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Title: Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition

Abstract

Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and T S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1376393
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 16; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Borreguero, Jose M., and Mamontov, Eugene. Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b01226.
Borreguero, Jose M., & Mamontov, Eugene. Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition. United States. doi:10.1021/acs.jpcb.7b01226.
Borreguero, Jose M., and Mamontov, Eugene. Tue . "Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition". United States. doi:10.1021/acs.jpcb.7b01226. https://www.osti.gov/servlets/purl/1376393.
@article{osti_1376393,
title = {Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition},
author = {Borreguero, Jose M. and Mamontov, Eugene},
abstractNote = {Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature TH = 235 K predicts divergence at TS = 228 K. The “no-man’s land” between the TH and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both TH and TS on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the TH and TS, must be associated specifically with the hydrogen-bonding network.},
doi = {10.1021/acs.jpcb.7b01226},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 16,
volume = 121,
place = {United States},
year = {Tue Apr 11 00:00:00 EDT 2017},
month = {Tue Apr 11 00:00:00 EDT 2017}
}

Journal Article:
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