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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
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Abstract

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

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