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

Abstract

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 andmore » self-diffusion coefficient of water and these properties decrease rapidly below 235 K.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [4]; ORCiD logo [3];  [5];  [5]; ORCiD logo [5];  [5];  [5];  [5]; ORCiD logo [5]; ORCiD logo [1]
+ Show Author Affiliations
  1. Stockholm Univ. (Sweden)
  2. AlbaNova Univ. Center, Stockholm (Sweden)
  3. Pohang Univ. of Science and Technology (South Korea)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. SwissFEL, Villigen (Switzerland)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); Swedish Research Council (SRC); National Research Foundation of Korea (NRF)
OSTI Identifier:
1777412
Grant/Contract Number:  
AC02-76SF00515; 667205; 2013-8823; 2017-05128; 2019-05542; 730872; 1808; 1909; 2044; 2020R1A5A1019141
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 118; Journal Issue: 6; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; supercooled water; specific-heat capacity; fragile-to-strong transition; liquid-liquid; critical point

Citation Formats

Pathak, Harshad, Späh, Alexander, Esmaeildoost, Niloofar, Sellberg, Jonas A., Kim, Kyung Hwan, Perakis, Fivos, Amann-Winkel, Katrin, Ladd-Parada, Marjorie, Koliyadu, Jayanath, Lane, Thomas J., Yang, Cheolhee, Lemke, Henrik Till, Oggenfuss, Alexander Roland, Johnson, Philip M., Deng, Yunpei, Zerdane, Serhane, Mankowsky, Roman, Beaud, Paul, and Nilsson, Anders. Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry. United States: N. p., 2021. Web. doi:10.1073/pnas.2018379118.
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Pathak, Harshad, Späh, Alexander, Esmaeildoost, Niloofar, Sellberg, Jonas A., Kim, Kyung Hwan, Perakis, Fivos, Amann-Winkel, Katrin, Ladd-Parada, Marjorie, Koliyadu, Jayanath, Lane, Thomas J., Yang, Cheolhee, Lemke, Henrik Till, Oggenfuss, Alexander Roland, Johnson, Philip M., Deng, Yunpei, Zerdane, Serhane, Mankowsky, Roman, Beaud, Paul, & Nilsson, Anders. Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry. United States. https://doi.org/10.1073/pnas.2018379118
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Pathak, Harshad, Späh, Alexander, Esmaeildoost, Niloofar, Sellberg, Jonas A., Kim, Kyung Hwan, Perakis, Fivos, Amann-Winkel, Katrin, Ladd-Parada, Marjorie, Koliyadu, Jayanath, Lane, Thomas J., Yang, Cheolhee, Lemke, Henrik Till, Oggenfuss, Alexander Roland, Johnson, Philip M., Deng, Yunpei, Zerdane, Serhane, Mankowsky, Roman, Beaud, Paul, and Nilsson, Anders. Tue . "Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry". United States. https://doi.org/10.1073/pnas.2018379118. https://www.osti.gov/servlets/purl/1777412.
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@article{osti_1777412,
title = {Enhancement and maximum in the isobaric specific-heat capacity measurements of deeply supercooled water using ultrafast calorimetry},
author = {Pathak, Harshad and Späh, Alexander and Esmaeildoost, Niloofar and Sellberg, Jonas A. and Kim, Kyung Hwan and Perakis, Fivos and Amann-Winkel, Katrin and Ladd-Parada, Marjorie and Koliyadu, Jayanath and Lane, Thomas J. and Yang, Cheolhee and Lemke, Henrik Till and Oggenfuss, Alexander Roland and Johnson, Philip M. and Deng, Yunpei and Zerdane, Serhane and Mankowsky, Roman and Beaud, Paul and Nilsson, Anders},
abstractNote = {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.},
doi = {10.1073/pnas.2018379118},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 118,
place = {United States},
year = {Tue Feb 09 00:00:00 EST 2021},
month = {Tue Feb 09 00:00:00 EST 2021}
}
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