Solid State Chemistry: An Introduction, Third Edition

by Smart, Lesley; Moore, Elaine

• ISBN13: 9780748775163
• ISBN10: 0748775161
• Edition: 3rd
• Format: Paperback
• Copyright: 2005-06-24
• Publisher: CRC Press

Summary

Intended for first- and second-year undergraduates, this introduction to solid state chemistry includes practical examples of applications and modern developments to offer students the opportunity to apply their knowledge in real-life situations. The third edition of Solid State Chemistry: An Introductionhas been comprehensively revised and updated. Building a foundation with a thorough description of crystalline structures, the book presents a wide range of the synthetic and physical techniques used to prepare and characterize solids. Other fundamental discussions include:A bonding, superconductivity, and electrochemical, magnetic, optical, and conductive properties. The authors have added sections on fuel cells and electrochromic materials; conducting organic polymers, organic superconductors, and fullerenes; mesoporous solids and ALPOs; photonics; giant magnetoresistance (GMR) and colossal magnetoresistance (CMR); and p-wave (triplet) superconductors. The book also includes acompletely new chapter, which examines the solid state chemical aspects of nanoscience. Each chapter contains a set of review questions and an accompanying solutions manual is available. Solid State Chemistry: An Introduction, Third Editionis written in a clear, approachable style that enhances the material by integrating its concepts in the context of current applications and areas of promising research.

Table of Contents

Chapter 1 An Introduction to Crystal Structures	1	(76)
1.1 Introduction	1	(1)
1.2 Close-packing	2	(4)
1.3 Body-centred and Primitive Structures	6	(3)
1.4 Symmetry	9	(6)
1.4.1 Axes of Symmetry	10	(1)
1.4.2 Planes of Symmetry	10	(2)
1.4.3 Inversion	12	(1)
1.4.4 Inversion Axes and Improper Symmetry Axes	12	(1)
1.4.5 Symmetry in Crystals	13	(2)
1.5 Lattices and Unit Cells	15	(13)
1.5.1 Lattices	15	(1)
1.5.2 One- and Two-dimensional Unit Cells	15	(2)
1.5.3 Translational Symmetry Elements	17	(1)
1.5.4 Three-dimensional Unit Cells	18	(4)
1.5.5 Miller Indices	22	(3)
1.5.6 Interplanar Spacings	25	(1)
1.5.7 Packing Diagrams	25	(3)
1.6 Crystalline solids	28	(33)
1.6.1 Ionic Solids with Formula MX	29	(6)
1.6.2 Solids with General Formula MX2	35	(5)
1.6.3 Other Important Crystal Structures	40	(3)
1.6.4 Ionic Radii	43	(7)
1.6.5 Extended Covalent Arrays	50	(2)
1.6.6 Bonding In Crystals	52	(2)
1.6.7 Atomic Radii	54	(1)
1.6.8 Molecular Structures	55	(1)
1.6.9 Silicates	56	(5)
1.7 Lattice Energy	61	(10)
1.7.1 The Born-Haber Cycle	62	(1)
1.7.2 Calculating Lattice Energies	63	(5)
1.7.3 Calculations Using Thermochemical Cycles and Lattice Energies	68	(3)
1.8 Conclusion	71	(1)
Questions	72	(5)
Chapter 2 Physical Methods for Characterizing Solids	77	(48)
2.1 Introduction	77	(1)
2.2 X-ray Diffraction	77	(4)
2.2.1 Generation of X-rays	77	(2)
2.2.2 Diffraction of X-rays	79	(2)
2.3 Powder Diffraction	81	(10)
2.3.1 Powder Diffraction Patterns	81	(1)
2.3.2 Absences Due to Lattice Centring	82	(5)
2.3.3 Systematic Absences Due to Screw Axes and Glide Planes	87	(1)
2.3.4 Uses of Powder X-ray Diffraction	88	(3)
2.4 Single Cystal X-ray Diffraction	91	(6)
2.4.1 The Importance of Intensities	92	(3)
2.4.2 Solving Single Crystal Structures	95	(2)
2.5 Neutron Diffraction	97	(4)
2.5.1 Uses of Neutron Diffraction	98	(3)
2.6 Electron Microscopy	101	(3)
2.6.1 Scanning Electron Microscopy (SEM)	101	(1)
2.6.2 Transmission Electron Microscopy (TEM)	101	(1)
2.6.3 Scanning Transmission Electron Microscopy (STEM)	102	(1)
2.6.4 Energy Dispersive X-ray Analysis (EDAX)	102	(2)
2.7 X-ray Absorption Spectroscopy	104	(5)
2.7.1 Extended X-ray Absorption Fine Structure (EXAFS)	104	(4)
2.7.2 X-ray Absorption Near-Edge Structure (XANES)	108	(1)
2.8 Solid State Nuclear Magnetic Resonance Spectroscopy (MAS NMR)	109	(4)
2.9 Thermal Analysis	113	(1)
2.9.1 Differential Thermal Analysis (DTA)	113	(1)
2.9.2 Thermogravimetric Analysis (TGA)	114	(1)
2.9.3 Differential Scanning Calorimetry (DSC)	114	(1)
2.10 Scanning Tunnelling Microscopy (STM) and Atomic Force Microscopy (AFM)	114	(2)
2.11 Temperature Programmed Reduction (TPR)	116	(2)
2.12 Other Techniques	118	(1)
Questions	119	(6)
Chapter 3 Preparative Methods	125	(30)
3.1 Introduction	125	(1)
3.2 High Temperature Ceramic Methods	126	(8)
3.2.1 Direct Heating of Solids	126	(3)
3.2.2 Reducing the Particle Size and Lowering the Temperature	129	(5)
3.3 Microwave Synthesis	134	(2)
3.3.1 The High Temperature Superconductor YBa2Cu3O7-x	135	(1)
3.4 Combustion Synthesis	136	(1)
3.5 High Pressure Methods	137	(6)
3.5.1 Hydrothermal Methods	137	(4)
3.5.2 High Pressure Gases	141	(1)
3.5.3 Hydrostatic Pressures	141	(1)
3.5.4 Synthetic Diamonds	142	(1)
3.5.5 High Temperature Superconductors	143	(1)
3.5.6 Harder Than Diamond	143	(1)
3.6 Chemical Vapour Deposition (CVD)	143	(8)
3.6.1 Preparation of Semiconductors	143	(1)
3.6.2 Diamond Films	144	(1)
3.6.3 Lithium Niobate	145	(1)
3.7 Preparing Single Crystals	145	(1)
3.7.1 Epitaxy Methods	146	(1)
3.7.2 Chemical Vapour Transport	147	(3)
3.7.3 Solution Methods	150	(1)
3.8 Intercalation	151	(1)
3.8.1 Graphite Intercalation Compounds	151	(1)
3.8.2 Titanium Disulfide	152	(1)
3.8.3 Pillared Clays	152	(1)
3.9 Choosing a Method	152	(1)
Questions	153	(2)
Chapter 4 Bonding in Solids and Electronic Properties	155	(20)
4.1 Introduction	155	(1)
4.2 Bonding in Solids - Free Electron Theory	155	(6)
4.2.1 Electronic Conductivity	159	(2)
4.3 Bonding in Solids - Molecular Orbital Theory	161	(4)
4.3.1 Simple Metals	164	(1)
4.4 Semiconductors - Si and Ge	165	(6)
4.4.1 Photoconductivity	167	(1)
4.4.2 Doped Semiconductors	168	(1)
4.4.3 The p-n Junction - Field-Effect Transistors	169	(2)
4.5 Bands in Compounds - Gallium Arsenide	171	(1)
4.6 Bands in d-BlockCompounds - Transition Metal Monoxides	172	(1)
Questions	173	(2)
Chapter 5 Defects and Non-Stoichiometry	175	(68)
5.1 Point Defects - An Introduction	175	(1)
5.2 Defects and their Concentration	175	(8)
5.2.1 Intrinsic Defects	175	(3)
5.2.2 The Concentration of Defects	178	(4)
5.2.3 Extrinsic Defects	182	(1)
5.3 Ionic Conductivity in Solids	183	(5)
5.4 Solid Electrolytes	188	(22)
5.4.1 Fast-ion Conductors: Silver Ion Conductors	189	(3)
5.4.2 Fast-ion Conductors: Oxygen Ion Conductors	192	(3)
5.4.3 Fast-ion Conductors: Sodium Ion Conductors	195	(2)
5.4.4 Applications	197	(13)
5.5 Photography	210	(1)
5.6 Colour Centres	211	(1)
5.7 Non-stoichiometric Compounds	212	(10)
5.7.1 Introduction	212	(2)
5.7.2 Non-stoichiometry in Wustite	214	(4)
5.7.3 Uranium Dioxide	218	(2)
5.7.4 The Titanium Monoxide Structure	220	(2)
5.8 Planar Defects	222	(6)
5.8.1 Crystallographic Shear Planes	223	(4)
5.8.2 Planar Intergrowths	227	(1)
5.9 Three-dimensional Defects	228	(4)
5.9.1 Block Structures	228	(1)
5.9.2 Pentagonal Columns	229	(2)
5.9.3 Infinitely Adaptive Structures	231	(1)
5.10 Electronic Properties of Non-stoichiometric Oxides	232	(5)
5.11 Conclusions	237	(1)
Questions	238	(5)
Chapter 6 Carbon-Based Electronics	243	(16)
6.1 Introduction	243	(1)
6.2 Polyacetylene and Related Polymers	243	(5)
6.2.1 The Discovery of Polyacetylene	243	(3)
6.2.2 Bonding in Polyacetylene and Related Polymers	246	(1)
6.2.3 Organic LEDs	247	(1)
6.3 Molecular Metals	248	(3)
6.3.1 One-dimensional Molecular Metals	248	(1)
6.3.2 Two-dimensional Molecular Metals	248	(3)
6.4 Polymers and Ionic Conduction - Rechargeable Lithium Batteries	251	(2)
6.5 Carbon	253	(4)
6.5.1 Graphite	253	(2)
6.5.2 Intercalation Compounds of Graphite	255	(1)
6.5.3 Buckminster Fullerene	256	(1)
Questions	257	(2)
Chapter 7 Zeolites and Related Structures	259	(34)
7.1 Introduction	259	(1)
7.2 Composition and Structure	259	(11)
7.2.1 Frameworks	260	(3)
7.2.2 Nomenclature	263	(1)
7.2.3 Si/Al Ratios	264	(1)
7.2.4 Exchangeable Cations	264	(1)
7.2.5 Channels and Cavities	265	(5)
7.3 Synthesis of Zeolites	270	(2)
7.4 Structure Determination	272	(1)
7.5 Uses of Zeolites	273	(10)
7.5.1 Dehydrating Agents	273	(1)
7.5.2 Zeolites As Ion Exchangers	274	(1)
7.5.3 Zeolites As Adsorbents	274	(2)
7.5.4 Zeolites As Catalysts	276	(7)
7.6 Mesoporous Aluminosilicate Structures	283	(2)
7.7 Other Framework Structures	285	(2)
7.8 New Materials	287	(1)
7.9 Clay Minerals	288	(2)
7.10 Postscript	290	(1)
Questions	291	(2)
Chapter 8 Optical Properties of Solids	293	(20)
8.1 Introduction	293	(1)
8.2 The Interaction of Light with Atoms	293	(6)
8.2.1 The Ruby Laser	295	(3)
8.2.2 Phosphors in Fluorescent Lights	298	(1)
8.3 Absorption and Emission of Radiation in Semiconductors	299	(7)
8.3.1 Light-Emitting Diodes	303	(1)
8.3.2 The Gallium Arsenide Laser	304	(1)
8.3.3 Quantum Wells - Blue Lasers	305	(1)
8.4 Optical Fibres	306	(2)
8.5 Photonic Crystals	308	(2)
Questions	310	(3)
Chapter 9 Magnetic and Dielectric Properties	313	(26)
9.1 Introduction	313	(1)
9.2 Magnetic Susceptibility	313	(3)
9.3 Paramagnetism in Metal Complexes	316	(2)
9.4 Ferromagnetic Metals	318	(6)
9.4.1 Ferromagnetic Domains	321	(2)
9.4.2 Permanent Magnets	323	(1)
9.5 Ferromagnetic Compounds - Chromium Dioxide	324	(1)
9.5.1 Audiotapes	324	(1)
9.6 Antiferromagnetism - Transition Metal Monoxides	325	(1)
9.7 Ferrimagnetism - Ferrites	326	(2)
9.8 Giant, Tunnelling, and Colossal Magnetoresistance	328	(3)
9.8.1 Giant Magnetoresistance	328	(1)
9.8.2 Hard Disk Read Heads	329	(1)
9.8.3 Tunnelling and Colossal Magnetoresistance	330	(1)
9.9 Electrical Polarisation	331	(1)
9.10 Piezoelectric Crystals - α-quartz	332	(2)
9.11 The Ferroelectric Effect	334	(4)
9.11.1 Multilayer Ceramic Capacitors	337	(1)
Questions	338	(1)
Chapter 10 Superconductivity	339	(16)
10.1 Introduction	339	(1)
10.2 Conventional Superconductors	340	(5)
10.2.1 The Discovery of Superconductors	340	(1)
10.2.2 The Magnetic Properties of Superconductors	340	(3)
10.2.3 Josephson Effects	343	(1)
10.2.4 The BCS Theory of Superconductivity	343	(2)
10.3 High Temperature Superconductors	345	(6)
10.3.1 The Crystal Structures of High Temperature Superconductors	346	(4)
10.3.2 Theory of High Tc Superconductors	350	(1)
10.4 Ferromagnetic Superconductors	351	(1)
10.5 Uses of High Temperature Superconductors	351	(2)
Questions	353	(2)
Chapter 11 Nanoscience	355	(22)
11.1 Introduction	355	(1)
11.2 Consequences of the Nanoscale	356	(9)
11.2.1 Nanoparticle Morphology	356	(1)
11.2.2 Electronic Structure	357	(3)
11.2.3 Optical Properties	360	(3)
11.2.4 Magnetic Properties	363	(2)
11.2.5 Mechanical Properties	365	(1)
11.2.6 Melting	365	(1)
11.3 Examples	365	(7)
11.3.1 One-dimensional Nanomaterials	365	(2)
11.3.2 Two-dimensional Nanomaterials	367	(2)
11.3.3 Three-dimensional Nanomaterials	369	(3)
11.4 Manipulating Atoms and Molecules	372	(5)
11.4.1 Scanning Tunnelling Microscopy	373	(1)
11.4.2 Atomic Force Microscopy	374	(1)
11.4.3 Nanostencils	375	(1)
11.4.4 Optical Tweezers	375	(1)
11.4.5 Molecular Lithography	376	(1)
11.4.6 Data Storage	376	(1)
Further Reading	377	(4)
Answers Odd Number Questions	381	(16)
Index	397