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Princeton University Press, 1996. 424 p. ISBN:0691085951; 9780691085951Metastable 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 govern 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
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