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Title: The puzzling first-order phase transition in water–glycerol mixtures

Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentration of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscositymore » and nucleation, and finally by crystallization, that might lead to significant misinterpretations.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4]
  1. Hebrew Univ. of Jerusalem (Israel). Dept. of Applied Physics; Kazan Federal Univ., Kazan (Russia)
  2. (Gutina), Anna [Hebrew Univ. of Jerusalem (Israel). Dept. of Applied Physics
  3. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry and Joint Inst. for Neutron Sciences; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  4. Hebrew Univ. of Jerusalem (Israel). Dept. of Applied Physics
Publication Date:
Grant/Contract Number:
AC05-00OR22725; CHE-1213444
Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 17; Journal Issue: 27; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE; Kazan Federal University, Russia; National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1319195

Popov, Ivan, Greenbaum, Sokolov, Alexei P., and Feldman, Yuri. The puzzling first-order phase transition in water–glycerol mixtures. United States: N. p., Web. doi:10.1039/C5CP02851E.
Popov, Ivan, Greenbaum, Sokolov, Alexei P., & Feldman, Yuri. The puzzling first-order phase transition in water–glycerol mixtures. United States. doi:10.1039/C5CP02851E.
Popov, Ivan, Greenbaum, Sokolov, Alexei P., and Feldman, Yuri. 2015. "The puzzling first-order phase transition in water–glycerol mixtures". United States. doi:10.1039/C5CP02851E. https://www.osti.gov/servlets/purl/1319195.
@article{osti_1319195,
title = {The puzzling first-order phase transition in water–glycerol mixtures},
author = {Popov, Ivan and Greenbaum and Sokolov, Alexei P. and Feldman, Yuri},
abstractNote = {Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentration of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscosity and nucleation, and finally by crystallization, that might lead to significant misinterpretations.},
doi = {10.1039/C5CP02851E},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 27,
volume = 17,
place = {United States},
year = {2015},
month = {6}
}