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.- 2.1. Fick’s Laws.- 2.2. Self-Diffusion and Chemical Diffusion. The Kirkendall Effect.- 2.3. Experimental Methods for Measuring Diffusion Coefficients.- 2.4. The Thermodynamic Description of Diffusion.- 3. The Atomic Theory of Diffusion.- 3.1. The Basic Random Walk Expressions.- 3.2. Chemical Diffusion.- 3.3. Self-Diffusion Correlation.- 3.4. The Theory of Atomic Jump Rates.- 3.5. The Temperature and Pressure Dependence of D.- 4. Experimental and Theoretical Results. A Brief Summary.- 4.1. Diffusion in Metals.- 4.2. Diffusion in Ionic Crystals.- References.- 2 Factors Influencing the Reactivity of Solids.- 1. General Outline.- 2. Decomposition and Related Reactions.- 2.1. General.- 2.2. The Effect of Mechanical Strain, Additives, and Pre-irradiation upon the Thermal Decomposition of an Inorganic Compound: Ammonium Perchlorate.- 2.3. The Role of Surface Impurities and of Shear Structures in the Thermal Decomposition of Transition Metal Oxides.- 2.4. The Significance of Localized Energy Levels in the Photolysis of Inorganic Compounds.- 2.5. Topochemical Effects in the Photodimerization of Organic Molecules.- 3. Solid-Gas Reactions.- 3.1. Tarnishing Reactions.- 3.2. Other Reactions; The Role of Hydrogen Pressure and of Vacancies in the Reduction of Additives in an Alkali Halide Matrix.- 4. Solid-Solid Reactions.- 4.1. General.- 4.2. Factors Influencing Solid-Solid Reactivity.- 5. Solid-Liquid Reactions.- 5.1. General.- 5.2. Dissolution of Semiconductors: Influence of Conductivity Type, Illumination, Applied Voltage, Crystal Face, and Inhibitors in Solution.- 5.3. The Role of Dislocations in Etching.- 6. Reactions at the Surface of Solids.- 6.1. Heterogeneous Catalysis.- 6.2. Electrode Reactions.- 7. Conclusions.- References.- 3 High-Temperature Reactivity.- 1. Introduction.- 2. Equilibrium Thermodynamics for High-Temperature Reactivity.- 2.1. Free Energy Equations and Calculations.- 2.2. Enthalpy and Entropy.- 2.3. Thermodynamic Data Compilations.- 3. Phase Diagrams and Chemical Reactions.- 3.1. The Phase Rule.- 3.2. Writing Chemical Equations.- 3.3. High-Temperature Reactions.- 4. General Behavior and Trends in High-Temperature Reactions..- 4.1. High-Temperature versus Room-Temperature Reactions.- 4.2. Trends in Reaction Entropies.- 4.3. Principle of Successive Entropy States.- 4.4. Chemical Behavior of Solid-Gas Systems.- 4.5. Examples of Reaction Types in Solid-Gas Systems.- 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.- 4.1. Single-Step Nucleation.- 4.2. Multistep Nucleation.- 5. Nucleus Growth.- 6. Kinetic Equations of Nucleus Formation and Growth.- 7. Exponential Acceleratory Period.- 8. Abnormal Initial Growth.- 8.1. Calculation of Normal Growth Constant.- 8.2. The Induction Period.- 9. Reversible Decompositions.- 10. Aging.- 11. General Discussion.- References.- 5 Solid-State Reactions.- 1. Introduction.- 1.1. General Remarks.- 1.2. Brief Summary of Defect Thermodynamics.- 1.3. Some Aspects of the Phenomenological Diffusion Theory Relevant to Solid-Solid Reactions.- 1.4. Descriptive Examples of Solid-State Reactions.- 2. Chemical Reactions in the Solid State.- 2.1. Reactions between Atomic Defects.- 2.2. Reactions between Ionic Crystals.- 2.3. Reactions in and between Metals.- 3. Special Solid-Solid Reactions.- 3.1. Powder Reactions.- 3.2. Topochemical Reactions.- 3.3. Double Reactions.- 3.4. Concluding Remarks.- Acknowledgment.- References.- 6 Solid-State Electrochemistry.- 1. General Aspects of Solid Electrolytes.- 1.1. Disorder Equilibria in Solid Electrolytes and between Solid Electrolytes and the Environment.- 1.2. Transport Phenomena of Ions and Electrons in Solid Electrolytes.- 2. Galvanic Cells with Solid Electrolytes for Thermodynamic Measurement.- 2.1. General Properties of Cells with Solid Electrolytes.- 2.2. Galvanic Cells with Solid Electrolytes for AG Measurements.- 2.3. Galvanic Cells with Solid Electrolytes for Activity Measurements.- 2.4. Coulometric Titration.- 3. Galvanic Cells with Solid Electrolytes for Kinetic Investigations.- 3.1. Electrochemical Measurements of Oxygen Diffusion in Metals at High Temperatures using a Zirconia-Based Electrolyte.- 3.2. The Kinetics of the Formation of Solid Nickel Sulfide on Nickel at 400°C.- 3.3. Electrochemical Studies of the Transfer of Silver, Silver Ions, and Electrons across the Phase Boundary Solid Silver/Solid Silver Sulfide.- 3.4. Electrochemical Investigations of the Evaporation of Iodine from Copper Iodide.- 3.5. Electrochemical Knudsen Cells for Investigating the Thermodynamics of Vapors.- 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 Band Structure.- 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.- 3.1. Defect Structure in Silver Halides.- 3.2. Defect Structure in p-Type Oxides and Sulfides.- 3.3. Defect Structure in n-Type Oxides and Sulfides.- 4. General Nature of Transport Processes in Ionic Crystals.- 4.1. Diffusion-Controlled Oxidation—The Parabolic Rate.- Law.- 4.2. Local Cell Action during Metal Oxidation.- 4.3. Grain Boundary and Short-Circuit Diffusion in the Growing Oxide Layer.- 4.4. Metal Oxidation with Simultaneous Diffusion of Oxygen in the Metal.- 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.- 8.1. The Semiconductor Valence Approach to Alloy Oxidation.- 8.2. Selective Oxidation of Noble Alloys.- 8.3. Formation of Complex Oxide Layers.- 8.4. Internal Oxidation.- 9. Passivity and Inhibition in High-Temperature Metal Oxidation.- 10. Thin Oxide Layer Formation.- 10.1. The Linear Rate Law.- 10.2. A Cubic Rate Law.- 10.3. Space-Charge Effects in Oxide Growth—The Fourth-Power Rate Law.- 10.4. Logarithmic and Reciprocal Logarithmic Rate Laws.- 11. Concluding Remarks.- References.- 9 Metal-Liquid Reactions: Corrosion.- 1. Definitions of Corrosion.- 2. Thermodynamic Considerations.- 3. Kinetic Considerations.- 4. Alloy Corrosion.- 4.1. Dealloying.- 4.2. Other Significant Alloying Effects.- 5. Passivity.- 5.1. Anodic Passivation.- 5.2. Mechanism of Passivation.- 6. Aggravating Factors in Corrosion.- 6.1. Galvanic Corrosion.- 6.2. Crevice Corrosion.- 6.3. Concentration Cell Corrosion.- 6.4. Erosion Corrosion.- 6.5. Corrosion in the Presence of Cyclic Stresses.- 7. Control of Corrosion.- 7.1. Cathodic Protection:.- 7.2. Anodic Protection.- 7.3. Inhibition.- 7.4. Organic Coatings.- 8. Morphology of Corrosion.- 8.1. General Corrosion.- 8.2. Pitting.- 9. Metallurgical Factors.- 9.1. Introduction.- 9.2. Orientation of Grains.- 9.3. Effects of Dislocations and Cold Work.- 9.4. Grain Boundaries.- 9.5. Compositionally Different Phases.- 9.6. Effect of Deformation on Corrosion Processes.- 9.7. Tunneling.- 9.8. Interaction of Corrosion and Deformation Processes.- 9.9. Interaction of Hydrogen with Metals.- 10. Intergranular and Interfacial Corrosion.- 10.1. Introduction.- 10.2. Intergranular Corrosion in Sensitized Stainless Steel.- 10.3. Exfoliation of Aluminum.- 10.4. Intergranular Attach in the Absence of Precipitation.- 10.5. Grain Boundary Fracture Simulated by Hydrogen Entry.- 11. Environmentally Induced Cracking Phenomena.- 11.1. Introduction.- 11.2. Organization of the Data.- 11.3. Fundamental Aspects of Environmental Effects on Crack Propagation.- 11.4. Phenomenological Influences on Stress Corrosion Cracking.- 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.- 3.1. Particle Joining.- 3.2. Sintering Temperature.- 4. The Driving Force for Sintering.- 4.1. The Kelvin Equation.- 4.2. Curvature in Three Dimensions.- 4.3. Application to Particle Joining and Pore Elimination.- 4.4. Importance of Grain Boundary Energy.- 4.5. Powder Activity.- 5. Grain Growth during Sintering.- 5.1. Particle Growth during the Early Stages of Sintering.- 5.2. Grain Boundary Motion in Solids.- 5.3. Interactions between Pores or Other Inclusions and Grain Boundaries.- 5.4. Exaggerated Grain Growth.- 5.5. Pore-Free Products from Sintering.- 6. Other Sintering Modes.- 6.1. Liquid-Phase Sintering.- 6.2. Hot Pressing.- 6.3. Reaction Sintering.- 7. Theory of Sintering.- 7.1. Driving Force and Mechanisms.- 7.2. Common Characteristics of Sintering Models.- 7.3. Development of Microstructure.- 7.4. Sintering Stages.- 7.5. Initial-Stage Sintering Models.- 7.6. Intermediate-Stage Sintering Models.- 7.7. Final-Stage Sintering Models.- 8. Summary.- Acknowledgment.- References.- 11 Reactions of Solid Polymers.- 1. Introduction.- 1.1. The Chain Structure of Addition Polymers.- 1.2. Molecular Weight Distribution.- 1.3. Chain Conformation and Polymer Morphology.- 1.4. Types of Polymer Reactions.- 2. Chain Scission and Cross-Linking; General.- 2.1. Effects of Chain Scission.- 2.2. Effects of Cross-Linking.- 2.3. Simultaneous Scission and Cross-Linking.- 3. Degradation and Oxidation.- 3.1. Thermal Degradation.- 3.2. Oxidative Degradation.- 3.3. Ozone Degradation.- 3.4. Flammability.- 3.5. Chemical Degradation.- 4. Cross-Linking.- 4.1. Cross-Linking and Mechanical Properties.- 4.2. Cross-Linking Reactions.- 5. Effects of Radiation.- 5.1. Ultraviolet Photooxidation.- 5.2. High-Energy Radiation.- 5.3. Photoresists and Electron-Resists.- 6. Reactions under Mechanical Stress.- References.