Reisman / Loebl Phase Equilibria

Basic Principles, Applications, Experimental Techniques
1. Auflage 2013
ISBN: 978-1-4832-6584-1
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, 560 Seiten, Web PDF

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.

Autoren/Hrsg.

Reisman, Arnold

Loebl, Ernest M.

Inhaltsverzeichnis

1;Front Cover;1
2;Phase Equilibria: Basic Principles, Applications, Experimental Techniques;4
3;Copyrigh Page;5
4;Table of Contents;6
5;Preface;14
6;Acknowledgments;16
7;Chapter 1. Some Preliminary Remarks and Observations;18
8;Chapter 2. Thermodynamics and the Phase Rule;21
9;Chapter 3. Definition of Terms and Concepts;26
9.1;A. INTRODUCTION;26
9.2;B. SYSTEMS;26
9.3;C. PHASES;27
9.4;D. THE LIMITS IMPOSED BY AN EXPERIMENTAL SITUATION;28
9.5;E. THE COMPONENT, SPECIES, AND MOLE TERMS;36
9.6;F. DEFINING THE NUMBER OF COMPONENTS PRESENT;41
9.7;G. CHEMICAL, COMPOUND, SUBSTANCE, AND CONSTITUENT;42
10;Chapter 4. The Thermodynamic Basis of the Phase Rule;44
10.1;A. INTRODUCTION;44
10.2;B. THE PHASE RULE AND ITS BASIS;46
10.3;C. CHOICE OF SYSTEMS AND THE REDUCED PHASE RULE;49
10.4;D. THE VAPOR PRESSURE, THE EVAPORATION RATE, AND THE REDUCED PHASE RULE;50
11;Chapter 5. Systems of One Component—Temperature Effects;55
11.1;A. INTRODUCTION;55
11.2;B. THE ANALYTICAL DESCRIPTION OF UNIVARIANCE
;57
11.3;C. UNIVARIANT EQUILIBRIA INVOLVING SOLIDS AND GASES;58
11.4;D. UNIVARIANT EQUILIBRIA INVOLVING LIQUIDS AND GASES;60
11.5;E. UNIVARIANT EQUILIBRIA INVOLVING SOLIDS AND LIQUIDS;62
11.6;F. FURTHER ASPECTS OF UNIVARIANT SYSTEMS;64
11.7;G. METASTABILITY IN ONE-COMPONENT SYSTEMS;64
11.8;H. STRUCTURE CHANGES IN UNARY SYSTEMS;69
12;Chapter 6. Systems of One Component—Pressure Effects and the Continuous Nature of Metastability;78
12.1;A. METASTABLE-TO-STABLE TRANSFORMATIONS WITH INCREASING PRESSURE;78
12.2;B. SOLID PHASES THAT DO NOT EXHIBIT STABLE SOLID–VAPOR EQUILIBRIA AT ANY TEMPERATURE: MONOTROPES;80
13;Chapter 7. Complex Metastability in One-Component Systems;88
13.1;A. SYSTEMS WITH SOLID–VAPOR UNIVARIANCE;88
13.2;B. STABLE HIGH-PRESSURE SYSTEMS;91
14;Chapter 8. Other Aspects of One-Component Behavior;96
14.1;A. THE EFFECTS OF INERT GAS PRESSURES ON THE VAPOR PRESSURE OF SINGLE-COMPONENT SOLIDS OR LIQUIDS;96
14.2;B. THE EFFECT OF SURFACE TENSION ON THE VAPOR PRESSURE OF A SINGLE COMPONENT;99
15;Chapter 9. Enthalpy and Entropy Diagrams of State for Unary Systems;102
15.1;A. INTRODUCTION;102
15.2;B. ENTHALPIC RELATIONSHIPS AND THE ENTHALPY DIAGRAMS OF STATE;103
15.3;C. ENTROPIO RELATIONSHIPS AND ENTROPY DIAGRAMS OF STATE;106
16;Chapter I0. Multicomponent Systems, Homogeneous Systems, and the Equilibrium Constant;109
16.1;A. INTRODUCTION;109
16.2;B. THE SPECIES AND THE HOMOGENEOUS EQUILIBRIUM CONSTANT;110
16.3;C. STANDARD STATES AND THEIR SIGNIFICANCE;118
16.4;D. THE HOMOGENEOUS EQUILIBRIUM CONSTANT IN TERMS OF MOLE FRACTIONS;120
16.5;E. THE VARIATION OF EQUILIBRIUM CONSTANT WITH TEMPERATURE;122
17;Chapter II. Multicomponent Systems, the Equilibrium Constant, and Heterogeneous Systems;125
17.1;A. INTRODUCTION;125
17.2;B. THE CHEMICAL POTENTIAL FOR COMPONENTS AND SPECIES;126
17.3;C. EQUILIBRIUM CONSTANTS IN TERMS OF PARTIAL MOLAR QUANTITIES;129
18;Chapter 12. The Thermodynamic Parameters—Fugacity and Activity;134
18.1;A. INTRODUCTION;134
18.2;B. RATIONALE FOR A THERMODYNAMIC APPROACH TO THE TREATMENT OF REAL SYSTEMS;135
18.3;C. THE FUGACITY, STANDARD STATES, AND FREE ENERGY RELATIONS;139
18.4;D. THERMODYNAMIC CONCENTRATIONS—THE ACTIVITY;140
19;Chapter 13. Two-Component Systems—Systems in Which One Phase Is Pure and in Which Species and Component Mole Terms Are Equivalent—Simple Eutectic Interactions;142
19.1;A. INTRODUCTION;142
19.2;B. THE ANALYTICAL EXPRESSION OF UNIVARIANCE IN A SIMPLE EUTECTIC INTERACTION;144
19.3;C. AN ALTERNATIVE DERIVATION OF UNIVARIANT EQUATIONS FOR EUTECTIC SYSTEMS;148
20;Chapter 14. Graphical Representations of Simple Eutectic Interactions;156
20.1;A. INTRODUCTION;156
20.2;B. THE PHASE DIAGRAM—A QUALITATIVE VIEW;157
20.3;C. THE LEVER ARM PRINCIPLE;162
20.4;D. SPECIFICS OF APPLICATION OF THE LEVER ARM PRINCIPLE;166
21;Chapter 15. Eutectic Systems Continued—The Parameter .H fusion/T meiting and Its Influence on the Contour of Eutectic Liquidus Curves;169
21.1;A. INTRODUCTION;169
21.2;B. THEORETICAL ANALYSIS;173
21.3;C. APPLICATION OF THE .HA/TA PRINCIPLE TO REAL SYSTEMS;175
21.4;D. PSEUDOBINARY SYSTEMS;181
22;Chapter I6. Eutectic Interactions Continued—The Effects of Homogeneous Equilibria on Liquidus Contours;183
22.1;A. INTRODUCTION;183
22.2;B. DISSOCIATION OF ONE OF THE LIQUID-PHASE SPECIES;185
22.3;C. SOLUTION FOR THE AB LIQUIDUS CURVE;187
22.4;D. THE LIQUIDUS FOR THE NONDISSOCIATING COMPONENT;190
23;Chapter 17. Common Species Effects in Simple Eutectic Systems;194
23.1;A. INTRODUCTION;194
23.2;B. THE LIQUIDUS CURVE FOR AB;198
23.3;C. THE LIQUIDUS FOR B;199
24;Chapter 18. Eutectic Interactions Continued—The Effectsof Association on Liquidus Contours;202
24.1;A. INTRODUCTION;202
24.2;B. THE A LIQUIDUS;203
24.3;C. THE LIQUIDUS FOR THE COMPONENT B;206
25;Chapter 19. Eutectic Interactions Continued—Effects of End Member Species Interactions on Liquidus Contours;209
25.1;A. INTRODUCTION;209
25.2;B. SOLUTION OF THE A LIQUIDUS;212
25.3;C. SOLUTION OF THE B LIQUIDUS;213
26;Chapter 20. Eutectic Interactions Continued—Effects of Complete Dissociation on Liquidus Contours;214
26.1;A. INTRODUCTION;214
26.2;B. THE AB LIQUIDUS;218
26.3;C. THE B LIQUIDUS;220
27;Chapter 21. Eutectic Interactions Continued—Graphical Description of the Results of Chapters 16–20;221
27.1;A. INTRODUCTION;221
27.2;B. TEST CASES;222
27.3;C. DISSOCIATION OF A PSEUDOUNARY COMPONENT IN THE SYSTEM AB–C;223
27.4;D. DISSOCIATION WITH A COMMON SPECIES EFFECT;227
27.5;E. ASSOCIATION OF ONE OF THE LIQUID-PHASE SPECIES;228
27.6;F. REACTION BETWEEN LIQUID-PHASE SPECIES;230
27.7;G. EFFECTS OF COMPLETE DISSOCIATION ON LIQUIDUS CONTOURS;232
28;Chapter 22. Eutectic Interactions Continued—Single Compound Formation in Binary Systems and Coordinate Transformations;234
28.1;A. INTRODUCTION;234
28.2;B. A SINGLE COMPOUND IS GENERATED;234
28.3;C. SCALING FACTORS AND COORDINATE TRANSFORMATIONS;239
28.4;D. EXAMINATION OF SOLUBILITY CURVES IN SYSTEMS EXHIBITING COMPOUND FORMATION;244
29;Chapter 23. Eutectic Interactions Continued—Multiple Compound Formation in Binary Systems and Coordinate Transformations in Multiple Compound Systems;246
29.1;A. INTRODUCTION;246
29.2;B. Two COMPOUNDS ARE GENERATED;247
30;Chapter 24. Eutectic Interactions Continued—p–T–Mx Representations and Phase Changes;251
30.1;A. INTRODUCTION;251
30.2;B. THE T–p–Mx DIAGRAM OF STATE;253
30.3;C. PHASE CHANGES—A SECOND QUADRUPLE POINT;272
31;Chapter 25. Eutectic Interactions Continued—Intermediate Compound Instability—Incongruently Melting Compounds;274
31.1;A. INTRODUCTION;274
31.2;B. THE INTERMEDIATE COMPOUND AxBy MELTS INCONGRUENTLY;275
31.3;C. THE THREE-DIMENSIONAL MODEL OF INCONGRUENTLY MELTING SYSTEMS;281
31.4;D. THE EFFECT OF PRESSURE WHEN THE S–L SLOPE OF THE INTERMEDIATE INCONGRUENTLY MELTING COMPOUND Is POSITIVE;284
32;Chapter 26. Liquid Immiscibility in Eutectic Systems;288
32.1;A. INTRODUCTION;288
32.2;B. THE MISCIBILITY GAP Is CONFINED TO THE LIQUID REGIONS;289
32.3;C. THE T–p–Mx REPRESENTATION OF THE EUTECTIC SYSTEM SHOWING LIQUID PHASE IMMISCIBILITY;290
32.4;D. THE INTERSECTION OF A MISCIBILITY GAP WITH THE LIQUIDUS REGIONS;293
32.5;E. THE T–p–Mx REPRESENTATION OF THE MG INTERSECTING A LIQUIDUS;295
33;Chapter 27. Systems Exhibiting Solid Solubility—Ascending Solid Solutions;301
33.1;A. INTRODUCTION;301
33.2;B. THE ANALYTICAL DESCRIPTION OF UNIVARIANCE FOR ASCENDING SOLID SOLUTIONS;303
33.3;C. THE GRAPHICAL REPRESENTATION OF ASCENDING SOLID SOLUTIONS;306
33.4;D. THE PURIFICATION OF MATERIALS;307
33.5;E. THE GENERAL EXPERIMENTAL APPROACH TO THE RESOLUTION OF SOLID SOLUTION DIAGRAMS;311
33.6;F. THE SPACE MODEL FOR SOLID SOLUTION SYSTEMS;312
34;Chapter 28. Solid Solutions Continued—Graphical Representation of Idealized Systems and Some Comment on Real Systems;318
34.1;A. INTRODUCTION;318
34.2;B. TEMPERATURE–COMPOSITION DIAGRAMS FOR CASES I–XIV;319
34.3;C. REAL SYSTEMS;329
35;Chapter 29. Solid Solutions Continued—Complete Liquid Phase Dissociation and Minimum Type Solid Solutions;330
35.1;A. INTRODUCTION;330
35.2;B. THE QUALITATIVE ASPECTS OF FIG. 1;332
35.3;C. COMPLETE DISSOCIATION IN SOLID SOLUTION SYSTEMS;332
35.4;D. CASE I—DIMER-MONOMER BEHAVIOR;334
35.5;E. CASE II;338
35.6;F. THE CASE WHERE BOTH COMPONENTS ARE DIMERS IN THE SOLID;341
35.7;G. SPACE MODELS;343
36;Chapter 30. Hypothetical Examples Using the Equations of Chapter 29
;347
36.1;A. INTRODUCTION;347
36.2;B. SOME HYPOTHETICAL EXAMPLES;348
36.3;C. THE SYSTEM Na2CO3–K2CO3—A COMPARISON BETWEEN EXPERIMENTAL AND THEORETICAL SOLIDUS AND LIQUIDUS CURVES;352
37;Chapter 31. Condensed-Vapor Phase Binary Diagrams;357
37.1;A. INTRODUCTION;357
37.2;B. BOILING AND SUBLIMATION POINT DIAGRAMS (CONSTANT PRESSURE DIAGRAMS);358
37.3;C. CONSTANT TEMPERATURE CONDENSED-VAPOR PHASE DIAGRAMS;361
37.4;D. SOME HYPOTHETICAL EXAMPLES OF MAXIMUM TYPE S–V EQUILIBRIA IN ISOTHERMAL DIAGRAMS;369
37.5;E. ISOTHERMAL DISTILLATIONS;376
37.6;F. ISOBARIC DISTILLATIONS;379
38;Chapter 32. Condensed-Vapor Phase Binary Diagrams Continued—Incongruently Vaporizing Systems;384
38.1;A. INTRODUCTION;384
38.2;B. VAPOROUS CURVES IN ISOTHERMAL DIAGRAMS;385
38.3;C. IMMISCIBLE SOLID–VAPOR SYSTEMS EXHIBITING CONGRUENTLY VAPORIZING COMPOUNDS;387
38.4;D. IMMISCIBLE SOLID–VAPOR SYSTEMS CONTAINING INCONGRUENTLY VAPORIZING COMPOUNDS;390
38.5;E. HYDRATE SYSTEMS;394
38.6;F. FURTHER REMARKS ON THE REGIONS OF VARIABLE COMPOSITION;399
38.7;G. DELIQUESCENCE AND EFFLORESCENCE OF HYDRATE SYSTEMS;402
39;Chapter 33. Limited Solid Solubility;406
39.1;A. INTRODUCTION;406
39.2;B. LIMITED SOLUBILITY SYSTEMS EXHIBITING A EUTECTIC;407
39.3;C. THE CASE WHERE LIMITED SOLUBILITY OCCURS BELOW THE SOLIDUS;414
39.4;D. THREE-DIMENSIONAL REPRESENTATIONS OF LIMITED SOLID SOLUBILITY SYSTEMS;418
40;Chapter 34. Three-Component Systems;424
40.1;A. INTRODUCTION;424
40.2;B. REPRESENTATION OF THREE-COMPONENT CONDENSED-PHASE EQUILIBRIA;425
40.3;C. SIMPLE TERNARY EUTECTIC INTERACTIONS;432
40.4;D. TERNARY DIAGRAMS FOR SYSTEMS IN WHICH BINARY CONGRUENTLY MELTING COMPOUNDS ARE FORMED;449
40.5;E. TERNARY DIAGRAMS FOR SYSTEMS IN WHICH BINARY CONGRUENTLY MELTING COMPOUNDS OCCUR, ONE OF WHOSE EUTECTIC EXTENSIONS GENERATES A TERNARY PERITECTIC;453
40.6;F. TERNARY SYSTEMS IN WHICH INCONGRUENTLY MELTING BINARY COMPOUNDS ARE PRESENT;464
40.7;G. TERNARY COMPOUND FORMATION—CONGRUENTLY MELTING TERNARY COMPOUNDS;465
40.8;H. TERNARY COMPOUND FORMATION—AN INCONGRUENTLY MELTING TERNARY COMPOUND Is PRESENT;465
40.9;I. ISOTHERMAL SECTIONS FOR SELECTED TERNARY SYSTEMS;468
40.10;J. SYSTEMS EXHIBITING SOLID SOLUBILITY;476
41;Chapter 35. Three-Component Solid-Vapor Equilibria—Chemical Vapor Transport Reactions;494
41.1;A. INTRODUCTION;494
41.2;B. DlSPROPORTIONATION PROCESSES;497
42;Chapter 36. Experimental Techniques;504
42.1;A. INTRODUCTION;504
42.2;B. PRESSURE MEASUREMENTS;506
42.3;B. PRESSURE MEASUREMENTS;506
42.4;C. MEASUREMENT OF THERMAL ANOMALIES;516
43;Appendix: References and Additional Remarks for Chapters 1–36, General Bibliography;534
44;Subject Index;553
45;Physical Chemistry;559