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Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-9284-4774
Stockholm University, Faculty of Science, Department of Physics.
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2021 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 118, no 6, article id e2018379118Article in journal (Refereed) Published
Abstract [en]

Knowledge of the temperature dependence of the isobaric specific heat (Cp) upon deep supercooling can give insights regarding the anomalous properties of water. If a maximum in Cp exists at a specific temperature, as in the isothermal compressibility, it would further validate the liquid–liquid critical point model that can explain the anomalous increase in thermodynamic response functions. The challenge is that the relevant temperature range falls in the region where ice crystallization becomes rapid, which has previously excluded experiments. Here, we have utilized a methodology of ultrafast calorimetry by determining the temperature jump from femtosecond X-ray pulses after heating with an infrared laser pulse and with a sufficiently long time delay between the pulses to allow measurements at constant pressure. Evaporative cooling of ∼15-µm diameter droplets in vacuum enabled us to reach a temperature down to ∼228 K with a small fraction of the droplets remaining unfrozen. We observed a sharp increase in Cp, from 88 J/mol/K at 244 K to about 218 J/mol/K at 229 K where a maximum is seen. The Cp maximum is at a similar temperature as the maxima of the isothermal compressibility and correlation length. From the Cp measurement, we estimated the excess entropy and self-diffusion coefficient of water and these properties decrease rapidly below 235 K.

Place, publisher, year, edition, pages
2021. Vol. 118, no 6, article id e2018379118
Keywords [en]
supercooled water, specific-heat capacity, fragile-to-strong transition, liquid liquid critical point
National Category
Condensed Matter Physics Physical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-190883DOI: 10.1073/pnas.2018379118ISI: 000617355300060OAI: oai:DiVA.org:su-190883DiVA, id: diva2:1532923
Note

The importance of molecular understanding of the structure, dynamics. and properties of liquid water is recognized in many scientific disciplines. Here, we study experimentally the structure and thermodynamics of bulk liquid water as it is supercooled by evaporation down to ∼228 K. The unique aspect of this work is the use of ultrafast calorimetry that enables us to determine the specific-heat capacity of water to unprecedentedly low temperatures. The observed maximum of about 218 J/mol/K at 229 K is consistent with the liquid–liquid critical point model and supports a proposed fragile-to-strong transition at ∼220 K to explain the steep decrease in the estimated self-diffusion coefficient below 235 K. 

Available from: 2021-03-03 Created: 2021-03-03 Last updated: 2022-02-25Bibliographically approved

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Pathak, HarshadSpäh, AlexanderPerakis, FivosAmann-Winkel, KatrinLadd-Parada, Marjorie
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