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Title: Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, and Pb2+ equilibrated at 43% relative humidity (RH) and mixed with 2H2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with the 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H2O molecules around their dipoles, reorientation of the 2H2O molecules, and exchange of the 2H2O molecules between interlayer sites coordinated to and not coordinated to the cations.
Authors:
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Publication Date:
OSTI Identifier:
1327128
Report Number(s):
PNNL-SA-119096
Journal ID: ISSN 1932-7447; 48812; KP1704020
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 120; Journal Issue: 16
Publisher:
American Chemical Society
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Environmental Molecular Sciences Laboratory