Semiconductor and Metal Binary Systems: Phase Equilibria and Chemical Thermodynamics

This book is devoted to the fundamentals of the theoretical analysis of phase equilibrium diagrams. Phase diagrams are known to play an important role in met­ allurgy and materials science, chemical engineering, petroleum refining, etc. A study of phase diagrams can help in choosing the optimal composition of mixtures and alloys and in determining the appropriate conditions for their thermal treatment, as well as in determining the efficiency of such processes as distillation, rectifica­ tion, zone refining, and controlled crystallization for the separation and purifi(;ation of materials. In spite of this, the extensive thermodynamic information which can be extracted from phase diagrams has scarcely been utilized until recently, due to the of the analysis of phase equilibria. comparatively poorly developed foundations We have attempted to present a general picture of the thermodynamic analysis of phase diagrams, and to demonstrate the broad possibilities of this approach in elucidating the nature of the interaction of the components and the structure of the phases. This book summarizes research carried out at the Moscow Institute of Electronic Engineering over the past decade. Extensive summaries of published data are also included. In the course of our work we have made extensive use of modern computing methods, which allowed solutions to be obtained to many problems.

Table of Contents:
1 Some General Relations of Chemical Thermodynamics.- 1. Systems, Their Properties and Classification. Thermodynamic Parameters and the Equation of State. Thermodynamic Processes.- 2. Partial Molar Quantities and Their Properties.- 3. The Zeroth, First, and Second Laws of Thermodynamics.- 4. Entropy Relations and Some Expressions Involving Derivatives of Thermodynamic Functions.- 5. Characteristic Thermodynamic Functions and the Gibbs-Helmholtz Equation.- 2 Theory of Chemical Potentials and the General Theory of Thermodynamic Equilibrium.- 1. Fundamental Theorems and Equations. The Gibbs-Duhem Equation.- 2. The Equilibrium Principle of Gibbs.- 3. Conditions for Phase Equilibrium. Real and Virtual Components.- 4. Conditions for Chemical Equilibrium. The Law of Mass Action.- 5. Criteria of Phase Stability in Heterogeneous Systems.- 6. The Principle of Equilibrium Displacement (the Gibbs-Le Chatelier Principle).- 7. Displacement along Equilibrium Lines. Generalized van der Waals Differential Equations.- 8. The Adequacy of Various Deductions of the Principle of Displacements along Equilibrium Lines.- 3 Phase Equilibria in Two-Component Systems.- 1. General Considerations on State Diagrams.- 2. The Isobaric-Isothermal Potential as a Function of Temperature, Pressure, and Concentration.- 3. Thermodynamic Derivation of Basic Types of State Diagrams in Two-Component Systems.- 4 Fundamentals of the Thermodynamic Theory of Solutions of Condensed Systems.- 1. Generalized Concept of Solution. Thermodynamic Classification of Solutions.- 2. Thermodynamic Functions of Mixing. Basic Properties and the Law of Ideal Solutions.- 3. The Law of Nonideal Solutions. Excess Thermodynamic Functions. Classification of Deviations from Ideality.- 4. The Concept of a Regular Solution. Lattice Modelof Solutions. Strictly Regular Solution and Its Modifications.- 5. Formal Description of the Thermodynamic Properties of Real Systems.- 6. Associated Solution Model.- 5 Thermodynamic Analysis of Phase Diagrams within Various Approximate Theories of Solutions.- 1. Analysis of Phase Equilibria Curves in Two-Component Systems Based on the Theory of Ideal Solutions.- 2. Interrelation of Various Types of Phase Equilibrium Diagrams and the Nature of Intermolecular Interactions.- 3. Analysis of Liquidus and Solidus Curves in Systems with Restricted and Unrestricted Solubilities.- 4. Thermodynamic Justification of the Retrograde Solidus. Calculation of the Retrograde Solidus in Various Approximations.- 5. Analysis of the Liquidus Curve of a Congruently Melting Compound AmBn in Various Approximations of Ideal Solutions.- 6. Equation of the Liquidus Curve and Thermodynamic Analysis of Systems with Incongruently Melting Compounds.- 7. Various Methods of Estimating the Exchange Energy from Experimental Data.- 8. Calculation of Thermodynamic Properties of Alloys from Data on Phase Equilibria.- 9. Choice of Model Solution Based on Matching with Experimental Phase Equilibrium Data.- 6 Thermodynamic Analysis of the Dissociation of Chemical Compounds.- 1. Shape and Position of Maxima in the Liquidus and Solidus Curves.- 2. Thermodynamic Basis of Various Estimation Procedures for the Dissociation Parameters of Congruently Melting Compounds.- 3. Estimates of the Degree of Dissociation of Chemical Compounds in Various Approximations of the Thermodynamics of Solutions.- 4. Dissociation of Binary Compounds in Quasibinary Solutions of Three-Component Systems.- Conclusion.- References.