Princeton University Press, 1996. 424 p. ISBN:0691085951;
9780691085951
Metastable Liquids provides a comprehensive treatment of the properties of liquids under conditions where the stable state is a vapor, a solid, or a liquid mixture of different composition. It examines the fundamental principles that gove the equilibrium properties, stability, relaxation mechanisms, and relaxation rates of metastable liquids.
Building on the interplay of kinetics and thermodynamics that determines the thermophysical properties and structural relaxation of metastable liquids, it offers an in-depth treatment of thermodynamic stability theory, the statistical mechanics of metastability, nucleation, spinodal decomposition, supercooled liquids, and the glass transition.
An introductory chapter illustrates, with numerous examples, the importance and ubiquity of metastable liquids.
Examples include the ascent of sap in plants, the strategies adopted by many living organisms to survive prolonged exposure to sub-freezing conditions, the behavior of proteins at low temperatures, metastability in mineral inclusions, ozone depletion, the preservation and storage of labile biochemicals, and the prevention of natural gas clathrate hydrate formation.
All mathematical symbols are defined in the text and key equations are clearly explained. More complex mathematical explanations are available in the appendixes.
Contents
Preface and acknowledgments
Introduction: Metastable Liquids in Nature and Technology
Introduction
Definitions
Two Experiments: Superheated and Supercooled Water in the Laboratory
Metastable Liquids in Nature
Life at Low Temperatures
Proteins at Low Temperatures
The Ascent of Sap in Plants
Mineral Inclusions
Clouds
Metastable Liquids in Technology
Storage of Proteins and Cells by Supercooling
Some Uses of Liquids under Tension
Vapor Explosions
Kinetic Inhibition of Natural Gas Clathratc Hydrates
References
Thermodynamics
Phenomenological Approach: Stability Criteria
Phenomenological Approach: Stability of Pure Fluids
Superheated Liquids
The Spinodal Envelope
The van der Waals Fluid
Pseudocritical and Critical Exponents
Stability Limit Predictions with Equations of State
Continuity and Divergences in Superheated Liquids
The "Pseudospinodal"
Liquids That Expand When Cooled: The Stability Limit Conjecture
Metasiable Phase Equilibrium
Phenomenological Approach: Stability of Fluid Mixtures
Binary Mixtures
Multicomponent Mixtures
Critique of the Phenomenological Approach: Metastability and Statistical Mechanics
Stability of Liquids with Respect to Crystalline Solids
References
Kinetics
Homogeneous Nucleation
Classical Nucleation Theory
Energetics of Embryo Formation: Rigorous Approaches
Kinetic Nucleation Theories
Homogeneous Nucleation in Superheated Liquids
Homogeneous Nucleation in Supercooled Liquids
The Approach to Steady State
Spinodal Decomposition
The Transition From Nucleation to Spinodal Decomposition
Heterogeneous Nucleation
References
Supercooled Liquids
Crystallization and Vitrification
Elementary Phenomenology of Vitrification upon Supercooling
Thermodynamic Viewpoint of the Glass Transition
Kauzmann's Paradox
Cooperative Relaxations and the Entropy Viewpoint
Free Volume Theory
Dynamic Viewpoint of the Glass Transition: Mode Coupling
Strong and Fragile Liquids
Supercooled and Glassy Water
Experiments
Interpretation
Glassy Water
Computer Simulation of Supercooled Liquids
References
Outlook
APPENDIX I: Stability of Fluids: Thermodynamic and Mathematical Proofs
Appendix 2: Thermodynamics of Fluid Interfaces
Appendix 3: Definitions of Microscopic and Statistical Quantities
Index
Metastable Liquids provides a comprehensive treatment of the properties of liquids under conditions where the stable state is a vapor, a solid, or a liquid mixture of different composition. It examines the fundamental principles that gove the equilibrium properties, stability, relaxation mechanisms, and relaxation rates of metastable liquids.
Building on the interplay of kinetics and thermodynamics that determines the thermophysical properties and structural relaxation of metastable liquids, it offers an in-depth treatment of thermodynamic stability theory, the statistical mechanics of metastability, nucleation, spinodal decomposition, supercooled liquids, and the glass transition.
An introductory chapter illustrates, with numerous examples, the importance and ubiquity of metastable liquids.
Examples include the ascent of sap in plants, the strategies adopted by many living organisms to survive prolonged exposure to sub-freezing conditions, the behavior of proteins at low temperatures, metastability in mineral inclusions, ozone depletion, the preservation and storage of labile biochemicals, and the prevention of natural gas clathrate hydrate formation.
All mathematical symbols are defined in the text and key equations are clearly explained. More complex mathematical explanations are available in the appendixes.
Contents
Preface and acknowledgments
Introduction: Metastable Liquids in Nature and Technology
Introduction
Definitions
Two Experiments: Superheated and Supercooled Water in the Laboratory
Metastable Liquids in Nature
Life at Low Temperatures
Proteins at Low Temperatures
The Ascent of Sap in Plants
Mineral Inclusions
Clouds
Metastable Liquids in Technology
Storage of Proteins and Cells by Supercooling
Some Uses of Liquids under Tension
Vapor Explosions
Kinetic Inhibition of Natural Gas Clathratc Hydrates
References
Thermodynamics
Phenomenological Approach: Stability Criteria
Phenomenological Approach: Stability of Pure Fluids
Superheated Liquids
The Spinodal Envelope
The van der Waals Fluid
Pseudocritical and Critical Exponents
Stability Limit Predictions with Equations of State
Continuity and Divergences in Superheated Liquids
The "Pseudospinodal"
Liquids That Expand When Cooled: The Stability Limit Conjecture
Metasiable Phase Equilibrium
Phenomenological Approach: Stability of Fluid Mixtures
Binary Mixtures
Multicomponent Mixtures
Critique of the Phenomenological Approach: Metastability and Statistical Mechanics
Stability of Liquids with Respect to Crystalline Solids
References
Kinetics
Homogeneous Nucleation
Classical Nucleation Theory
Energetics of Embryo Formation: Rigorous Approaches
Kinetic Nucleation Theories
Homogeneous Nucleation in Superheated Liquids
Homogeneous Nucleation in Supercooled Liquids
The Approach to Steady State
Spinodal Decomposition
The Transition From Nucleation to Spinodal Decomposition
Heterogeneous Nucleation
References
Supercooled Liquids
Crystallization and Vitrification
Elementary Phenomenology of Vitrification upon Supercooling
Thermodynamic Viewpoint of the Glass Transition
Kauzmann's Paradox
Cooperative Relaxations and the Entropy Viewpoint
Free Volume Theory
Dynamic Viewpoint of the Glass Transition: Mode Coupling
Strong and Fragile Liquids
Supercooled and Glassy Water
Experiments
Interpretation
Glassy Water
Computer Simulation of Supercooled Liquids
References
Outlook
APPENDIX I: Stability of Fluids: Thermodynamic and Mathematical Proofs
Appendix 2: Thermodynamics of Fluid Interfaces
Appendix 3: Definitions of Microscopic and Statistical Quantities
Index