile-montmorillonite complexes. Journal of Physical Chemistry, 78, 42–44.CrossRefGoogle Scholar
  20. Yamanaka, S., Kanamaru, F., and Koizumi, M. (1975) Studies on the orientation of acrylonitrile adsorbed on interlamellar surfaces of montmorillonites. Journal of Physical Chemistry, 79, 1285–1288.CrossRefGoogle Scholar

Copyright information

© The Clay Minerals Society 1999

Authors and Affiliations

  • Masanobu Onikata
    • 1
  • Mrrsuji Kondo
    • 1
  • Naoki Hayashi
    • 2
  • Shoji Yamanaka
    • 2
  1. 1.Laboratory of Applied Clay Technology (LACT)Hojun Kogyo Co., Ltd.Annaka, GunmaJapan
  2. 2.Department of Applied Chemistry, Faculty of EngineeringHiroshima UniversityHigashi-HiroshimaJapan

Personalised recommendations