Solid-State Chemistry : A Modern Approach

Solid-state reactions have been growing in importance in the preparation of solids, crystal growth, and single crystals of elements. In this new volume, the author discusses in depth recent advances in solid-state chemistry, the latest techniques of characterization of solids, and several new dimensions of solid-state problems. Solid-state reactions, their kinetics, phase transitions, and magnetic properties are discussed in detail, along with electrical properties, semiconductors, metals, and insulators, with examples and explanations. Dielectric, piezoelectric, and ferroelectric properties of solids have been considered as well. Different theories of catalysis and adsorption isotherms are covered, and the author includes several experimental findings as well. And of course, preparation of new solids by taking advantage of recent experimental techniques have also been included in this volume. This volume provides a complete description of solid-state reactions, electrical conductivity, characterization of solids, organic solids, and intercalation between layers of solids. The band theories of metals, semiconductors, and insulators are covered. In characterization of solids, TGA, DTA, DSC, FTIR and PXRD techniques have been described. Preparation and properties of organic solids are also explained. Dielectric properties, photovoltaic effects, piezo electricity, ferroelectricity, and antiferroelectricity have been dealt with, giving relatable examples. A number of excitation energy levels giving rise to luminescence and photoluminescence have been explained under the topic optical processes. Diamagnetic, paramagnetic, and ferromagnetic behaviors of solids are also explained. Cover Half Title Solid-State Chemistry: A Modern Approach Copyright About the Author Contents Abbreviations Preface Acknowledgments Introduction 1. Solid-State Reactions 1.1 INTRODUCTION 1.2 SPINEL OXIDES 1.3 REACTION RATES 1.4 WAGNER REACTION MECHANISM 1.5 FACTORS AFFECTING THE RATE 1.5.1 SURFACE AREA OF SOLIDS 1.5.2 REACTIVITY OF SOLIDS 1.5.3 SURFACE STRUCTURE 1.6 DIFFICULTIES 1.7 EXPERIMENTAL 1.7.1 HEAT TREATMENT 1.7.2 REAGENTS 1.7.3 MIXING 1.7.4 ANALYSIS 1.8 CO-PRECIPITATION 1.8.1 LIMITATIONS 1.9 KINETIC STUDY 1.10 INTERCALATION CHEMISTRY 1.10.1 TRANSITION-METAL DICHALCOGENIDES 1.10.2 INTERCALATION COMPOUNDS OF TRANSITION METAL DICHALCOGENIDES WITH METAL CATION 1.10.3 PREPARATION 1.10.4 ELECTROCHEMICAL INTERCALATION OF LITHIUM BY TiS2 1.10.5 PREPARATION OF THIN FILMS 1.10.6 CATHODIC DEPOSITION 1.10.7 ELECTROLESS DEPOSITION 1.10.8 ANODIC OXIDATION 1.10.9 THERMAL OXIDATION 1.10.10 CHEMICAL VAPOR DEPOSITION 1.10.11 VACUUM EVAPORATION 1.11 GROWTH OF SINGLE CRYSTALS 1.11.1 CZOCHROLSKI METHOD 1.11.2 BRIDGMAN AND STOCKBARGER METHODS 1.11.3 ZONE MELTING 1.11.4 FLUX METHOD OR PRECIPITATION METHOD 1.11.5 EPITAXIAL GROWTH OF THIN LAYERS 1.11.6 HYDROTHERMAL METHODS KEYWORDS 2. Characterization of Solids 2.1 INTRODUCTION 2.2 THERMOGRAVIMETRIC ANALYSIS (TGA) 2.3 PHASE TRANSITION 2.4 TGA AND DTA OF BENTONITE MINERAL 2.4.1 KINETICS 2.4.2 DECOMPOSITION STEPS 2.5 SCANNING ELECTRON MICROSCOPY (SEM) 2.5.1 SALIENT FEATURES OF SEM 2.6 SCANNING TUNNELING MICROSCOPY (STM) 2.6.1 SALIENT FEATURES OF TEM 2.7 X-RAY ABSORPTION SPECTROSCOPY (EXAFS) 2.8 X-RAY DIFFRACTION 2.8.1 X-RAY DIFFRACTION APPARATUS 2.8.2 IMPORTANCE OF INTENSITIES 2.9 FOURIER TRANSFORMS INFRARED SPECTROSCOPY KEYWORDS 3. Crystal Structure 3.1 INTRODUCTION 3.2 LATTICE TRANSLATION VECTORS 3.3 PRIMITIVE LATTICE CELL OR UNIT CELL 3.3.1 THREE-DIMENSIONAL LATTICE TYPES 3.3.2 RECIPROCAL LATTICE 3.4 THE NUMBER OF ATOMS PER UNIT CELL 3.5 PACKING FRACTION 3.6 INDEX SYSTEM FOR CRYSTAL PLANES 3.7 DISTANCE BETWEEN CONSECUTIVE PLANES 3.8 POWDER METHOD DIFFRACTOMETER 3.8.1 POWDER DIFFRACTOMETER 3.9 BRAGG’S LAW 3.10 IMPORTANT CHARACTERISTICS OF CRYSTAL 3.11 SOME IMPORTANT IONIC STRUCTURE 3.11.1 ROCK SALT STRUCTURE (NACL) 3.11.2 CESIUM CHLORIDE STRUCTURE (CSCL) 3.11.3 AX STRUCTURE, FEO 3.11.4 AX COMPOUNDS WITH DIFFERENT STRUCTURES 3.11.5 ZINC BLENDE STRUCTURE (ZNS) 3.11.6 DIFFERENCE BETWEEN ZINC BLENDE AND WURTZITE 3.11.7 CUBIC ZINC SULFIDE (ZNS) STRUCTURE 3.11.8 FLUORITE STRUCTURES 3.11.9 ANTIFLUORITE STRUCTURE 3.11.10 CADMIUM IODIDE (CDI2) STRUCTURE 3.11.11 DIFFERENCE BETWEEN THE STRUCTURES OF CDI2 AND CDCL2 3.11.12 STRUCTURE OF CS2O 3.11.13 RUTILE STRUCTURE (TIO2) 3.11.14 PEROVSKITE STRUCTURE 3.12 SPINELS 3.13 NONCRYSTALLINE SOLID 3.13.1 STRUCTURE OF VITREOUS SILICA, SiO2 3.13.2 SILICATE GLASSES 3.13.3 BORATE GLASSES 3.13.4 PHASE SEPARATION IN GLASSES 3.13.5 THERMODYNAMIC CRITERIA 3.13.6 MECHANISM OF PHASE SEPARATION 3.13.7 VISCOSITY OF GLASS 3.13.8 COMMERCIAL GLASSES 3.14 AMORPHOUS SEMICONDUCTORS 3.14.1 AMORPHOUS FERROMAGNETS 3.15 METALLIC GLASSES 3.15.1 PROPERTIES 3.16 GLASS-CERAMICS 3.16.1 PROPERTIES 3.17 OPTICAL FIBRES KEYWORDS 4. Space Groups and Point Group 4.1 POINT GROUPS 4.2 REPRESENTATION OF POINT GROUPS KEYWORDS 5. Superconductivity 5.1 INTRODUCTION 5.2 BASIC PRINCIPLE 5.2.1 MEISSNER EFFECT 5.2.2 SPECIFIC HEAT 5.2.3 ISOTOPE EFFECT 5.3 SUPERCONDUCTOR WITH BI AND TL 5.4 SUPERCONDUCTORS WITHOUT CU OR LANTHANIDE 5.5 THEORY OF SUPERCONDUCTIVITY 5.5.1 LIMITATIONS 5.5.2 CHARACTERISTICS OF BCS THEORY 5.6 ORGANIC SUPERCONDUCTORS 5.6.1 FULLERENES 5.6.2 APPLICATION KEYWORDS 6. Thermal Properties of Solids 6.1 INTRODUCTION 6.2 EINSTEIN MODEL 6.3 DEBYE MODEL FOR DENSITY OF STATES 6.4 PHONONS 6.4.1 PHONON MOMENTUM 6.4.2 GROUP VELOCITY 6.5 ONE-DIMENSIONAL MONOATOMIC LATTICE 6.6 QUANTIZATION OF ELASTIC WAVE 6.7 ANHARMONIC CRYSTAL INTERACTIONS 6.8 THERMAL CONDUCTIVITY KEYWORDS 7. Energy Bands: Metals, Insulators, Semiconductors, and Organic Solid 7.1 INTRODUCTION 7.2 ELEMENTAL SEMICONDUCTOR 7.3 COMPOUND SEMICONDUCTORS 7.4 BAND THEORY AND MOLECULAR ORBITAL THEORY 7.5 FREE ELECTRON THEORY 7.6 SIMPLE BAND THEORY 7.7 BAND ENERGY OF METALS 7.8 SEMICONDUCTORS 7.8.1 INTRINSIC SEMICONDUCTOR 7.8.2 EXTRINSIC SEMICONDUCTORS 7.8.2.1 P-TYPE SEMICONDUCTOR 7.8.2.2 N-TYPE SEMI 7.8.2.2.1 Temperature Dependence KEYWORDS 8. Electrical Properties 8.1 PELTIER EFFECT (METAL-SEMICONDUCTOR JUNCTIONS) 8.2 METAL–METAL JUNCTIONS 8.3 THE HALL EFFECT 8.3.1 P-n JUNCTION 8.4 PHOTOVOLTAIC EFFECT 8.5 DIELECTRIC MATERIALS 8.6 PIEZOELECTRICITY 8.7 FERROELECTRICITY 8.8 ANTIFERROELECTRIC MATERIAL 8.9 PYROELECTRICITY 8.10 CENTROSYMMETRIC 8.11 OPTICAL PROCESSES 8.12 CO-ORDINATE MODEL 8.13 LUMINESCENCE IN ALKALI HALIDES 8.13.1 LUMINESCENCE IN ZNS TYPE PHOSPHOROUS 8.14 ANTISTOKES PHOSPHORS 8.15 LASER AND MASER ACTIONS KEYWORDS 9. Magnetic Properties 9.1 INTRODUCTION 9.2 MAGNETIZATION VECTOR (I) 9.2.1 EFFECT OF TEMPERATURE 9.3 LANGEVIN EQUATION 9.3.1 CALCULATION OF MAGNETIC MOMENTS 9.3.2 QUENCHING OF ORBITAL CONTRIBUTION 9.4 EXPERIMENTAL DETERMINATION OF MAGNETIC SUSCEPTIBILITY BY GOUY’S METHOD 9.4.1 MAGNETIC PROPERTIES OF TRANSITION METAL OXIDES KEYWORDS 10. Phase Transition, Phase Rule, and Diagrams 10.1 INTRODUCTION 10.2 THERMODYNAMIC CRITERIA 10.3 SIO2 SYSTEM 10.4 PHASE TRANSITION WITH STRUCTURAL CHANGES 10.5 PHASE RULE 10.5.1 PHASE 10.5.2 DEGREE OF FREEDOM 10.5.3 COMPONENT 10.6 PHASE EQUILIBRIUM 10.6.1 ONE-COMPONENT SYSTEM 10.6.2 TWO-COMPONENT SYSTEM 10.7 SIMPLE EUTECTIC SYSTEMS 10.7.1 LEAD–SILVER SYSTEM 10.8 BINARY SYSTEM WITH COMPOUNDS 10.8.1 COOLING EFFECT 10.9 BINARY SYSTEMS WITH SOLID SOLUTION 10.10 BINARY SOLID SOLUTIONS WITH THERMAL MINIMUM 10.11 BINARY SOLID SOLUTION WITH THERMAL MAXIMA 10.12 BINARY SYSTEM WITH PARTIALLY MISCIBLE SOLID SOLUTION 10.12.1 EUTECTIC SYSTEM OF TWO SOLUTIONS 10.13 BINARY SYSTEMS WITH SOLID–SOLID PHASE TRANSITION 10.14 PERITECTIC SYSTEM OF TWO SOLID SOLUTION 10.15 FORMATION OF STEEL ALLOY 10.16 THREE COMPONENT CONDENSED SYSTEM 10.17 SIMPLE EUTECTIC SYSTEM IN TERNARY COMPOUNDS 10.18 TERNARY SYSTEMS CONTAINING BINARY COMPOUNDS 10.19 SUBSOLIDUS EQUILIBRIUM 10.19.1 MECHANISM OF PHASE TRANSITION 10.20 ORDER–DISORDER TRANSITIONS 10.20.1 NUCLEATION AND GROWTH TRANSITIONS 10.20.2 KINETICS OF PHASE TRANSITION 10.20.3 CRITICAL SIZE OF NUCLEI 10.21 AVRAMI EQUATION 10.22 FACTORS AFFECTING KINETICS OF PHASE TRANSITION 10.23 ENTROPY CHANGE IN ORDER–DISORDER TRANSITIONS KEYWORDS REFERENCES 11. Solid Surface, Heterogeneous Catalysis, and Adsorption 11.1 INTRODUCTION 11.2 ALLOYS 11.3 PHYSISORPTION 11.4 CHEMISORPTION 11.4.1 ACTIVE SITES 11.4.2 ENERGY OF ACTIVATION 11.4.3 PROMOTERS 11.5 POISONING OF A CATALYST 11.6 ZEOLITES 11.6.1 2:1 TYPE 11.6.2 1:1 TYPE 11.6.2.1.1 Corrensite 11.6.2.1.2 Pyrophyllite and Talc 11.7 BENTONITE–MONTMORILLONITE 11.7.1 ORIGIN AND OCCURRENCE OF BENTONITES 11.7.2 THESE CLAY MINERALS HAVE THE FOLLOWING CHEMICAL COMPOSITION 11.7.3 SURFACE PROPERTIES 11.8 LANGMUIR’S THEORY OF ADSORPTION 11.9 DIFFERENCE BETWEEN PHYSISORPTION AND CHEMISORPTION 11.10 BRAUNER, EMMETT, AND TELLER (BET ISOTHERM) 11.10.1 DERIVATION 11.10.2 SURFACE AREA OF ADSORBENT 11.11 ADSORPTION FROM SOLUTION 11.12 SURFACE STRUCTURE 11.12.1 LEED METHOD 11.13 TEMKIN ISOTHERM 11.14 ELOVICH MODEL 11.15 LAGERGREN MODEL 11.16 DUBININ–RADUSHKEVICH ISOTHERM 11.17 INTRAPARTICLE DIFFUSION 11.18 HARKIN–JURA ISOTHERM 11.19 JOVANOVIC ISOTHERM REFERENCES Examination Problems CHAPTER 2: QUESTIONS CHAPTER 3: OBJECTIVE CHAPTER 4: PROBLEMS CHAPTER 5: PROBLEMS CHAPTER 6: QUESTIONS CHAPTER 8: QUESTIONS CHAPTER 9: QUESTIONS CHAPTER 11: EXAMINATION PROBLEMS Solved Problems Practice Problems Answer Key Index