JOURNAL ARTICLE
RESEARCH SUPPORT, U.S. GOV'T, NON-P.H.S.
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Disruption of Hydrogen-Bonding Network Eliminates Water Anomalies Normally Observed on Cooling to Its Calorimetric Glass Transition.

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.

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