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.

Growth rate of crystalline ice and the diffusivity of supercooled water from 126 to 262 K

“…Anomalies are observed in thermodynamic response functions (such as the isobaric heat capacity and the isothermal compressibility) and dynamic properties (such as diffusion, viscosity, and dielectric relaxation) over a wide range of pressures, P, and temperatures, T. These anomalies become more pronounced for supercooled water, and it is generally believed that the unusual properties arise as water adopts a more ice-like structure as the temperature decreases. However, the underlying reasons are fiercely debated (5,11,(14)(15)(16)(17). At ambient pressures, many of the anomalous properties appear to diverge at a temperature, T s , around 228 K leading to the "stability-limit conjecture" in which the liquid becomes unstable below T s (2).…”

Sub-T g features of glasses formed by cooling glycerol under pressure – Additional incompatibility of vibrational with configurational states in the depressurized, high density glass

“…12,13 On the basis of that sub-T g endotherm, one of us concluded 14 that the corresponding endotherm previously observed on heating annealed high-density solid water had been mistaken as a second T g of water, and that this high-density solid water is an ill-defined state. 20 The intriguing nature of the above-mentioned sub-T g decrease in  made it necessary to study this feature in detail by varying the T and p protocol for glass formation as well as the protocol for studying the glass formed. It also required a corresponding study of C p measured in the same experiment as .…”

Micro- and Nano-Liquid Phases Coexistent with Ice as Separation and Reaction Media.

“…However, some studies have shown that the QLL is well developed at the interface of a solid material with ice; therefore, the electrode surface is also likely to be in contact with the FCS. [20] Cyclic voltammograms measured with the Fe(CN) 6 4 À /Fe(CN) 6 3 À reversible redox couple, show a strong dependence on the experimental parameters, including the size of the working electrode, concentration ratio, and the thermal history of the frozen sample. [54a] For concentration ratios higher than 100, voltam- Reproduced with permission from reference [47].…”

“…At the nanometer range, a liquid phase can remain unfrozen far below its normal freezing point, allowing studies of supercooled liquids. This approach is often used to find the liquid–liquid transition of water in the so‐called “no man's land” ,. Some other properties or phenomena of fundamental interest, e. g., high liquid viscosity, high proton conductance, slip flow at the wall, have also been reported for liquid phases at such small dimensions.…”

“…This approach is often used to find the liquid-liquid transition of water in the so-called "no man's land". [3,6] Some other properties or phenomena of fundamental interest, e. g., high liquid viscosity, [7] high proton conductance, [1b] slip flow at the wall, [8] have also been reported for liquid phases at such small dimensions.…”