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Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry

Harshad Pathak, Alexander Späh, Niloofar Esmaeildoost, Jonas A. Sellberg, Kyung Hwan Kim, Fivos Perakis, Katrin Amann-Winkel, Marjorie Ladd-Parada, Jayanath Koliyadu, Thomas J. Lane, Cheolhee Yang, Henrik Till Lemke (+7 others)
2021 Proceedings of the National Academy of Sciences of the United States of America  

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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
more » ... 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.
doi:10.1073/pnas.2018379118 pmid:33526683 fatcat:i7kdbfvjvjdnnh3mipxtfialha
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Harshad Pathak, Alexander Späh, Niloofar Esmaeildoost, Jonas A. Sellberg, Kyung Hwan Kim, Fivos Perakis, Katrin Amann-Winkel, Marjorie Ladd-Parada, Jayanath Koliyadu, Thomas J. Lane, Cheolhee Yang, Henrik Till Lemke, Alexander Roland Oggenfuss, Philip J. M. Johnson, Yunpei Deng, Serhane Zerdane, Roman Mankowsky, Paul Beaud, Anders Nilsson. "Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry." Proceedings of the National Academy of Sciences of the United States of America 118.6 (2021) e2018379118