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
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.
Springer Book Archives