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The state of water in rhyolitic glasses: A deuterium NMR study

Eckert, Hellmut and Yesinowski, James P. and Stolper, Edward M. and Stanton, Thomas R. and Holloway, John (1987) The state of water in rhyolitic glasses: A deuterium NMR study. Journal of Non Crystalline Solids, 93 (1). pp. 93-114. ISSN 0022-3093.

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The first application of ^2H NMR to the study of water in glasses is reported. Naturally occurring volcanic glass (Los Posos rhyolite) was autoclaved with D_2O to yield samples with total “D_2O” contents ranging from 1.6–4.8 wt%. Infrared results show that, in concordance with results from proton-containing glasses, the ratio of molecular D_2O to OD groups increases with increasing total “D_2O” content. Variable-temperature deuterium NMR spectra obtained at 11.7 T, using composite-pulse quadrupolar-echo pulse sequences, indicate the presence of two species with differing motional behavior. The species that is rigid over the entire temperature range investigated (173–393 K) is assigned to OD groups, and yields a powder pattern governed by a distribution of nuclear quadrupole coupling constants (NQCCs) and with a peak-to-peak splitting of ca. 160 kHz. The species that undergoes thermally activated motional processes in this temperature range is assigned to molecular D_2O. At room temperature, this species gives rise to a powder pattern characterized by a reduced quadrupole coupling constant and an asymmetry parameter (η) close to one, indicating that the D_2O molecules undergo twofold rotations about the bisector axis on a lime scale faster than ca. 10^(−5) s. Separation of both spectral components on the basis of their different spin-lattice relaxation times yields reasonable agreement with the D_2O/OD ratio determined from infrared spectroscopy. Lineshape changes at elevated temperatures suggest the activation of additional motional processes; however, even at 375 K only a minor fraction of isotropically mobile species is observed, indicating that “pools” of liquid-water do not exist in significant amounts in these glasses. Low-temperature studies indicate a gradual freezing-out of D_2O motion on the NMR time scale (ca. 10^(−5) s), resulting in a broad lineshape at 173 K governed by a distribution of NQCCs. The well-established correlation between the NQCC and the O-D ··· O distance, a measure of the hydrogen bonding strength, can be used to simulate the low-temperature ^2H NMR spectrum from an assumed distribution of O-D ··· O bond distances. The resultant spectrum, based on a distribution function obtained from independent IR data, is characterized by a mean NQCC of 223 kHz and is in good agreement with the experimental lineshape.

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Additional Information:© 1987 Elsevier Science Publishers. Received 20 November 1986. Revised 5 February 1987. Available online 22 November 2004. The NMR experiments were carried out at the Southern California Regional NMR Facility, supported by NSF grant CHE 84-40137. EMS acknowledges additional support by NSF grant EAR 84-17434. We thank the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research (grant number 17737-AC2). TRS and JRH acknowledge the support of NSF grant EAR 84-07742. We thank Paula Rosener and Sally Newman for their assistance with the infrared analyses. Caltech Division of Geological and Planetary Sciences contribution number 4421.
Funding AgencyGrant Number
NSFCHE 84-40137
NSFEAR 84-17434
American Chemical Society Petroleum Research Fund17737-AC2
NSFEAR 84-07742
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Caltech Division of Geological and Planetary Sciences4421
Record Number:CaltechAUTHORS:20120823-104814629
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Official Citation:Hellmut Eckert, James P. Yesinowski, Edward M. Stolper, Thomas R. Stanton, John Holloway, The state of water in rhyolitic glasses: A deuterium NMR study, Journal of Non-Crystalline Solids, Volume 93, Issue 1, August 1987, Pages 93-114, ISSN 0022-3093, 10.1016/S0022-3093(87)80031-5. (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33483
Deposited By: Ruth Sustaita
Deposited On:23 Aug 2012 18:21
Last Modified:23 Aug 2012 18:21

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