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

Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan; Bowden, Mark; Yazaydin, A. Ozgur; Kirkpatrick, R. James

doi:10.1021/acs.jpcc.6b03431

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

Journal Article · Wed Apr 06 00:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b03431· OSTI ID:1327128

Reddy, U. Venkateswara ^[1]; Bowers, Geoffrey M. ^[2]; Loganathan, Narasimhan ^[1]; Bowden, Mark ^[3]; Yazaydin, A. Ozgur ^[4]; Kirkpatrick, R. James ^[1]

Michigan State Univ., East Lansing, MI (United States)
Alfred Univ., NY (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Michigan State Univ., East Lansing, MI (United States); Univ. College London (United Kingdom)

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. Here, 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.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

DOE Contract Number:: AC05-76RL01830; FG02-08ER15929

OSTI ID:: 1327128

Report Number(s):: PNNL-SA--119096; 48812; KP1704020

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 16 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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

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