Phase Equilibria: Basic Principles, Applications, Experimental Techniques presents an analytical treatment in the study of the theories and principles of phase equilibria.
The book is organized to afford a deep and thorough understanding of such subjects as the method of species model systems; condensed phase-vapor phase equilibria and vapor transport reactions; zone refining techniques; and nonstoichiometry.
Physicists, physical chemists, engineers, and materials scientists will find the book a good reference material.

Contenu

Contents

Preface

Acknowledgments

Some Preliminary Remarks and Observations
Thermodynamics and the Phase Rule
Definition of Terms and Concepts
A. Introduction
B. Systems
C. Phases
D. The Limits Imposed by an Experimental Situation
E. The Component, Species, and Mole Terms
F. Defining the Number of Components Present
G. Chemical, Compound, Substance and Constituent
The Thermodynamic Basis of the Phase Rule
A. Introduction
B. The Phase Rule and Its Basis
C. Choice of Systems and the Reduced Phase Rule
D. The Vapor Pressure, the Evaporation Rate and the Reduced Phase Rule
E. The Time Factor in a Non-Time-Dependent Science
Systems of One Component-Temperature Effects
A. Introduction
B. The Analytical Description of Univariance
C. Univariant Equilibria Involving Solids and Gases
D. Univariant Equilibria Involving Liquids and Gases
E. Univariant Equilibria Involving Solids and Liquids
F. Further Aspects of Univariant Systems
G. Metastability in One-Component Systems
H. Structure Changes in Unary Systems
Systems of One Component-Pressure Effects and the Continuous Nature of Metastability
A. Metastable-to-Stable Transformations with Increasing Pressure
B. Solid Phases That Do Not Exhibit Stable Solid-Vapor Equilibria at Any Temperature: Monotropes
Complex Metastability in One-Component Systems
A. Systems with Solid-Vapor Univariance
B. Stable High-Pressure Systems
Other Aspects of One-Component Behavior
A. The Effects of Inert Gas Pressures on the Vapor Pressure of Single-Component Solids or Liquids
B. The Effect of Surface Tension on the Vapor Pressure of a Single Component
Enthalpy and Entropy Diagrams of State for Unary Systems
A. Introduction
B. Enthalpie Relationships and the Enthalpy Diagrams of State
C. Entropie Relationships and Entropy Diagrams of State
Multicomponent Systems, Homogeneous Systems, and the Equilibrium Constant
A. Introduction
B. The Species and the Homogeneous Equilibrium Constant
C. Standard States and Their Significance
D. The Homogeneous Equilibrium Constant in Terms of Mole Fractions
E. The Variation of Equilibrium Constant with Temperature
Multicomponent Systems, the Equilibrium Constant, and Heterogeneous Systems
A. Introduction
B. The Chemical Potential for Components and Species
C. Equilibrium Constants in Terms of Partial Molar Quantities
The Thermodynamic Parameters-Fugacity and Activity
A. Introduction
B. Rationale for a Thermodynamic Approach to the Treatment of Real Systems
C. The Fugacity, Standard States, and Free Energy Relations
D. Thermodynamic Concentrations-The Activity
Two-Component Systems-Systems in Which One Phase Is Pure and in Which Species and Component Mole Terms Are Equivalent-Simple Eutectic Interactions
A. Introduction
B. The Analytical Expression of Univariance in a Simple Eutectic Interaction
C. An Alternative Derivation of Univariant Equations for Eutectic Systems
Graphical Representations of Simple Eutectic Interactions
A. Introduction
B. The Phase Diagram-A Qualitative View
C. The Lever Arm Principle
D. Specifics of Application of the Lever Arm Principle
Eutectic Systems Continued-The Parameter Hfusion/Tmelting and Its Influence on the Contour of Eutectic Liquidus Curves
A. Introduction
B. Theoretical Analysis
C. Application of the / A Principle to Real Systems
D. Pseudobinary Systems
Eutectic Interactions Continued-The Effects of Homogeneous Equilibria on Liquidus Contours
A. Introduction
B. Dissociation of One of the Liquid-Phase Species
C. Solution for the AB Liquidus Curve
D. The Liquidus for the Nondissociating Component
Common Species Effects in Simple Eutectic Systems
A. Introduction
B. The Liquidus Curve for AB
C. The Liquidus for B
Eutectic Interactions Continued-The Effects of Association on Liquidus Contours
A. Introduction
B. The A Liquidus
C. The Liquidus for the Component B
Eutectic Interactions Continued-Effects of End Member Species Interactions on Liquidus Contours
A. Introduction
B. Solution of the A Liquidus,
C. Solution of the B Liquidus,
Eutectic Interactions Continued-Effects of Complete Dissociation on Liquidus Contours
A. Introduction
B. The AB Liquidus
C. The B Liquidus
Eutectic Interactions Continued-Graphical Description of the Results of Chapters 16-20
A. Introduction
B. Test Cases
C. Dissociation of a Pseudounary Component in the System AB-C
D. Dissociation with a Common Species Effect
E. Association of One of the Liquid-Phase Species
F. Reaction between Liquid-Phase Species
G. Effects of Complete Dissociation on Liquidus Contours
Eutectic Interactions Continued-Single Compound Formation in Binary Systems and Coordinate Transformations
A. Introduction
B. A Single Compound Is Generated
C. Scaling Factors and Coordinate Transformations
D. Examination of Solubility Curves in Systems Exhibiting Compound Formation
Eutectic Interactions Continued-Multiple Compound Formation in Binary Systems and Coordinate Transformations in Multiple Compound Systems
A. Introduction
B. Two Compounds Are Generated
Eutectic Interactions Continued-p-T-Mx Representations and Phase Changes
A. Introduction
B. The -p- x Diagram of State
C. Phase Changes-A Second Quadruple Point
Eutectic Interactions Continued-Intermediate Compound Instability-Incongruently Melting Compounds
A. Introduction
B. The Intermediate Compound AxBy Melts Incongruently
C. The Three-Dimensional Model of Incongruently Melting Systems
D. The Effect of Pressure When the S-L Slope of the Intermediate Incongruently Melting Compound Is Positive
Liquid Immiscibility in Eutectic Systems
A. Introduction
B. The Miscibility Gap Is Confined to the Liquid Regions
C. The T-p- x Representation of the Eutectic System Showing Liquid Phase Immiscibility
D. The Intersection of a Miscibility Gap with the Liquidus Regions
E. The T-p- Representation of the MG Intersecting a Liquidus
Systems Exhibiting Solid Solubility-Ascending Solid Solutions
A. Introduction
B. The Analytical Description of Univariance for Ascending Solid Solutions
C. The Graphical Representation of Ascending Solid Solutions
D. The Purification of Materials
E. The General Experimental Approach to the Resolution of Solid Solution Diagrams
F. The Space Model for Solid Solution Systems
Solid Solutions Continued-Graphical Representation of Idealized Systems and Some Comment on Real Systems
A. Introduction
B. Temperature-Composition Diagrams for Cases I-XIV
C. Real Systems
Solid Solutions Continued-Complete Liquid Phase Dissociation and Minimum Type Solid Solutions
A. Introduction
B. The Qualitative Aspects of Fig. 1
C. Complete Dissociation in Solid Solutio…