371457 Behavior of Supercooled Aqueous Solutions Stemming from Hiddle Liquid-Liquid Transition in Water

Tuesday, November 18, 2014: 2:22 PM
Crystal Ballroom A/F (Hilton Atlanta)
John Biddle1, Vincent Holten1 and Mikhail A. Anisimov2, (1)Institute for Physical Science and Technology, University of Maryland, College Park, College Park, MD, (2)Department of Chemical Engineering, University of Maryland, College Park, MD

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, H2O-NaCl and H2O-Glycerol.  We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter, to be consistent with the presence of the metastable liquid-liquid transition. We suggest an interpretation of the experiments on aqueous solutions of glycerol, reported by Murata and Tanaka, elucidating the non-conserved nature of the order parameter, its coupling with density and concentration, and the peculiarity of spinodal decomposition without phase separation". We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

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See more of this Session: Thermophysical Properties and Phase Behavior I
See more of this Group/Topical: Engineering Sciences and Fundamentals