DOI: 10.1063/1.1453399. Parametric crossover model and physical limit of stability in supercooled water

Parametric crossover model and physical limit of stability in supercooled water

10.1063/1.1453399

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The two-critical point (TCP) scenario for supercooled water was tested against experimental data with the crossover equation of state (CR EOS) based on the fundamental results of the fluctuation theory of critical phenomena. The CR EOS predicts a second critical point, CP2, in supercooled water with the parameters Tc2=188 K, ρc2=1100 kg⋅m−3, Pc2=230 MPa, and represents the experimental values of the isothermal compressibility in liquid and supercooled water with an average absolute deviation (AAD) of about 1.7% in the pressure range P=0.1–190 MPa, the liquid densities with an AAD of about 0.1%, and the heat capacity with an AAD of about 1.0% in the temperature range 245 K⩽T⩽300 K. The CR EOS also allows calculation of the physical limit of stability in supercooled water—the kinetic spinodal, TKS. At all pressures P&lt;190 MPa, the kinetic spinodal calculated with the CR EOS lies below the homogeneous nucleation temperature, TH, thus satisfying a physically obvious condition TKS⩽TH. We show that the CP2 is always lying in the region where no thermodynamic state is possible—the “nonthermodynamic habitat” for supercooled water; therefore, we consider our result as a strong argument for the TCP scenario, but with the unphysical—“virtual,” rather than real physical, CP2.

Bibliography

Kiselev, S. B., & Ely, J. F. (2002). Parametric crossover model and physical limit of stability in supercooled water. The Journal of Chemical Physics, 116(13), 5657â5665.

Authors 2

S. B. Kiselev (first)
J. F. Ely (additional)

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Dates

Type	When
Created	23 years ago (July 26, 2002, 9:27 a.m.)
Deposited	1 year, 6 months ago (Feb. 7, 2024, 12:23 p.m.)
Indexed	2 weeks, 6 days ago (Aug. 2, 2025, 12:50 a.m.)
Issued	23 years, 4 months ago (April 1, 2002)
Published	23 years, 4 months ago (April 1, 2002)
Published Print	23 years, 4 months ago (April 1, 2002)

Funders 0

None

BibTeX

@article{Kiselev_2002, title={Parametric crossover model and physical limit of stability in supercooled water}, volume={116}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1453399}, DOI={10.1063/1.1453399}, number={13}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Kiselev, S. B. and Ely, J. F.}, year={2002}, month=apr, pages={5657–5665} }

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  "abstract": "<jats:p>The two-critical point (TCP) scenario for supercooled water was tested against experimental data with the crossover equation of state (CR EOS) based on the fundamental results of the fluctuation theory of critical phenomena. The CR EOS predicts a second critical point, CP2, in supercooled water with the parameters Tc2=188\u200aK,\u2008\u03c1c2=1100\u200akg\u22c5m\u22123,\u2008Pc2=230\u200aMPa, and represents the experimental values of the isothermal compressibility in liquid and supercooled water with an average absolute deviation (AAD) of about 1.7% in the pressure range P=0.1\u2013190\u200aMPa, the liquid densities with an AAD of about 0.1%, and the heat capacity with an AAD of about 1.0% in the temperature range 245\u200aK\u2a7dT\u2a7d300\u200aK. The CR EOS also allows calculation of the physical limit of stability in supercooled water\u2014the kinetic spinodal, TKS. At all pressures P&amp;lt;190\u200aMPa, the kinetic spinodal calculated with the CR EOS lies below the homogeneous nucleation temperature, TH, thus satisfying a physically obvious condition TKS\u2a7dTH. We show that the CP2 is always lying in the region where no thermodynamic state is possible\u2014the \u201cnonthermodynamic habitat\u201d for supercooled water; therefore, we consider our result as a strong argument for the TCP scenario, but with the unphysical\u2014\u201cvirtual,\u201d rather than real physical, CP2.</jats:p>",
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