Does water need a new Tg?
10.1063/1.1466469
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

The basis for the conjecture that water’s Tg may be 165±5 K [Velikov, Borick, and Angell, Science 294, 2335 (2001)] has been examined. It is shown that (i) differential scanning calorimetry (DSC) scans provided by Hallbrucker and Mayer [J. Phys. Chem. 91, 503 (1987)], and used as a basis for the conjecture, do not represent the heat capacity of the assumed, slow-cooled glassy water or of hyperquenched glassy water, and (ii) there is no fundamental requirement that the excess heat capacity show a peak at T<Tg—instead the peak may appear at T<Tg, at Tg, or at T>Tg. On heating, the enthalpy of glasses produced by hyperquenching or rapid cooling begins to decrease at a much lower T than that of the glasses obtained by slow cooling. Annealing increases this temperature toward Tg, and the enthalpy decrease continues at T above Tg. In the enthalpy relaxation region, the diffusion coefficient of the hyperquenched glassy state is higher than that of a slow-cooled glassy state at a given T, and a local minimum in the DSC scan does not appear at T<Tg in several glasses. These findings remove the basis for the conjecture that water’s Tg may be ∼165 K. Several analyses confirm that the known sigmoid-shape endotherm of glassy water represents the glass-softening range with onset temperature of 136 K. The DSC scans of a glassy state similar to that of water have been simulated by using a nonlinear, nonexponential enthalpy relaxation formalism. These show that a peak in the difference scan of the simulated glass appears above its Tg of 136 K.

Bibliography

Johari, G. P. (2002). Does water need a new Tg? The Journal of Chemical Physics, 116(18), 8067–8073.

Authors 1
  1. G. P. Johari (first)
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Dates
Type When
Created 23 years ago (July 26, 2002, 10:24 a.m.)
Deposited 1 year, 6 months ago (Feb. 5, 2024, 6:23 p.m.)
Indexed 2 weeks, 1 day ago (Aug. 6, 2025, 10 a.m.)
Issued 23 years, 3 months ago (May 8, 2002)
Published 23 years, 3 months ago (May 8, 2002)
Published Print 23 years, 3 months ago (May 8, 2002)
Funders 0

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@article{Johari_2002, title={Does water need a new Tg?}, volume={116}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1466469}, DOI={10.1063/1.1466469}, number={18}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Johari, G. P.}, year={2002}, month=may, pages={8067–8073} }