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Book Details
Abstract
Now in its fifth edition, Housecroft & Sharpe's Inorganic Chemistry, continues to provide an engaging, clear and comprehensive introduction to core physical-inorganic principles.
This widely respected and internationally renowned textbook introduces the descriptive chemistry of the elements and the role played by inorganic chemistry in our everyday lives. The stunning full-colour design has been further enhanced for this edition with an abundance of three-dimensional molecular and protein structures and photographs, bringing to life the world of inorganic chemistry.
Updated with the latest research, this edition also includes coverage relating to the extended periodic table and new approaches to estimating lattice energies and to bonding classifications of organometallic compounds.
A carefully developed pedagogical approach guides the reader through this fascinating subject with features designed to encourage thought and to help students consolidate their understanding and learn how to apply their understanding of key concepts within the real world. Features include:
· Thematic boxed sections with a focus on areas of Biology and Medicine, the Environment, Applications, and Theory engage students and ensure they gain a deep, practical and topical understanding
· A wide range of in-text self-study exercises including worked examples, reflective questions and end of chapter problems aid independent study
· Definition panels and end-of-chapter checklists provide students with excellent revision aids
· Striking visuals throughout the book have been carefully crafted to illustrate molecular and protein structures and to entice students further into the world of inorganic chemistry
Inorganic Chemistry 5th edition is also accompanied by an extensive companion website, available at www.pearsoned.co.uk/housecroft . This features multiple choice questions and rotatable 3D molecular structures.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Front Cover | Front Cover | ||
| IFC | IFC | ||
| Periodic Table | i | ||
| Title Page | iii | ||
| Copyright Page | iv | ||
| Summary of Contents | v | ||
| Contents | vii | ||
| Guided tour | xxxiv | ||
| Preface to the fifth edition | xxxvii | ||
| Acknowledgements | xxxix | ||
| 1 Basic concepts: atoms | 1 | ||
| 1.1 Introduction | 1 | ||
| Inorganic chemistry: it is not an isolated branch of chemistry | 1 | ||
| The aims of Chapters 1 and 2 | 1 | ||
| 1.2 Fundamental particles of an atom | 1 | ||
| 1.3 Atomic number, mass number and isotopes | 2 | ||
| Nuclides, atomic number and mass number | 2 | ||
| Relative atomic mass | 2 | ||
| Isotopes | 2 | ||
| 1.4 Successes in early quantum theory | 4 | ||
| Some important successes of classical quantum theory | 4 | ||
| Bohr’s theory of the atomic spectrum of hydrogen | 5 | ||
| 1.5 An introduction to wave mechanics | 7 | ||
| The wave-nature of electrons | 7 | ||
| The uncertainty principle | 7 | ||
| The Schrodinger wave equation | 7 | ||
| 1.6 Atomic orbitals | 9 | ||
| The quantum numbers n , l and ml | 9 | ||
| The radial part of the wavefunction, R (r ) | 10 | ||
| The radial distribution function, 4\x01r2R(r)2 | 12 | ||
| The angular part of the wavefunction, A.\x03; \x04. | 12 | ||
| Orbital energies in a hydrogen-like species | 15 | ||
| Size of orbitals | 16 | ||
| The spin quantum number and the magnetic spin quantum number | 16 | ||
| The ground state of the hydrogen atom | 18 | ||
| 1.7 Many-electron atoms | 18 | ||
| The helium atom: two electrons | 18 | ||
| Ground state electronic configurations: experimental data | 18 | ||
| Penetration and shielding | 20 | ||
| 1.8 The periodic table | 22 | ||
| 1.9 The aufbau principle | 22 | ||
| Ground state electronic configurations | 22 | ||
| Valence and core electrons | 24 | ||
| Diagrammatic representations of electronic configurations | 24 | ||
| 1.10 Ionization energies and electron affinities | 25 | ||
| Ionization energies | 25 | ||
| Electron affinities | 27 | ||
| 2 Basic concepts: molecules | 32 | ||
| 2.1 Bonding models: an introduction | 32 | ||
| A historical overview | 32 | ||
| Lewis structures | 32 | ||
| 2.2 Homonuclear diatomic molecules: valence bond (VB) theory | 33 | ||
| Uses of the term homonuclear | 33 | ||
| Covalent bond distance, covalent radius and van der Waals radius | 33 | ||
| The valence bond (VB) model of bonding in H2 | 34 | ||
| The valence bond (VB) model applied to F2 , O2 and N2 | 35 | ||
| 2.3 Homonuclear diatomic molecules: molecular orbital (MO) theory | 35 | ||
| An overview of the MO model | 35 | ||
| Molecular orbital theory applied to the bonding in H2 | 36 | ||
| The bonding in He2; Li2 and Be2 | 38 | ||
| The bonding in F2 and O2 | 39 | ||
| What happens if the s–p separation is small? | 41 | ||
| 2.4 The octet rule and isoelectronic species | 42 | ||
| The octet rule: first row p-block elements | 42 | ||
| Isoelectronic species | 43 | ||
| The octet rule: heavier p-block elements | 44 | ||
| 2.5 Electronegativity values | 44 | ||
| Pauling electronegativity values, \x05P | 44 | ||
| Mulliken electronegativity values, \x05M | 45 | ||
| Allred–Rochow electronegativity values, \x05AR | 46 | ||
| Electronegativity: final remarks | 46 | ||
| 2.6 Dipole moments | 47 | ||
| Polar diatomic molecules | 47 | ||
| Molecular dipole moments | 48 | ||
| 2.7 MO theory: heteronuclear diatomic molecules | 49 | ||
| Which orbital interactions should be considered? | 49 | ||
| Hydrogen fluoride | 50 | ||
| Carbon monoxide | 52 | ||
| 2.8 Molecular shape and the VSEPR model | 52 | ||
| Valence-shell electron-pair repulsion model | 52 | ||
| Structures derived from a trigonal bipyramid | 55 | ||
| Limitations of the VSEPR model | 56 | ||
| 2.9 Molecular shape: stereoisomerism | 56 | ||
| Square planar species | 56 | ||
| Octahedral species | 57 | ||
| Trigonal bipyramidal species | 57 | ||
| High coordination numbers | 57 | ||
| Double bonds | 58 | ||
| 3 Introduction to molecular symmetry | 62 | ||
| 3.1 Introduction | 62 | ||
| 3.2 Symmetry operations and symmetry elements | 62 | ||
| Rotation about an n-fold axis of symmetry | 63 | ||
| Reflection through a plane of symmetry (mirror plane) | 63 | ||
| Reflection through a centre of symmetry (inversion centre) | 65 | ||
| Rotation about an axis, followed by reflection through a plane perpendicular to this axis | 66 | ||
| Identity operator | 66 | ||
| 3.3 Successive operations | 68 | ||
| 3.4 Point groups | 69 | ||
| C1 point group | 69 | ||
| C1v point group | 70 | ||
| D1h point group | 70 | ||
| Td, Oh or Ih point groups | 70 | ||
| Determining the point group of a molecule or molecular ion | 70 | ||
| 3.5 Character tables: an introduction | 73 | ||
| 3.6 Why do we need to recognize symmetry elements? | 74 | ||
| 3.7 Vibrational spectroscopy | 74 | ||
| How many vibrational modes are there for a given molecular species? | 74 | ||
| Selection rules for an infrared or Raman active mode of vibration | 75 | ||
| Linear (D1h or C1v ) and bent (C2v ) triatomic molecules | 76 | ||
| Bent molecules XY2 : using the C2v character table | 77 | ||
| XY3 molecules with D3h symmetry | 78 | ||
| XY3 molecules with C3v symmetry | 80 | ||
| XY4 molecules with Td or D4h symmetry | 81 | ||
| XY6 molecules with Oh symmetry | 81 | ||
| Metal carbonyl complexes, M(CO)n | 82 | ||
| Metal carbonyl complexes M(CO)6\x02n Xn | 82 | ||
| Observing IR spectroscopic absorptions | 84 | ||
| 3.8 Chiral molecules | 85 | ||
| 4 Experimental techniques | 90 | ||
| 4.1 Introduction | 90 | ||
| 4.2 Separation and purification techniques | 90 | ||
| Gas chromatography (GC) | 90 | ||
| Liquid chromatography (LC) | 91 | ||
| High-performance liquid chromatography (HPLC) | 92 | ||
| Recrystallization | 93 | ||
| 4.3 Elemental analysis | 93 | ||
| CHN analysis by combustion | 93 | ||
| Atomic absorption spectroscopy (AAS) | 94 | ||
| 4.4 Compositional analysis: thermogravimetry (TG) | 96 | ||
| 4.5 Mass spectrometry | 97 | ||
| Electron ionization (EI) | 97 | ||
| Fast atom bombardment (FAB) | 98 | ||
| Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) | 99 | ||
| Electrospray ionization (ESI) | 101 | ||
| 4.6 Infrared and Raman spectroscopies | 102 | ||
| Energies and wavenumbers of molecular vibrations | 102 | ||
| The Fourier transform infrared (FT-IR) spectrometer and sample preparation | 103 | ||
| Diagnostic absorptions | 103 | ||
| Deuterium/hydrogen exchange | 104 | ||
| Raman spectroscopy | 106 | ||
| 4.7 Electronic spectroscopy | 108 | ||
| UV-VIS absorption spectroscopy | 108 | ||
| Types of absorption | 108 | ||
| Absorbance and the Beer–Lambert Law | 109 | ||
| Emission spectroscopy | 110 | ||
| 4.8 Nuclear magnetic resonance (NMR) spectroscopy | 110 | ||
| NMR active nuclei and isotope abundance | 111 | ||
| Which nuclei are suitable for NMR spectroscopic studies? | 111 | ||
| Resonance frequencies and chemical shifts | 112 | ||
| Chemical shift ranges | 112 | ||
| Solvents for solution studies | 112 | ||
| Integration of signals and signal broadening | 114 | ||
| Homonuclear spin–spin coupling: 1 H–1 H | 114 | ||
| Heteronuclear spin–spin coupling: 13 C–1 H | 115 | ||
| Case studies | 115 | ||
| Stereochemically non-rigid species | 117 | ||
| Exchange processes in solution | 120 | ||
| 4.9 Electron paramagnetic resonance (EPR) spectroscopy | 121 | ||
| What is EPR spectroscopy? | 121 | ||
| The Zeeman electronic effect | 121 | ||
| EPR spectra | 122 | ||
| 4.10 Mo¨ssbauer spectroscopy | 124 | ||
| The technique of MoÅN ssbauer spectroscopy | 124 | ||
| What can isomer shift data tell us? | 125 | ||
| 4.11 Structure determination: diffraction methods | 126 | ||
| X-ray diffraction (XRD) | 126 | ||
| Single crystal X-ray diffraction | 127 | ||
| Powder X-ray diffraction | 129 | ||
| Single crystal neutron diffraction | 129 | ||
| Electron diffraction | 130 | ||
| Low-energy electron diffraction (LEED) | 130 | ||
| Structural databases | 130 | ||
| 4.12 Photoelectron spectroscopy (PES, UPS, XPS, ESCA) | 130 | ||
| 4.13 Computational methods | 131 | ||
| Hartree–Fock theory | 132 | ||
| Density functional theory | 132 | ||
| Hu¨ckel MO theory | 132 | ||
| Molecular mechanics (MM) | 132 | ||
| 5 Bonding in polyatomic molecules | 144 | ||
| 5.1 Introduction | 144 | ||
| 5.2 Valence bond theory: hybridization of atomic orbitals | 144 | ||
| What is orbital hybridization? | 144 | ||
| sp Hybridization: a scheme for linear species | 145 | ||
| sp2 Hybridization: a scheme for trigonal planar species | 146 | ||
| sp3 Hybridization: a scheme for tetrahedral and related species | 147 | ||
| Other hybridization schemes | 148 | ||
| 5.3 Valence bond theory: multiple bonding in polyatomic molecules | 149 | ||
| C2 H4 | 149 | ||
| HCN | 149 | ||
| BF3 | 150 | ||
| 5.4 Natural bond orbitals | 151 | ||
| 5.5 Molecular orbital theory: the ligand group orbital approach and | 151 | ||
| Molecular orbital diagrams: moving from a diatomic to polyatomic species | 151 | ||
| MO approach to bonding in linear XH2 : symmetry matching by inspection | 152 | ||
| MO approach to bonding in linear XH2 : working from molecular symmetry | 153 | ||
| A bent triatomic: H2 O | 153 | ||
| 5.6 Molecular orbital theory applied to the polyatomic molecules BH3 , NH3 and CH4 | 156 | ||
| BH3 | 156 | ||
| NH3 | 157 | ||
| CH4 | 159 | ||
| A comparison of the MO and VB bonding models | 160 | ||
| 5.7 Molecular orbital theory: bonding analyses soon become complicated | 161 | ||
| 5.8 Molecular orbital theory: learning to use the theory objectively -Bonding in CO2 | 164 | ||
| p-Bonding in CO2 | 164 | ||
| .NO3 | 165 | ||
| SF6 | 165 | ||
| Three-centre two-electron interactions | 167 | ||
| A more advanced problem: B2 H6 | 169 | ||
| 6 Structures and energetics of metallic and ionic solids | 177 | ||
| 6.1 Introduction | 177 | ||
| 6.2 Packing of spheres | 177 | ||
| Cubic and hexagonal close-packing | 177 | ||
| The unit cell: hexagonal and cubic close-packing | 178 | ||
| Interstitial holes: hexagonal and cubic close-packing | 179 | ||
| Non-close-packing: simple cubic and body-centred cubic arrays | 180 | ||
| 6.3 The packing-of-spheres model applied to the structures of elements | 180 | ||
| Group 18 elements in the solid state | 180 | ||
| H2 and F2 in the solid state | 181 | ||
| Metallic elements in the solid state | 181 | ||
| 6.4 Polymorphism in metals | 182 | ||
| Polymorphism: phase changes in the solid state | 182 | ||
| Phase diagrams | 183 | ||
| 6.5 Metallic radii | 183 | ||
| 6.6 Melting points and standard enthalpies of atomization of metals | 184 | ||
| 6.7 Alloys and intermetallic compounds | 184 | ||
| Substitutional alloys | 185 | ||
| Interstitial alloys | 185 | ||
| Intermetallic compounds | 188 | ||
| 6.8 Bonding in metals and semiconductors | 188 | ||
| Electrical conductivity and resistivity | 188 | ||
| Band theory of metals and insulators | 189 | ||
| The Fermi level | 190 | ||
| 6.9 Semiconductors | 190 | ||
| Intrinsic semiconductors | 191 | ||
| Extrinsic (n- and p-type) semiconductors | 191 | ||
| 6.10 Sizes of ions | 191 | ||
| Ionic radii | 193 | ||
| Periodic trends in ionic radii | 193 | ||
| 6.11 Ionic lattices | 195 | ||
| The rock salt (NaCl) structure type | 196 | ||
| The caesium chloride (CsCl) structure type | 197 | ||
| The fluorite (CaF2) structure type | 198 | ||
| The antifluorite structure type | 198 | ||
| The zinc blende (ZnS) structure type: a diamond-type network | 198 | ||
| The b -cristobalite (SiO2) structure type | 199 | ||
| The wurtzite (ZnS) structure type | 199 | ||
| The rutile (TiO2) structure type | 199 | ||
| CdI2 and CdCl2 : layer structures | 200 | ||
| The perovskite (CaTiO3) structure type: a double oxide | 200 | ||
| 6.12 Crystal structures of semiconductors | 201 | ||
| 6.13 Lattice energy: estimates from an electrostatic model | 201 | ||
| Coulombic attraction within an isolated ion-pair | 201 | ||
| Coulombic interactions in an ionic lattice | 202 | ||
| Born forces | 202 | ||
| The Born–LandeÅL equation | 203 | ||
| Madelung constants | 203 | ||
| Refinements to the Born–LandeÅL equation | 204 | ||
| Overview | 204 | ||
| 6.14 Lattice energy: the Born–Haber cycle | 204 | ||
| 6.15 Lattice energy: ‘calculated’ versus ‘experimental’ values | 206 | ||
| 6.16 Estimating lattice energies of new materials | 206 | ||
| The Kapustinskii equation | 206 | ||
| The volume-based thermodynamic (VBT) approach | 206 | ||
| 6.17 Applications of lattice energies | 208 | ||
| Estimation of electron affinities | 208 | ||
| Fluoride affinities | 208 | ||
| Estimation of standard enthalpies of formation and disproportionation | 209 | ||
| 6.18 Defects in solid state lattices | 210 | ||
| Schottky defect | 210 | ||
| Frenkel defect | 211 | ||
| Experimental observation of Schottky and Frenkel defects | 211 | ||
| Non-stoichiometric compounds | 211 | ||
| Colour centres (F-centres) | 212 | ||
| Thermodynamic effects of crystal defects | 212 | ||
| 7 Acids, bases and ions in aqueous solution | 218 | ||
| 7.1 Introduction | 218 | ||
| 7.2 Properties of water | 218 | ||
| Structure and hydrogen bonding | 218 | ||
| The self-ionization of water | 220 | ||
| Water as a Bronsted acid or base | 220 | ||
| 7.3 Definitions and units in aqueous solution | 221 | ||
| Molarity and molality | 221 | ||
| Standard state | 221 | ||
| Activity | 222 | ||
| 7.4 Some Brønsted acids and bases | 222 | ||
| Carboxylic acids: examples of mono-, di- and polybasic acids | 222 | ||
| Inorganic acids | 224 | ||
| Inorganic bases: hydroxides | 225 | ||
| Inorganic bases: nitrogen bases | 225 | ||
| 7.5 The energetics of acid dissociation in aqueous solution | 226 | ||
| Hydrogen halides | 226 | ||
| H2 S; H2 Se and H2 Te | 227 | ||
| 7.6 Trends within a series of oxoacids EOn (OH)m | 227 | ||
| 7.7 Aquated cations: formation and acidic properties | 228 | ||
| Water as a Lewis base | 228 | ||
| Aquated cations as Bronsted acids | 230 | ||
| 7.8 Amphoteric oxides and hydroxides | 231 | ||
| Amphoteric behaviour | 231 | ||
| Periodic trends in amphoteric properties | 231 | ||
| 7.9 Solubilities of ionic salts | 232 | ||
| Solubility and saturated solutions | 232 | ||
| Sparingly soluble salts and solubility products | 232 | ||
| The energetics of the dissolution of an ionic salt: \x01solG | 233 | ||
| The energetics of the dissolution of an ionic salt: hydration of ions | 234 | ||
| Solubilities: some concluding remarks | 236 | ||
| 7.10 Common-ion effect | 236 | ||
| 7.11 Coordination complexes: an introduction | 237 | ||
| Definitions and terminology | 237 | ||
| Investigating coordination complex formation | 238 | ||
| 7.12 Stability constants of coordination complexes | 239 | ||
| Determination of stability constants | 241 | ||
| Trends in stepwise stability constants | 241 | ||
| Thermodynamic considerations of complex formation: an introduction | 242 | ||
| 7.13 Factors affecting the stabilities of complexes containing only monodentate ligands | 246 | ||
| Ionic size and charge | 246 | ||
| Hard and soft metal centres and ligands | 246 | ||
| 8 Reduction and oxidation | 255 | ||
| 8.1 Introduction | 255 | ||
| Oxidation and reduction | 255 | ||
| Oxidation states | 256 | ||
| Stock nomenclature | 256 | ||
| 8.2 Standard reduction potentials, Eo , and relationships between Eo ,\x01Go and K | 257 | ||
| Half-cells and galvanic cells | 257 | ||
| Defining and using standard reduction potentials, E | 258 | ||
| Dependence of reduction potentials on cell conditions | 261 | ||
| 8.3 The effect of complex formation or precipitation on Mz+/M reduction potentials | 265 | ||
| Half-cells involving silver halides | 266 | ||
| Modifying the relative stabilities of different oxidation states of a metal | 267 | ||
| 8.4 Disproportionation reactions | 269 | ||
| Disproportionation | 269 | ||
| Stabilizing species against disproportionation | 270 | ||
| 8.5 Potential diagrams | 270 | ||
| 8.6 Frost–Ebsworth diagrams | 272 | ||
| Frost–Ebsworth diagrams and their relationship to potential diagrams | 272 | ||
| Interpretation of Frost–Ebsworth diagrams | 273 | ||
| 8.7 The relationships between standard reduction potentials and some other quantities | 275 | ||
| Factors influencing the magnitudes of standard reduction potentials | 275 | ||
| Values of \x01fG for aqueous ions | 276 | ||
| 8.8 Applications of redox reactions to the extraction of elements from their ores | 277 | ||
| Ellingham diagrams | 277 | ||
| 9 Non-aqueous media | 283 | ||
| 9.1 Introduction | 283 | ||
| 9.2 Relative permittivity | 284 | ||
| 9.3 Energetics of ionic salt transfer from water to an organic solvent | 285 | ||
| 9.4 Acid–base behaviour in non-aqueous solvents | 286 | ||
| Strengths of acids and bases | 286 | ||
| Levelling and differentiating effects | 286 | ||
| ‘Acids’ in acidic solvents | 286 | ||
| Acids and bases: a solvent-oriented definition | 287 | ||
| Proton-containing and aprotic solvents | 287 | ||
| 9.5 Liquid sulfur dioxide | 287 | ||
| 9.6 Liquid ammonia | 288 | ||
| Physical properties | 288 | ||
| Self-ionization | 288 | ||
| Reactions in liquid NH3 | 288 | ||
| Solutions of s-block metals in liquid NH3 | 290 | ||
| Redox reactions in liquid NH3 | 291 | ||
| 9.7 Liquid hydrogen fluoride | 291 | ||
| Physical properties | 291 | ||
| Acid–base behaviour in liquid HF | 291 | ||
| Electrolysis in liquid HF | 293 | ||
| 9.8 Sulfuric acid and fluorosulfonic acid | 293 | ||
| Physical properties of sulfuric acid | 293 | ||
| Acid–base behaviour in liquid H2 SO4 | 293 | ||
| Physical properties of fluorosulfonic acid | 294 | ||
| 9.9 Superacids | 294 | ||
| 9.10 Bromine trifluoride | 296 | ||
| Physical properties | 296 | ||
| Behaviour of fluoride salts and molecular fluorides in BrF3 | 296 | ||
| Reactions in BrF3 | 297 | ||
| 9.11 Dinitrogen tetraoxide | 297 | ||
| Physical properties | 297 | ||
| Reactions in N2 O4 | 297 | ||
| 9.12 Ionic liquids | 299 | ||
| Molten salt solvent systems | 299 | ||
| Ionic liquids at ambient temperatures | 300 | ||
| 9.13 Supercritical fluids | 307 | ||
| Properties of supercritical fluids and their uses as solvents | 307 | ||
| Supercritical fluids as media for inorganic chemistry | 309 | ||
| 10 Hydrogen | 314 | ||
| 10.1 Hydrogen: the simplest atom | 314 | ||
| 10.2 The H. and H\x02 ions | 314 | ||
| The hydrogen ion (proton) | 314 | ||
| The hydride ion | 315 | ||
| 10.3 Isotopes of hydrogen | 315 | ||
| Protium and deuterium | 315 | ||
| Kinetic isotope effects | 316 | ||
| Deuterated compounds | 316 | ||
| Tritium | 318 | ||
| 10.4 Dihydrogen | 318 | ||
| Occurrence | 318 | ||
| Physical properties | 318 | ||
| Synthesis and uses | 318 | ||
| Reactivity | 322 | ||
| 10.5 Polar and non-polar E–H bonds | 323 | ||
| 10.6 Hydrogen bonding | 324 | ||
| The hydrogen bond | 324 | ||
| Trends in boiling points, melting points and enthalpies of vaporization for p -block binary hydrides | 327 | ||
| Infrared spectroscopy | 328 | ||
| Solid state structures | 329 | ||
| Hydrogen bonding in biological systems | 331 | ||
| 10.7 Binary hydrides: classification and general properties | 332 | ||
| Classification | 332 | ||
| Metallic hydrides | 334 | ||
| Saline hydrides | 334 | ||
| Molecular hydrides and complexes derived from them | 335 | ||
| Covalent hydrides with extended structures | 336 | ||
| 11 Group 1: the alkali metals | 341 | ||
| 11.1 Introduction | 341 | ||
| 11.2 Occurrence, extraction and uses | 341 | ||
| Occurrence | 341 | ||
| Extraction | 342 | ||
| Major uses of the alkali metals and their compounds | 343 | ||
| 11.3 Physical properties | 344 | ||
| General properties | 344 | ||
| Atomic spectra and flame tests | 344 | ||
| Radioactive isotopes | 346 | ||
| NMR active nuclei | 348 | ||
| 11.4 The metals | 348 | ||
| Appearance | 348 | ||
| Reactivity | 348 | ||
| 11.5 Halides | 350 | ||
| 11.6 Oxides and hydroxides | 351 | ||
| Oxides, peroxides, superoxides, suboxides and ozonides | 351 | ||
| Hydroxides | 353 | ||
| 11.7 Salts of oxoacids: carbonates and hydrogencarbonates | 353 | ||
| 11.8 Aqueous solution chemistry and macrocyclic complexes | 354 | ||
| Hydrated ions | 354 | ||
| Complex ions | 355 | ||
| 11.9 Non-aqueous coordination chemistry | 359 | ||
| 12 The group 2 metals | 364 | ||
| 12.1 Introduction | 364 | ||
| 12.2 Occurrence, extraction and uses | 364 | ||
| Occurrence | 364 | ||
| Extraction | 365 | ||
| Major uses of the group 2 metals and their compounds | 365 | ||
| 12.3 Physical properties | 367 | ||
| General properties | 367 | ||
| Flame tests | 367 | ||
| Radioactive isotopes | 367 | ||
| 12.4 The metals | 369 | ||
| Appearance | 369 | ||
| Reactivity | 369 | ||
| 12.5 Halides | 370 | ||
| Beryllium halides | 370 | ||
| Halides of Mg, Ca, Sr and Ba | 372 | ||
| 12.6 Oxides and hydroxides | 374 | ||
| Oxides and peroxides | 374 | ||
| Hydroxides | 377 | ||
| 12.7 Salts of oxoacids | 378 | ||
| 12.8 Complex ions in aqueous solution | 378 | ||
| Aqua species of beryllium | 378 | ||
| Aqua species of Mg2+, Ca2+, Sr2+ and Ba2 | 379 | ||
| Complexes with ligands other than water | 380 | ||
| 12.9 Complexes with amido or alkoxy ligands | 381 | ||
| 12.10 Diagonal relationships between Li and Mg, and between Be and Al | 382 | ||
| Lithium and magnesium | 382 | ||
| Beryllium and aluminium | 383 | ||
| 13 The group 13 elements | 387 | ||
| 13.1 Introduction | 387 | ||
| 13.2 Occurrence, extraction and uses | 387 | ||
| Occurrence | 387 | ||
| Extraction | 387 | ||
| Major uses of the group 13 elements and their compounds | 389 | ||
| 13.3 Physical properties | 391 | ||
| Electronic configurations and oxidation states | 391 | ||
| NMR active nuclei | 395 | ||
| 13.4 The elements | 395 | ||
| Appearance | 395 | ||
| Structures of the elements | 395 | ||
| Reactivity | 395 | ||
| 13.5 Simple hydrides | 396 | ||
| Neutral hydrides | 396 | ||
| The [MH4]- ions | 402 | ||
| 13.6 Halides and complex halides | 403 | ||
| Boron halides: BX3 and B2 X4 | 403 | ||
| Al(III), Ga(III), In(III) and Tl(III) halides and their complexes | 406 | ||
| Lower oxidation state Al, Ga, In and Tl halides | 409 | ||
| 13.7 Oxides, oxoacids, oxoanions and hydroxides | 411 | ||
| Boron oxides, oxoacids and oxoanions | 411 | ||
| Aluminium oxides, oxoacids, oxoanions and hydroxides | 414 | ||
| Oxides of Ga, In and Tl | 416 | ||
| 13.8 Compounds containing nitrogen | 416 | ||
| Nitrides | 416 | ||
| Ternary boron nitrides | 416 | ||
| Molecular species containing B–N or B–P bonds | 419 | ||
| Molecular species containing group 13 metal–nitrogen bonds | 422 | ||
| 13.9 Aluminium to thallium: salts of oxoacids, aqueous solution chemistry and complexes | 423 | ||
| Aluminium sulfate and alums | 423 | ||
| Aqua ions | 423 | ||
| Redox reactions in aqueous solution | 424 | ||
| Coordination complexes of the M3+ ions | 425 | ||
| 13.10 Metal borides | 426 | ||
| 13.11 Electron-deficient borane and carbaborane clusters: an introduction | 426 | ||
| 14 The group 14 elements | 443 | ||
| 14.1 Introduction | 443 | ||
| 14.2 Occurrence, extraction and uses | 443 | ||
| Occurrence | 443 | ||
| Extraction and manufacture | 444 | ||
| Uses | 444 | ||
| 14.3 Physical properties | 448 | ||
| Ionization energies and cation formation | 448 | ||
| Some energetic and bonding considerations | 450 | ||
| NMR active nuclei | 452 | ||
| Mossbauer spectroscopy | 452 | ||
| 14.4 Allotropes of carbon | 452 | ||
| Graphite and diamond: structure and properties | 452 | ||
| Graphite: intercalation compounds | 454 | ||
| Fullerenes: synthesis and structure | 455 | ||
| Fullerenes: reactivity | 456 | ||
| Carbon nanotubes | 461 | ||
| 14.5 Structural and chemical properties of silicon, germanium, tin and lead | 461 | ||
| Structures | 461 | ||
| Chemical properties | 461 | ||
| 14.6 Hydrides | 462 | ||
| Binary hydrides | 463 | ||
| Halohydrides of silicon and germanium | 465 | ||
| 14.7 Carbides, silicides, germides, stannides and plumbides | 466 | ||
| Carbides | 466 | ||
| Silicides | 467 | ||
| Zintl ions containing Si, Ge, Sn and Pb | 467 | ||
| 14.8 Halides and complex halides | 471 | ||
| Carbon halides | 471 | ||
| Silicon halides | 473 | ||
| Halides of germanium, tin and lead | 474 | ||
| 14.9 Oxides, oxoacids and hydroxides | 477 | ||
| Oxides and oxoacids of carbon | 477 | ||
| Silica, silicates and aluminosilicates | 480 | ||
| Oxides, hydroxides and oxoacids of germanium, tin and lead | 488 | ||
| 14.10 Siloxanes and polysiloxanes (silicones) | 490 | ||
| 14.11 Sulfides | 491 | ||
| 14.12 Cyanogen, silicon nitride and tin nitride | 494 | ||
| Cyanogen and its derivatives | 494 | ||
| Silicon nitride | 496 | ||
| Tin(IV) nitride | 496 | ||
| 14.13 Aqueous solution chemistry and salts of oxoacids of germanium, tin and lead | 496 | ||
| 15 The group 15 elements | 502 | ||
| 15.1 Introduction | 502 | ||
| 15.2 Occurrence, extraction and uses | 503 | ||
| Occurrence | 503 | ||
| Extraction | 504 | ||
| Uses | 505 | ||
| 15.3 Physical properties | 507 | ||
| Bonding considerations | 508 | ||
| NMR active nuclei | 509 | ||
| Radioactive isotopes | 510 | ||
| 15.4 The elements | 510 | ||
| Nitrogen | 510 | ||
| Phosphorus | 510 | ||
| Arsenic, antimony and bismuth | 512 | ||
| 15.5 Hydrides | 513 | ||
| Trihydrides, EH3 (E. N, P, As, Sb and Bi) | 513 | ||
| Hydrides E2 H4 (E. N, P, As) | 517 | ||
| Chloramine and hydroxylamine | 518 | ||
| Hydrogen azide and azide salts | 520 | ||
| 15.6 Nitrides, phosphides, arsenides, antimonides and bismuthides | 521 | ||
| Nitrides | 521 | ||
| Phosphides | 523 | ||
| Arsenides, antimonides and bismuthides | 524 | ||
| 15.7 Halides, oxohalides and complex halides | 525 | ||
| Nitrogen halides | 525 | ||
| Oxofluorides and oxochlorides of nitrogen | 527 | ||
| Phosphorus halides | 528 | ||
| Phosphoryl trichloride, POCl3 | 531 | ||
| Arsenic and antimony halides | 531 | ||
| Bismuth halides | 533 | ||
| 15.8 Oxides of nitrogen | 534 | ||
| Dinitrogen monoxide, N2O | 534 | ||
| Nitrogen monoxide, NO | 535 | ||
| Dinitrogen trioxide, N2O3 | 537 | ||
| Dinitrogen tetraoxide, N2 O4 , and nitrogen dioxide, NO2 | 537 | ||
| Dinitrogen pentaoxide, N2O5 | 539 | ||
| 15.9 Oxoacids of nitrogen | 539 | ||
| Isomers of H2 N2 O2 | 539 | ||
| Nitrous acid, HNO2 | 540 | ||
| Nitric acid, HNO3 , and its derivatives | 540 | ||
| 15.10 Oxides of phosphorus, arsenic, antimony and bismuth | 544 | ||
| Oxides of phosphorus | 544 | ||
| Oxides of arsenic, antimony and bismuth | 545 | ||
| 15.11 Oxoacids of phosphorus | 545 | ||
| Phosphinic acid, H3 PO2 | 547 | ||
| Phosphonic acid, H3 PO3 | 547 | ||
| Hypodiphosphoric acid, H4 P2 O6 | 547 | ||
| Phosphoric acid, H3 PO4 , and its derivatives | 548 | ||
| Chiral phosphate anions | 550 | ||
| 15.12 Oxoacids of arsenic, antimony and bismuth | 550 | ||
| 15.13 Phosphazenes | 553 | ||
| 15.14 Sulfides and selenides | 556 | ||
| Sulfides and selenides of phosphorus | 556 | ||
| Arsenic, antimony and bismuth sulfides | 557 | ||
| 15.15 Aqueous solution chemistry and complexes | 558 | ||
| 16 The group 16 elements | 564 | ||
| 16.1 Introduction | 564 | ||
| 16.2 Occurrence, extraction and uses | 565 | ||
| Occurrence | 565 | ||
| Extraction | 565 | ||
| Uses | 565 | ||
| 16.3 Physical properties and bonding considerations | 567 | ||
| NMR active nuclei and isotopes as tracers | 569 | ||
| 16.4 The elements | 570 | ||
| Dioxygen | 570 | ||
| Ozone | 571 | ||
| Sulfur: allotropes | 573 | ||
| Sulfur: reactivity | 574 | ||
| Selenium and tellurium | 575 | ||
| 16.5 Hydrides | 576 | ||
| Water, H2O | 576 | ||
| Hydrogen peroxide, H2O2 | 577 | ||
| Hydrides H2E (E = S, Se, Te) | 580 | ||
| Polysulfanes | 581 | ||
| 16.6 Metal sulfides, polysulfides, polyselenides and polytellurides | 581 | ||
| Sulfides | 581 | ||
| Polysulfides | 581 | ||
| Polyselenides and polytellurides | 582 | ||
| 16.7 Halides, oxohalides and complex halides | 584 | ||
| Oxygen fluorides | 584 | ||
| Sulfur fluorides and oxofluorides | 585 | ||
| Sulfur chlorides and oxochlorides | 588 | ||
| Halides of selenium and tellurium | 589 | ||
| 16.8 Oxides | 591 | ||
| Oxides of sulfur | 591 | ||
| Oxides of selenium and tellurium | 596 | ||
| 16.9 Oxoacids and their salts | 597 | ||
| Dithionous acid, H2S2O4 | 597 | ||
| Sulfurous and disulfurous acids, H2SO3 and H2S2O5 | 599 | ||
| Dithionic acid, H2S2O6 | 600 | ||
| Sulfuric acid, H2SO4 | 600 | ||
| Fluoro- and chlorosulfonic acids, HSO3F and HSO3 Cl | 602 | ||
| Polyoxoacids with S–O–S units | 602 | ||
| Peroxysulfuric acids, H2S2O8 and H2SO5 | 602 | ||
| Thiosulfuric acid, H2S2O3, and polythionates | 602 | ||
| Oxoacids of selenium and tellurium | 603 | ||
| 16.10 Compounds of sulfur and selenium with nitrogen | 604 | ||
| Sulfur–nitrogen compounds | 604 | ||
| Tetraselenium tetranitride | 606 | ||
| 16.11 Aqueous solution chemistry of sulfur, selenium and tellurium | 606 | ||
| 17 The group 17 elements | 611 | ||
| 17.1 Introduction | 611 | ||
| Fluorine, chlorine, bromine and iodine | 611 | ||
| Astatine and tennessine | 612 | ||
| 17.2 Occurrence, extraction and uses | 612 | ||
| Occurrence | 612 | ||
| Extraction | 612 | ||
| Uses | 613 | ||
| 17.3 Physical properties and bonding considerations | 615 | ||
| NMR active nuclei and isotopes as tracers | 618 | ||
| 17.4 The elements | 620 | ||
| Difluorine | 620 | ||
| Dichlorine, dibromine and diiodine | 620 | ||
| Charge transfer complexes | 621 | ||
| Clathrates | 623 | ||
| 17.5 Hydrogen halides | 623 | ||
| 17.6 Metal halides: structures and energetics | 624 | ||
| 17.7 Interhalogen compounds and polyhalogen ions | 626 | ||
| Interhalogen compounds | 626 | ||
| Bonding in . [XY2]- ions | 630 | ||
| Polyhalogen cations | 630 | ||
| Polyhalide anions | 631 | ||
| 17.8 Oxides and oxofluorides of chlorine, bromine and iodine | 631 | ||
| Oxides | 632 | ||
| Oxofluorides | 633 | ||
| 17.9 Oxoacids and their salts | 634 | ||
| Hypofluorous acid, HOF | 634 | ||
| Oxoacids of chlorine, bromine and iodine | 634 | ||
| 17.10 Aqueous solution chemist | 638 | ||
| 18 The group 18 elements | 645 | ||
| 18.1 Introduction | 645 | ||
| 18.2 Occurrence, extraction and uses | 646 | ||
| Occurrence | 646 | ||
| Extraction | 647 | ||
| Uses | 647 | ||
| 18.3 Physical properties | 648 | ||
| NMR active nuclei | 648 | ||
| 18.4 Compounds of xenon | 650 | ||
| Fluorides | 650 | ||
| Chlorides | 654 | ||
| Oxides | 654 | ||
| Oxofluorides and oxochlorides | 654 | ||
| Other compounds of xenon | 655 | ||
| 18.5 Compounds of argon, krypton and radon | 657 | ||
| 19 d-Block metal chemistry: general considerations | 661 | ||
| 19.1 Topic overview | 661 | ||
| 19.2 Ground state electronic configurations | 661 | ||
| d-Block metals versus transition elements | 661 | ||
| Electronic configurations | 662 | ||
| 19.3 Physical properties | 662 | ||
| 19.4 The reactivity of the metals | 664 | ||
| 19.5 Characteristic properties: a general perspective | 664 | ||
| Colour | 664 | ||
| Paramagnetism | 665 | ||
| Complex formation | 665 | ||
| Variable oxidation states | 665 | ||
| 19.6 Electroneutrality principle | 666 | ||
| 19.7 Coordination numbers and geometries | 667 | ||
| The Kepert model | 668 | ||
| Coordination numbers in the solid state | 669 | ||
| Coordination number 2 | 669 | ||
| Coordination number 3 | 669 | ||
| Coordination number 4 | 669 | ||
| Coordination number 5 | 671 | ||
| Coordination number 6 | 672 | ||
| Coordination number 7 | 673 | ||
| Coordination number 8 | 674 | ||
| Coordination number 9 | 675 | ||
| Coordination numbers of 10 and above | 676 | ||
| 19.8 Isomerism in d -block metal complexes | 676 | ||
| Structural isomerism: ionization isomers | 676 | ||
| Structural isomerism: hydration isomers | 677 | ||
| Structural isomerism: coordination isomerism | 677 | ||
| Structural isomerism: linkage isomerism | 677 | ||
| Stereoisomerism: diastereoisomers | 678 | ||
| Stereoisomerism: enantiomers | 679 | ||
| 20 d-Block metal chemistry: coordination complexes | 687 | ||
| 20.1 Introduction | 687 | ||
| High- and low-spin states | 687 | ||
| 20.2 Bonding in d -block metal complexes: valence bond theory | 688 | ||
| Hybridization schemes | 688 | ||
| 20.3 Crystal field theory | 689 | ||
| The octahedral crystal field | 689 | ||
| Crystal field stabilization energy: high- and low-spin octahedral complexes | 691 | ||
| Jahn–Teller distortions | 693 | ||
| The tetrahedral crystal field | 693 | ||
| The square planar crystal field | 695 | ||
| Other crystal fields | 696 | ||
| Crystal field theory: uses and limitations | 696 | ||
| 20.4 Molecular orbital theory: octahedral complexes | 697 | ||
| Complexes with no metal–ligand \x01 -bonding | 697 | ||
| Complexes with metal–ligand \x01 -bonding | 698 | ||
| 20.5 Ligand field theory | 703 | ||
| 20.6 Describing electrons in multi-electron systems | 703 | ||
| Quantum numbers L and ML for multi-electron species | 703 | ||
| Quantum numbers S and MS for multi-electron species | 704 | ||
| Microstates and term symbols | 704 | ||
| The quantum numbers J and MJ | 705 | ||
| Ground states of elements with Z=1-\x0210 | 706 | ||
| The d2 configuration | 708 | ||
| 20.7 Electronic spectra: absorption | 709 | ||
| Spectral features | 709 | ||
| Charge transfer absorptions | 710 | ||
| Selection rules | 711 | ||
| Electronic absorption spectra of octahedral and tetrahedral complexes | 712 | ||
| Interpretation of electronic absorption spectra: use of Racah parameters | 715 | ||
| Interpretation of electronic absorption spectra: Tanabe–Sugano diagrams | 718 | ||
| 20.8 Electronic spectra: emission | 719 | ||
| 20.9 Evidence for metal–ligand covalent bonding | 720 | ||
| The nephelauxetic effect | 720 | ||
| EPR spectroscopy | 721 | ||
| 20.10 Magnetic properties | 721 | ||
| Magnetic susceptibility and the spin-only formula | 721 | ||
| Spin and orbital contributions to the magnetic moment | 723 | ||
| The effects of temperature on \x06eff | 725 | ||
| Spin crossover | 726 | ||
| Ferromagnetism, antiferromagnetism and ferrimagnetism | 726 | ||
| 20.11 Thermodynamic aspects: ligand field stabilization energies (LFSE) | 728 | ||
| Trends in LFSE | 728 | ||
| Lattice energies and hydration energies of Mn+ ions | 729 | ||
| Octahedral versus tetrahedral coordination: spinels | 730 | ||
| 20.12 Thermodynamic aspects: the Irving–Williams series | 730 | ||
| 20.13 Thermodynamic aspects: oxidation states in aqueous solution | 731 | ||
| 21 d-Block metal chemistry: the first row metals | 738 | ||
| 21.1 Introduction | 738 | ||
| 21.2 Occurrence, extraction and uses | 738 | ||
| 21.3 Physical properties: an overview | 743 | ||
| 21.4 Group 3: scandium | 743 | ||
| The metal | 743 | ||
| Scandium(III) | 743 | ||
| 21.5 Group 4: titanium | 744 | ||
| The metal | 744 | ||
| Titanium(IV) | 745 | ||
| Titanium(III) | 748 | ||
| Low oxidation states | 748 | ||
| 21.6 Group 5: vanadium | 749 | ||
| The metal | 749 | ||
| Vanadium(V) | 749 | ||
| Vanadium(IV) | 750 | ||
| Vanadium(III) | 752 | ||
| Vanadium(II) | 753 | ||
| 21.7 Group 6: chromium | 754 | ||
| The metal | 754 | ||
| Chromium(VI) | 754 | ||
| Chromium(V) and chromium(IV) | 756 | ||
| Chromium(III) | 756 | ||
| Chromium(II) | 758 | ||
| Chromium–chromium multiple bonds | 759 | ||
| 21.8 Group 7: manganese | 761 | ||
| The metal | 761 | ||
| Manganese(VII) | 762 | ||
| Manganese(VI) | 763 | ||
| Manganese(V) | 763 | ||
| Manganese(IV) | 764 | ||
| Manganese(III) | 766 | ||
| Manganese(II) | 767 | ||
| Manganese(I) | 768 | ||
| 21.9 Group 8: iron | 769 | ||
| The metal | 769 | ||
| Iron(VI), iron(V) and iron(IV) | 769 | ||
| Iron(III) | 771 | ||
| Iron(II) | 775 | ||
| Iron in low oxidation states | 777 | ||
| 21.10 Group 9: cobalt | 777 | ||
| The metal | 777 | ||
| Cobalt(IV) | 778 | ||
| Cobalt(III) | 778 | ||
| Cobalt(II) | 781 | ||
| 21.11 Group 10: nickel | 785 | ||
| The metal | 785 | ||
| Nickel(IV) and nickel(III | 785 | ||
| Nickel(II) | 786 | ||
| Nickel(I) | 788 | ||
| 21.12 Group 11: copper | 788 | ||
| The metal | 788 | ||
| Copper(IV) and copper(III) | 789 | ||
| Copper(II) | 790 | ||
| Copper(I) | 793 | ||
| 21.13 Group 12: zinc | 796 | ||
| The metal | 796 | ||
| Zinc(II) | 796 | ||
| Zinc(I) | 797 | ||
| 22 d-Block metal chemistry: the heavier metals | 803 | ||
| 22.1 Introduction | 803 | ||
| 22.2 Occurrence, extraction and uses | 803 | ||
| 22.3 Physical properties | 806 | ||
| Effects of the lanthanoid contraction | 809 | ||
| Coordination numbers | 809 | ||
| NMR active nuclei | 809 | ||
| 22.4 Group 3: yttrium | 810 | ||
| The metal | 810 | ||
| Yttrium(III) | 810 | ||
| 22.5 Group 4: zirconium and hafnium | 810 | ||
| The metals | 810 | ||
| Zirconium(IV) and hafnium(IV) | 810 | ||
| Lower oxidation states of zirconium and hafnium | 812 | ||
| Zirconium clusters | 812 | ||
| 22.6 Group 5: niobium and tantalum | 812 | ||
| The metals | 812 | ||
| Niobium(V) and tantalum(V) | 813 | ||
| Niobium(IV) and tantalum(IV) | 815 | ||
| Lower oxidation state halides | 816 | ||
| 22.7 Group 6: molybdenum and tungsten | 817 | ||
| The metals | 817 | ||
| Molybdenum(VI) and tungsten(VI) | 818 | ||
| Molybdenum(V) and tungsten(V) | 823 | ||
| Molybdenum(IV) and tungsten(IV) | 823 | ||
| Molybdenum(III) and tungsten(III) | 825 | ||
| Molybdenum(II) and tungsten(II) | 826 | ||
| 22.8 Group 7: technetium and rhenium | 829 | ||
| The metals | 829 | ||
| High oxidation states of technetium and rhenium: M(VII), M(VI) and M(V) | 829 | ||
| Technetium(IV) and rhenium(IV) | 832 | ||
| Technetium(III) and rhenium(III) | 834 | ||
| Technetium(I) and rhenium(I) | 835 | ||
| 22.9 Group 8: ruthenium and osmium | 836 | ||
| The metals | 836 | ||
| High oxidation states of ruthenium and osmium: M(VIII), M(VII) and M(VI) | 836 | ||
| Ruthenium(V), (IV) and osmium(V), (IV) | 839 | ||
| Ruthenium(III) and osmium(III) | 841 | ||
| Ruthenium(II) and osmium(II) | 843 | ||
| Mixed-valence ruthenium complexes | 846 | ||
| 22.10 Group 9: rhodium and iridium | 847 | ||
| The metals | 847 | ||
| High oxidation states of rhodium and iridium: M(VI) and M(V) | 847 | ||
| Rhodium(IV) and iridium(IV) | 847 | ||
| Rhodium(III) and iridium(III) | 848 | ||
| Rhodium(II) and iridium(II) | 851 | ||
| Rhodium(I) and iridium(I) | 851 | ||
| 22.11 Group 10: palladium and platinum | 852 | ||
| The metals | 852 | ||
| The highest oxidation states: M(VI) and M(V) | 852 | ||
| Palladium(IV) and platinum(IV) | 853 | ||
| Palladium(III), platinum(III) and mixed-valence complexes | 854 | ||
| Palladium(II) and platinum(II) | 855 | ||
| Platinum(–II) | 858 | ||
| 22.12 Group 11: silver and gold | 860 | ||
| The metals | 860 | ||
| Gold(V) and silver(V) | 860 | ||
| Gold(III) and silver(III) | 860 | ||
| Gold(II) and silver(II) | 861 | ||
| Gold(I) and silver(I) | 863 | ||
| Gold(–I) and silver(–I) | 866 | ||
| 22.13 Group 12: cadmium and mercury | 866 | ||
| The metals | 866 | ||
| Cadmium(II) | 867 | ||
| Mercury(II) | 867 | ||
| Mercury(I) | 868 | ||
| 23 Organometallic compounds of s- and p-block elements | 875 | ||
| 23.1 Introduction | 875 | ||
| 23.2 Group 1: alkali metal organometallics | 875 | ||
| 23.3 Group 2 organometallics | 879 | ||
| Beryllium | 879 | ||
| Magnesium | 880 | ||
| Calcium, strontium and barium | 882 | ||
| 23.4 Group 13 | 884 | ||
| Boron | 884 | ||
| Aluminium | 884 | ||
| Gallium, indium and thallium | 887 | ||
| 23.5 Group 14 | 892 | ||
| Silicon | 893 | ||
| Germanium | 895 | ||
| Tin | 897 | ||
| Lead | 901 | ||
| Coparallel and tilted C5 -rings in group 14 metallocenes | 903 | ||
| 23.6 Group 15 | 904 | ||
| Bonding aspects and E=E bond formation | 904 | ||
| Arsenic, antimony and bismuth | 905 | ||
| 23.7 Group 16 | 909 | ||
| Selenium and tellurium | 909 | ||
| 24 Organometallic compounds of d-block elements | 915 | ||
| 24.1 Introduction | 915 | ||
| 24.2 Common types of ligand: bonding and spectroscopy | 915 | ||
| \x07-Bonded alkyl, aryl and related ligands | 915 | ||
| Carbonyl ligands | 916 | ||
| Hydride ligands | 918 | ||
| Phosphane and related ligands | 918 | ||
| x01-Bonded organic ligands | 920 | ||
| Nitrogen monoxide | 922 | ||
| Dinitrogen | 923 | ||
| Dihydrogen | 924 | ||
| 24.3 The 18-electron rule | 925 | ||
| 24.4 Covalent bond classification (CBC) | 926 | ||
| 24.5 Metal carbonyls: synthesis, physical properties and structure | 928 | ||
| Synthesis and physical properties | 929 | ||
| Structures | 932 | ||
| 24.6 The isolobal principle and application of Wade’s rules | 934 | ||
| 24.7 Total valence electron counts in d-block organometallic clusters | 937 | ||
| Single cage structures | 937 | ||
| Condensed cages | 939 | ||
| Limitations of total valence counting schemes | 939 | ||
| 24.8 Types of organometallic reactions | 940 | ||
| Substitution of CO ligands | 940 | ||
| Oxidative addition | 940 | ||
| Alkyl and hydrogen migrations | 941 | ||
| b-Hydrogen elimination | 942 | ||
| a-Hydrogen abstraction | 943 | ||
| Summary | 943 | ||
| 24.9 Metal carbonyls: selected reactions | 944 | ||
| 24.10 Metal carbonyl hydrides and halides | 945 | ||
| 24.11 Alkyl, aryl, alkene and alkyne complexes | 947 | ||
| x07-Bonded alkyl and aryl ligands | 947 | ||
| Alkene ligands | 947 | ||
| Alkyne ligands | 950 | ||
| 24.12 Allyl and buta-1,3-diene complexes | 951 | ||
| Allyl and related ligands | 951 | ||
| Buta-1,3-diene and related ligands | 953 | ||
| 24.13 Carbene and carbyne complexes | 953 | ||
| 24.14 Complexes containing Z5 -cyclopentadienyl ligands | 955 | ||
| Ferrocene and other metallocenes | 956 | ||
| (Z5-Cp)2Fe2(CO)4 and derivatives | 958 | ||
| 24.15 Complexes containing Z6- and Z7-ligands | 962 | ||
| Z6-Arene ligands | 962 | ||
| Cycloheptatriene and derived ligands | 963 | ||
| 24.16 Complexes containing the Z4-cyclobutadiene ligand | 964 | ||
| 25 Catalysis and some industrial processes | 971 | ||
| 25.1 Introduction and definitions | 971 | ||
| 25.2 Catalysis: introductory concepts | 971 | ||
| Energy profiles for a reaction: catalysed versus non-catalysed | 971 | ||
| Catalytic cycles | 972 | ||
| Choosing a catalyst | 974 | ||
| 25.3 Homogeneous catalysis: alkene (olefin) and alkyne metathesis | 974 | ||
| 25.4 Homogeneous catalytic reduction of N2 to NH3 | 977 | ||
| 25.5 Homogeneous catalysis: industrial applications | 978 | ||
| Alkene hydrogenation | 978 | ||
| Monsanto and Cativa acetic acid syntheses | 982 | ||
| Tennessee–Eastman acetic anhydride process | 983 | ||
| Hydroformylation (Oxo-process) | 984 | ||
| Alkene oligomerization | 986 | ||
| 25.6 Homogeneous catalyst development | 986 | ||
| Polymer-supported catalysts | 986 | ||
| Biphasic catalysis | 987 | ||
| 25.7 Heterogeneous catalysis: surfaces and interactions with adsorbates | 989 | ||
| 25.8 Heterogeneous catalysis: commercial applications | 991 | ||
| Alkene polymerization: Ziegler–Natta catalysis and metallocene catalysts | 991 | ||
| Fischer–Tropsch carbon chain growth | 993 | ||
| Haber–Bosch process | 994 | ||
| Production of SO3 in the Contact process | 995 | ||
| Catalytic converters | 996 | ||
| Zeolites as catalysts for organic transformations: uses of ZSM-5 | 997 | ||
| 25.9 Heterogeneous catalysis: organometallic cluster models | 998 | ||
| 26 d-Block metal complexes: reaction mechanisms | 1007 | ||
| 26.1 Introduction | 1007 | ||
| 26.2 Ligand substitutions: some general points | 1007 | ||
| Kinetically inert and labile complexes | 1007 | ||
| Stoichiometric equations say nothing about mechanism | 1008 | ||
| Types of substitution mechanism | 1009 | ||
| Activation parameters | 1009 | ||
| 26.3 Substitution in square planar complexes | 1010 | ||
| Rate equations, mechanism and the trans-effect | 1010 | ||
| Ligand nucleophilicity | 1013 | ||
| 26.4 Substitution and racemization in octahedral complexes | 1015 | ||
| Water exchange | 1015 | ||
| The Eigen–Wilkins mechanism | 1017 | ||
| Stereochemistry of substitution | 1018 | ||
| Base-catalysed hydrolysis | 1020 | ||
| Isomerization and racemization of octahedral complexes | 1021 | ||
| 26.5 Electron-transfer processes | 1022 | ||
| Inner-sphere mechanism | 1022 | ||
| Outer-sphere mechanism | 1025 | ||
| 27 The f-block metals: lanthanoids and actinoids | 1033 | ||
| 27.1 Introduction | 1033 | ||
| 27.2 f-Orbitals and oxidation states | 1035 | ||
| 27.3 Atom and ion sizes | 1036 | ||
| The lanthanoid contraction | 1036 | ||
| Coordination numbers | 1036 | ||
| 27.4 Spectroscopic and magnetic properties | 1037 | ||
| Electronic spectra and magnetic moments: lanthanoids | 1037 | ||
| Luminescence of lanthanoid complexes | 1040 | ||
| Electronic spectra and magnetic moments: actinoids | 1041 | ||
| 27.5 Sources of the lanthanoids and actinoids | 1041 | ||
| Occurrence and separation of the lanthanoids | 1041 | ||
| The actinoids | 1041 | ||
| 27.6 Lanthanoid metals | 1043 | ||
| 27.7 Inorganic compounds and coordination complexes of the lanthanoids | 1045 | ||
| Halides | 1045 | ||
| Hydroxides and oxides | 1046 | ||
| Complexes of Ln(III) | 1046 | ||
| 27.8 Organometallic complexes of the lanthanoids | 1048 | ||
| x07-Bonded complexes | 1048 | ||
| Cyclopentadienyl complexes | 1051 | ||
| Bis(arene) derivatives | 1053 | ||
| Complexes containing the Z8-cyclooctatetraenyl ligand | 1053 | ||
| 27.9 The actinoid metals | 1053 | ||
| 27.10 Inorganic compounds and coordination complexes of thorium, uranium and plutonium | 1054 | ||
| Thorium | 1054 | ||
| Uranium | 1055 | ||
| Plutonium | 1057 | ||
| 27.11 Organometallic complexes of thorium and uranium | 1058 | ||
| -Bonded complexes | 1058 | ||
| Cyclopentadienyl derivatives | 1058 | ||
| Complexes containing the Z8-cyclooctatetraenyl ligand | 1059 | ||
| 28 Inorganic materials and nanotechnology | 1065 | ||
| 28.1 Introduction | 1065 | ||
| 28.2 Electrical conductivity in ionic solids | 1065 | ||
| Sodium and lithium ion conductors | 1066 | ||
| d-Block metal(II) oxides | 1068 | ||
| 28.3 Transparent conducting oxides and their applications in devices | 1068 | ||
| Sn-doped In2O3 (ITO) and F-doped SnO2 (FTO) | 1068 | ||
| Dye-sensitized solar cells (DSCs) | 1069 | ||
| Solid state lighting: OLEDs | 1070 | ||
| Solid state lighting: LECs | 1071 | ||
| 28.4 Superconductivity | 1072 | ||
| Superconductors: early examples and basic theory | 1072 | ||
| High-temperature superconductors | 1073 | ||
| Iron-based superconductors | 1075 | ||
| Chevrel phases | 1076 | ||
| Superconducting properties of MgB2 | 1077 | ||
| Applications of superconductors | 1077 | ||
| 28.5 Ceramic materials: colour pigments | 1078 | ||
| White pigments (opacifiers) | 1078 | ||
| Adding colour | 1079 | ||
| 28.6 Chemical vapour deposition (CVD) | 1079 | ||
| High-purity silicon for semiconductors | 1080 | ||
| a-Boron nitride | 1080 | ||
| Silicon nitride and carbide | 1080 | ||
| III–V Semiconductors | 1081 | ||
| Metal deposition | 1083 | ||
| Ceramic coatings | 1083 | ||
| Perovskites and cuprate superconductors | 1083 | ||
| 28.7 Inorganic fibres | 1085 | ||
| Boron fibres | 1085 | ||
| Carbon fibres | 1086 | ||
| Silicon carbide fibres | 1087 | ||
| Alumina fibres | 1088 | ||
| 28.8 Graphene | 1088 | ||
| 28.9 Carbon nanotubes | 1091 | ||
| 29 The trace metals of life | 1098 | ||
| 29.1 Introduction | 1098 | ||
| Amino acids, peptides and proteins: some terminology | 1100 | ||
| 29.2 Metal storage and transport: Fe, Cu, Zn and V | 1101 | ||
| Iron storage and transport | 1101 | ||
| Metallothioneins: transporting some toxic metals | 1108 | ||
| 29.3 Dealing with O2 | 1109 | ||
| Haemoglobin and myoglobin | 1109 | ||
| Haemocyanin | 1112 | ||
| Haemerythrin | 1114 | ||
| Cytochromes P-450 | 1116 | ||
| 29.4 Biological redox processes | 1117 | ||
| Blue copper proteins | 1117 | ||
| The mitochondrial electron-transfer chain | 1118 | ||
| Iron–sulfur proteins | 1120 | ||
| Cytochromes | 1127 | ||
| 29.5 The Zn2+ ion: Nature’s Lewis acid | 1130 | ||
| Carbonic anhydrase II | 1130 | ||
| Carboxypeptidase A | 1132 | ||
| Carboxypeptidase G2 | 1133 | ||
| Cobalt-for-zinc ion substitution | 1133 | ||
| Appendices | 1141 | ||
| 1 Greek letters with pronunciations | xxxii | ||
| 2 Abbreviations and symbols for quantities and units | xxxii | ||
| 3 Selected character tables | xxxii | ||
| 4 The electromagnetic spectrum | xxxii | ||
| 5 Naturally occurring isotopes and their abundances | xxxii | ||
| 6 Van der Waals, metallic, covalent and ionic radii | xxxii | ||
| 7 Pauling electronegativity values (\x05P) for selected elements of theperiodic table | xxxii | ||
| 8 Ground state electronic configurations of the elements andionization energies | xxxii | ||
| 9 Electron affinities | xxxii | ||
| 10 Standard enthalpies of atomization (aH) of the elements at 298 K | xxxii | ||
| 11 Selected standard reduction potentials (298 K) | xxxii | ||
| 12 Selected bond enthalpy terms | xxxii | ||
| Answers to non-descriptive problems | 1170 | ||
| Index | 1191 | ||
| IUPAC: Brief Guide to the Nomenclature of Inorganic Chemistry | 1248 | ||
| IBC | IBC | ||
| Back Cover | Back Cover |