Prediction of entropy and dynamic properties of water below the homogeneous nucleation temperature
β Scribed by Francis W. Starr; C.Austen Angell; H.Eugene Stanley
- Publisher
- Elsevier Science
- Year
- 2003
- Tongue
- English
- Weight
- 256 KB
- Volume
- 323
- Category
- Article
- ISSN
- 0378-4371
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β¦ Synopsis
The behavior of thermodynamic and dynamic properties of liquid water at atmospheric pressure in the temperature range between the lower limit of supercooling (TH β 235 K) and the onset of the glassy state at Tg has been the focus of much research, and many questions remain about the properties of water in this region. Since direct measurements on water in this temperature range remain largely infeasible, we use existing experimental measurements of the entropy, speciΓΏc heat, and enthalpy outside this range to construct a possible form of the entropy in the "di cult-to-probe" region. Assuming that the entropy is well-deΓΏned in extreme metastable states, and that there is no intervening discontinuity at atmospheric pressure, we estimate the excess entropy Sex of the liquid over the crystal within relatively narrow limits. We ΓΏnd that our approximate form for Sex shows atypical behavior when compared with other liquids: using a thermodynamic categorization of "strong" and "fragile" liquids, water appears to be fragile on initial cooling below the melting temperature, and strong in the temperature region near the glass transition. This thermodynamic construction can be used, with appropriate reservations, to estimate the behavior of the dynamic properties of water by means of the Adam-Gibbs equation-which relates conΓΏgurational entropy S conf to dynamic behavior. Although the Adam-Gibbs equation uses S conf rather than Sex as the control variable, the relation has been used successfully in a number of experimental studies with S conf replaced by Sex. This is likely a result of a proportionality between S conf and Sex, which we conΓΏrm for simulations of a model
π SIMILAR VOLUMES
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