Entropy-driven liquid-liquid separation in supercooled water
arXiv:1207.2101 · doi:10.1038/srep00713
Abstract
Twenty years ago Poole et al. (Nature 360, 324, 1992) suggested that the anomalous properties of supercooled water may be caused by a critical point that terminates a line of liquid-liquid separation of lower-density and higher-density water. Here we present an explicit thermodynamic model based on this hypothesis, which describes all available experimental data for supercooled water with better quality and with fewer adjustable parameters than any other model suggested so far. Liquid water at low temperatures is viewed as an 'athermal solution' of two molecular structures with different entropies and densities. Alternatively to popular models for water, in which the liquid-liquid separation is driven by energy, the phase separation in the athermal two-state water is driven by entropy upon increasing the pressure, while the critical temperature is defined by the 'reaction' equilibrium constant. In particular, the model predicts the location of density maxima at the locus of a near-constant fraction (about 0.12) of the lower-density structure.
7 pages, 6 figures. Version 2 contains an additional supplement with tables for the mean-field equation
Cited by in corpus (46)
- Understanding water's anomalies with locally favored structures
- Two-State Thermodynamics and the Possibility of a Liquid-Liquid Phase Transition in Supercooled TIP4P/2005 Water
- Two-structure thermodynamics for the TIP4P/2005 model of water covering supercooled and deeply stretched regions
- Thermodynamic behavior of supercritical matter
- Nature of the anomalies in the supercooled liquid state of the mW model of water
- Reversible structural transformations in supercooled water from 135 to 245 K
- Two-state thermodynamics of the ST2 model for supercooled water
- Equation of state for supercooled water at pressures up to 400 MPa
- Crystal nucleation as the ordering of multiple order parameters
- Local Structure Analysis in Liquid Water
- Polymer Glass Formation: Role of Activation Free Energy, Configurational Entropy, and Collective Motion
- Water-like anomalies as a function of tetrahedrality
- Unravelling the contribution of local structures to the anomalies of water: the synergistic action of several factors
- Thermodynamics of Fluid Polyamorphism
- Breakdown of the Stokes-Einstein Relation Above the Melting Temperature in a Liquid Phase-Change Material
- Thermal Conductivity of Supercooled Water
- Behavior of Supercooled Aqueous Solutions Stemming from Hidden Liquid-Liquid Transition in Water
- Persistent local order heterogeneity in the supercritical carbon dioxide
- The physics of Empty Liquids: from Patchy particles to Water
- Roles of liquid structural ordering in glass transition, crystallization, and water's anomalies
- Tunable liquid-liquid critical point in an ionic model of silica
- Optical Kerr effect of liquid and supercooled water: the experimental and data analysis perspective
- Minimum in the thermal conductivity of supercooled water: a computer simulation study
- Hydrogen bond correlated percolation in a supercooled water monolayer as a hallmark of the critical region
- Phase Transitions Affected by Natural and Forceful Molecular Interconversion
- Water above spinodal
- Helium at elevated pressures: Quantum liquid with non-static shear rigidity
- Identification of local structures in water from supercooled to ambient conditions
- A New Single Equation of State to describe the Dynamic Viscosity and Self-Diffusion Coefficient for all Fluid Phases of Water from 200 K to 1800 K based on a New Original Microscopic Model
- Predicting Glass-to-Glass and Liquid-to-Liquid Phase Transitions in Water using Classical Nucleation Temperature
- High-Resolution Adiabatic Calorimetry of Supercooled Water
- Dielectric Anomalies in Crystalline Ice: Indirect Evidence of the Existence of a Liquid-Liquid Critical Point in H2O
- Second critical point of water in supercooled confined water in L,L-diphenylalanine micro/nanotubes
- Modeling Fluid Polyamorphism Through a Maximum-Valence Approach
- Two state model for critical points and the negative slope of the melting-curve
- Interfacial Properties of Fluids Exhibiting Liquid Polyamorphism and Water-Like Anomalies
- Revealing the three-component structure of water with principal component analysis (PCA) on X-ray spectrum
- Manifestations of the structural origin of supercooled water's anomalies in the heterogeneous relaxation on the potential energy landscape
- Nonlocal density functional theory of water taking into account many-body dipole correlations: Binodal and surface tension of 'liquid-vapour' interface
- Shear and bulk viscosities of water up to 1.6 GPa and anomaly in the structural relaxation time
- Hamiltonian limited valence model for liquid polyamorphism
- Generic Maximum-Valence Model for Fluid Polyamorphism
- Supercritical-subcritical correspondence, asymmetric effects and antisymmetric corrections near a critical point
- Machine learning evaluation of structural descriptors for supercooled water
- Liquid-Liquid Crossover in Water Model: Local Structure vs. Kinetics of Hydrogen Bonds
- Thermodynamic Modeling of Fluid Polyamorphism in Hydrogen at Extreme Conditions