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The puzzling first-order phase transition in water–glycerol mixtures [electronic resource].

Published
Washington, D.C. : United States. Dept. of Energy, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy
Physical Description
pages 18,063-18,071 : digital, PDF file
Additional Creators
Oak Ridge National Laboratory, United States. Department of Energy, National Science Foundation (U.S.), and United States. Department of Energy. Office of Scientific and Technical Information
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Summary
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.
Report Numbers
E 1.99:1319195
Subject(s)
Note
Published through SciTech Connect.
06/05/2015.
Physical Chemistry Chemical Physics. PCCP (Print) 17 27 ISSN 1463-9076; PPCPFQ AM
Ivan Popov; Anna Greenbaum (Gutina); Alexei P. Sokolov; Yuri Feldman.
Kazan Federal University, Russia
Funding Information
AC05-00OR22725
CHE-1213444
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