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Title: Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid–liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid–liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H{sub 2}O-NaCl and H{sub 2}O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter [J. Phys. Chem. B 104, 8563 (2000)], to be consistent with the presence of the metastable liquid–liquid transition. We elucidate the non-conserved nature of the order parameter (extent of “reaction” between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.
Authors:
; ;  [1]
  1. Institute for Physical Science and Technology and Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, Maryland 20742 (United States)
Publication Date:
OSTI Identifier:
22419804
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 7; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AQUEOUS SOLUTIONS; CONTROL; COUPLING; DENSITY; GLYCEROL; LIQUIDS; NUCLEATION; SODIUM CHLORIDES; SOLUTES; SPECIFIC HEAT; WATER