Treatise on Solid State Chemistry, Softcover reprint of the original 1st ed. 1976 Volume 4 Reactivity of Solids

The last quarter-century has been marked by the extremely rapid growth of the solid-state sciences. They include what is now the largest subfield of physics, and the materials engineering sciences have likewise flourished. And, playing an active role throughout this vast area of science and engineer­ ing have been very large numbers of chemists. Yet, even though the role of chemistry in the solid-state sciences has been a vital one and the solid-state sciences have, in turn, made enormous contributions to chemical thought, solid-state chemistry has not been recognized by the general body of chemists as a major subfield of chemistry. Solid-state chemistry is not even well defined as to content. Some, for example, would have it include only the quantum chemistry of solids and would reject thermodynamics and phase equilibria; this is nonsense. Solid-state chemistry has many facets, and one of the purposes of this Treatise is to help define the field. Perhaps the most general characteristic of solid-state chemistry, and one which helps differentiate it from solid-state physics, is its focus on the chemical composition and atomic configuration of real solids and on the relationship of composition and structure to the chemical and physical properties of the solid. Real solids are usually extremely complex and exhibit almost infinite variety in their compositional and structural features.

1 Diffusion.- 1. Introduction.- 2. The Phenomenology of Diffusion.- 3. The Atomic Theory of Diffusion.- 4. Experimental and Theoretical Results. A Brief Summary.- References.- 2 Factors Influencing the Reactivity of Solids.- 1. General Outline.- 2. Decomposition and Related Reactions.- 3. Solid-Gas Reactions.- 4. Solid-Solid Reactions.- 5. Solid-Liquid Reactions.- 6. Reactions at the Surface of Solids.- 7. Conclusions.- References.- 3 High-Temperature Reactivity.- 1. Introduction.- 2. Equilibrium Thermodynamics for High-Temperature Reactivity.- 3. Phase Diagrams and Chemical Reactions.- 4. General Behavior and Trends in High-Temperature Reactions..- 5. Summary and Concluding Remarks.- Appendix: Sources of High-Temperature Thermodynamic Data.- Acknowledgments.- References.- 4 Decomposition Reactions.- 1. Introduction.- 2. Dislocations and Enhanced Reactivity.- 3. Kinetics of Solid Decomposition.- 4. Nucleus Formation.- 5. Nucleus Growth.- 6. Kinetic Equations of Nucleus Formation and Growth.- 7. Exponential Acceleratory Period.- 8. Abnormal Initial Growth.- 9. Reversible Decompositions.- 10. Aging.- 11. General Discussion.- References.- 5 Solid-State Reactions.- 1. Introduction.- 2. Chemical Reactions in the Solid State.- 3. Special Solid-Solid Reactions.- Acknowledgment.- References.- 6 Solid-State Electrochemistry.- 1. General Aspects of Solid Electrolytes.- 2. Galvanic Cells with Solid Electrolytes for Thermodynamic Measurement.- 3. Galvanic Cells with Solid Electrolytes for Kinetic Investigations.- References.- 7 The Photographic Process.- 1. Early Developments.- 2. The Emulsion System.- 3. Sensitometric Properties.- 4. Ionic Disorder in the Silver Halides.- 5. Electron and Hole Mobility.- 6. Photoelectric Effect in Emulsion Grains.- 7. Ultraviolet Response and BandStructure.- 8. Phonon- and Disorder-Assisted Processes.- 9. Luminescence and Induced Absorption.- 10. Mechanism of Latent Image Formation.- Acknowledgments.- References.- 8 Gas-Solid Reactions—Oxidation.- 1. Introduction.- 2. Chemisorption and Nucleation in the Initial Stage of Oxidation.- 3. Defect Structure of Halides, Oxides, and Sulfides.- 4. General Nature of Transport Processes in Ionic Crystals.- 5. Phase Boundary Reactions and Evaporation of the Scale—The Linear Rate Law.- 6. Catastrophic Oxidation.- 7. Oxide Layer Formation with Several Phases.- 8. Oxidation of Alloys.- 9. Passivity and Inhibition in High-Temperature Metal Oxidation.- 10. Thin Oxide Layer Formation.- 11. Concluding Remarks.- References.- 9 Metal-Liquid Reactions: Corrosion.- 1. Definitions of Corrosion.- 2. Thermodynamic Considerations.- 3. Kinetic Considerations.- 4. Alloy Corrosion.- 5. Passivity.- 6. Aggravating Factors in Corrosion.- 7. Control of Corrosion.- 8. Morphology of Corrosion.- 9. Metallurgical Factors.- 10. Intergranular and Interfacial Corrosion.- 11. Environmentally Induced Cracking Phenomena.- Acknowledgments.- References.- 10 Sintering.- 1. Introduction.- 2. Sintering of Powdered Metals and Ceramics.- 3. Phenomenological Description of Sintering in the Absence of a Liquid Phase.- 4. The Driving Force for Sintering.- 5. Grain Growth during Sintering.- 6. Other Sintering Modes.- 7. Theory of Sintering.- 8. Summary.- Acknowledgment.- References.- 11 Reactions of Solid Polymers.- 1. Introduction.- 2. Chain Scission and Cross-Linking; General.- 3. Degradation and Oxidation.- 4. Cross-Linking.- 5. Effects of Radiation.- 6. Reactions under Mechanical Stress.- References.