Hostname: page-component-7dd5485656-6kn8j Total loading time: 0 Render date: 2025-10-30T19:10:41.438Z Has data issue: false hasContentIssue false
  • English
  • Français

Deuterium Nuclear Magnetic Resonance Studies of Water Molecules Restrained by Their Proximity to a Clay Surface

Published online by Cambridge University Press:  02 April 2024

Jean Grandjean  and
Pierre Laszlo
Jean Grandjean
Affiliation:
Laboratoire de Chimie Fine aux Interfaces, Institut de Chimie B6, Université de Liège, Sart Tilman par 4000 Liège, Belgium
Pierre Laszlo
Affiliation:
Laboratoire de Chimie Fine, Biomimétique et aux Interfaces, Ecole Polytechnique, 91128 Palaiseau, France
Get access Rights & Permissions [Opens in a new window]

Abstract

Observation of quadrupolar splittings for 2H and 17O nuclei from D2O solvent molecules in suspensions of the Ecca Gum BP bentonite points unambiguously to the ordering of water molecules with respect to a static magnetic field. The application of the magnetic field apparently orients the clay platelets as tactoids. Some water molecules adhere to the platelets and are oriented. The magnitude of the quadrupolar splitting depends strongly on the nature of the interstitial cations. The sign of the splitting changes as the ratio of divalent to monovalent cation increases, reflecting a switch in the microdynamics of water molecules next to the plates. With the entry of divalent cations, the clay becomes more cohesive due to the vertical electrostatic attraction of the counterions to the charged plates. More of these hydrated divalent ions compared with monovalent ions condense onto the charged sheet, thereby increasing metal coordination to those water molecules in contact with the clay surface. The dominant reorientation mode of the water molecules switches from rotation of water molecules around hydrogen bonds to the charged sheets to rotation around the electrostatic bond to the divalent metal cation. The effect is spectacular and important in understanding the chemical properties of cation-exchanged montmorillonites.

Keywords

Nuclear magnetic resonanceOrientationQuadrupolar splittingSmectiteSurface acidityWater

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 37 , Issue 5 , October 1989 , pp. 403 - 408
Copyright
Copyright © 1989, 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

Chachaty, C. and Quaegebeur, J. P., 1984 Proton, deuteron and oxygen-17 nuclear magnetic relaxation and water reorientation in a lyotropic lamellar phase Mol. Phys 52 1081 – 1104.CrossRefGoogle Scholar
Edmonds, D. T. and Mackay, A. L., 1975 The pure quad-rupole resonance of deuteron in ice J. Magn. Resonance 20 515 – 519.Google Scholar
Edmonds, D. T. and Zussman, A., 1972 Pure quadrupole resonance of 17O in ice Phys. Lett. A 41A 167 – 169.CrossRefGoogle Scholar
Grandjean, J. and Laszlo, P., 1988 Multinuclear and pulsed gradient magnetic resonance studies of structure and dynamics at the interface of a clay Abstracts, 196th Amer. Chem. Soc. Meeting, Los Angeles, 1988 .Google Scholar
Grandjean, J., Laszlo, P., Coyne, L. M., McKeever, S. and Blake, D., 1989 Multinuclear magnetic resonance studies of structures of active sites in minerals Structures of Active Sites in Minerals .CrossRefGoogle Scholar
Grandjean, J. and Laszlo, P., 1989 Multinuclear and pulsed gradient magnetic resonance studies of sodium cations and of water reorientation at the interface of a clay J. Magn. Resonance .CrossRefGoogle Scholar
Guo, W. and Wong, T. C., 1987 17O and 2H nuclear magnetic resonance studies of the orientation of water molecules in several Iyotropic liquid crystals Langmuir 3 537 – 543.CrossRefGoogle Scholar
Hakala, M. R. and Wong, T. C., 1986 Phase structure and orientational order of water in the lyotropic mesophase of the hexadecyltriethyl-ammonium bromide-water-pentanol system by deuterium and oxygen-17 NMR Langmuir 2 83 – 89.CrossRefGoogle Scholar
Halle, B. and Wennerstrom, H., 1981 Interpretation of magnetic resonance data from water nuclei heterogeneous systems J. Chem. Phys 75 1928 – 1943.CrossRefGoogle Scholar
Hamilton, W. C., 1962 The structure of solids Ann. Rev. Phys. Chem 13 19 – 40.CrossRefGoogle Scholar
Huheey, J. E., 1983 Inorganic Chemistry New York Harper & Row 272.Google Scholar
Laszlo, P., 1987 Chemistry reactions on clays Science 235 1473 – 1477.CrossRefGoogle ScholarPubMed
Lindman, B. and Forsén, S. (1976) Chlorine, bromine and iodine NMR: Physico-chemical and biological applications: in NMR Basic Principles and Progress, Diehl, P., Fluck, E. and Kosfeld, R., eds., Springer-Verlag, Heidelberg, 12, 274 pp.Google Scholar
McConnell, H. M., 1958 Reaction rates by nuclear magnetic resonance J. Chem. Phys 28 430 – 431.CrossRefGoogle Scholar
Swift, T. J. and Connick, R. E., 1962 Nuclear magnetic resonance-relaxation mechanisms of 17O in aqueous solutions of paramagnetic cations and the lifetime of water molecules in the first coordination sphere J. Chem. Phys 37 307 – 320.CrossRefGoogle Scholar
Wong, T. C. and Hakala, M. R., 1985 On the determination of the orientational probability distribution of water in heterogeneous systems from 2H and 17O quadrupolar splittings Chem. Phys. Lett 119 85 – 88.CrossRefGoogle Scholar