title: Thermodynamic Analysis of the Two-Liquid Model for Anomalies of Water, HDL-LDL Fluctuations, and Liquid-Liquid Transition.
abstract: After reviewing the protocol-dependent properties of HDA, which thermally anneals to LDA, and the data gap over an unusually large T-range between HDA, LDA, and water, we investigate whether or not, despite HDA's ill-defined state and distinction from a glass, the HDL-LDL fluctuations view of the two-liquid model can explain water's anomalous behavior. An analysis of the density, ρ, compressibility, β, heat capacity, Cp, and thermal conductivity, κ, of water over a monotonic (continuous) path bridging this data gap shows the following: (i) Such a path between ρwater at 320 K and ρHDA yields an untenable thermal expansion coefficient of water. (ii) There is neither a continuous path between βwater at 353 K and βHDA, nor between Cp,water at 363 K and Cp,HDA. (iii) The same value of ρwater, of βwater, or of Cp,water at two temperatures separated by a maxima or a minima is incompatible with the HDL-LDL fluctuations view. (iv) κLDA at ∼140 K is about twice that of κ water at 253 K. (v) κHDA at 120 K is incompatible with κwater at T > 320 K. Thus, there is an internal inconsistency between the thermodynamics of HDA seen as a glass and that of water seen as an HDL-LDL mixture, which is incompatible with both the HDL-LDL fluctuations view and the liquid-liquid transition.
authors.affiliation: Department of Materials Science and Engineering, McMaster University , Hamilton, Ontario L8S 4L7, Canada.|Laboratoire Léon Brillouin (CEA/CNRS), CEA Saclay , 91191 Gif-sur-Yvette Cedex, France.
authors.forename: G P
authors.initials: GP
authors.lastname: Johari
authors.affiliation: Department of Materials Science and Engineering, McMaster University , Hamilton, Ontario L8S 4L7, Canada.|Laboratoire Léon Brillouin (CEA/CNRS), CEA Saclay , 91191 Gif-sur-Yvette Cedex, France.
authors.forename: J
authors.initials: J
authors.lastname: Teixeira