Inorganic Chemistry

, by Housecroft, Catherine E.; Sharpe, Alan G.

Note: Supplemental materials are not guaranteed with Rental or Used book purchases.

ISBN: 9780582310803 | 0582310806
Cover: Paperback
Copyright: 1/1/2001

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This new title from Catherine Housecroft and Alan Sharpe offers a fresh and exciting approach to teaching modern inorganic chemistry. Inorganic Chemistry 1e gives a clear introduction to key principles with strong coverage of descriptive chemistry of the elements. Special selected topics chapters are included covering kinetics and mechanism, catalysis, solid state chemistry and bioinorganic chemistry. The attractive two-colour text and three-dimensional illustrations bring inorganic chemistry to life, with over 140 topic boxes, many covering applications of inorganic chemicals in industry, day-to-day life and the laboratory, and environmental and biological resources.

Preface

xxxi

Some basic concepts

(49)

Introduction

(1)

Inorganic chemistry: it is not an isolated branch of chemistry

(1)

The aims of Chapter 1

(1)

Fundamental particles of an atom

(1)

Atomic number, mass number and isotopes

(1)

Nuclides, atomic number and mass number

(1)

Relative atomic mass

(1)

Isotopes

(1)

Successes in early quantum theory

(3)

Some important successes of classical quantum theory

(1)

Bohr's theory of the atomic spectrum of hydrogen

(1)

An introduction to wave mechanics

(1)

The wave-nature of electrons

(1)

The uncertainty principle

(1)

The Schrodinger wave equation

(1)

Atomic orbitals

(8)

The quantum numbers n, l and ml

(3)

The radial part of the wavefunction, R(r)

(1)

The radial distribution function, 4πr2 R(r)2

(1)

The angular part of the wavefunction, A(&thetas;,&phis;)

(2)

Orbital energies in a hydrogen-like species

(1)

Size of orbitals

(1)

The spin quantum number and the magnetic spin quantum number

(1)

The ground state of the hydrogen atom

(1)

Many-electron atoms

(3)

The helium atom: two electrons

(1)

Ground state electronic configurations: experimental data

(1)

Penetration and shielding

(2)

The periodic table

(1)

The aufbau principle

(4)

Ground state electronic configurations

(3)

Valence and core electrons

(1)

Diagrammatic representations of electronic configurations

(1)

Ionization energies and electron affinities

(3)

Ionization energies

(2)

Eleotron affinities

(1)

Bonding models: an introduction

(1)

A historical overview

(1)

Lewis structures

(1)

Homonuclear diatomic molecules: valence bond (VB) theory

(3)

Uses of the term homonuclear

(1)

Covalent bond distance, covalent radius and van der Waals radius

(1)

The valence bond (VB) model of bonding in H2

(1)

The valence bond (VB) model applied to F2, O2 and N2

(1)

Homonuclear diatomic molecules: molecular orbital (MO) theory

(6)

An overview of the MO model

(1)

Molecular orbital theory applied to the bonding in H2

(2)

The bonding in He2, Li2 and Be2

(1)

The bonding in F2 and O2

(1)

What happens if the s-p separation is small?

(3)

The octet rule

(1)

Electronegativity values

(3)

Pauling electronegativity values, XP

(1)

Mulliken electronegativity values, XM

(1)

Allred-Rochow electronegativity values, XAR

(1)

Electronegativity: final remarks

(1)

Dipole moments

(1)

Polar diatomic molecules

(1)

Molecular dipole moments

(1)

MO theory: heteronuclear diatomic molecules

(2)

Which orbital interactions should be considered?

(1)

Hydrogen fluoride

(1)

Carbon monoxide

(1)

Isoelectronic molecules

(1)

Molecular shape and the VSEPR model

(5)

Valence-shell electron-pair repulsion theory

(2)

Limitations of VSEPR theory

(3)

Molecular shape: geometrical isomerism

(4)

Square planar species

(1)

Octahedral species

(1)

Trigonal bipyramidal species

(1)

High coordination numbers

(1)

Double bonds

(3)

Nuclear properties

(24)

Introduction

(1)

Nuclear binding energy

(2)

Mass defect and binding energy

(1)

The average binding energy per nucleon

(1)

Radioactivity

(2)

Nuclear emissions

(1)

Nuclear transformations

(1)

The kinetics of radioative decay

(1)

Units of radioactivity

(1)

Artificial isotopes

(1)

Bombardment of nuclei by high-energy &alpha-particles and neutrons

(1)

Bombardment of nuclei by `slow' neutrons

(1)

Nuclear fission

(3)

The fission of uranium-235

(2)

The production of energy by nuclear fission

(1)

Nuclear reprocessing

(1)

Syntheses of transuranium elements

(1)

The separation of radioactive isotopes

(1)

Chemical separation

(1)

The Szilard-Chalmers effect

(1)

Nuclear fusion

(1)

Applications of isotopes

(3)

Infrared (IR) spectroscopy

(1)

Kinetic isotope effects

(1)

Radiocarbon dating

(1)

Analytical applications

(1)

Sources of 2H and 13C

(1)

Deuterium: electrolytic separation of isotopes

(1)

Carbon-13: chemical enrichment

(1)

Multinuclear NMR spectroscopy in inorganic chemistry

(8)

Which nuclei are suitable for NMR spectroscopic studies?

(1)

Chemical shift ranges

(1)

Spin-spin coupling

(4)

Stereochemically non-rigid species

(1)

Exchange processes in solution

(2)

Mossbauer spectroscopy in inorganic chemistry

(4)

The technique of Mossbauer spectroscopy

(1)

What can isomer shift data tell us?

(4)

An introduction to molecular symmetry

(17)

Introduction

(1)

Symmetry operations and symmetry elements

(4)

Rotation about an n-fold axis of symmetry

(1)

Reflection through a plane of symmetry (mirror plane)

(1)

Reflection through a centre of symmetry (inversion centre)

(1)

Rotation about an axis, followed by reflection through a plane perpendicular to this axis

(1)

Identity operator

(2)

Successive operations

(1)

Point groups

(4)

C1 point group

(1)

C∞v point group

(1)

D∞h point group

(1)

Td, Oh or Ih point groups

(1)

Determining the point group of a molecule or molecular ion

(3)

Character tables: an introduction

(1)

Why do we need to recognize symmetry elements?

(1)

Infrared spectroscopy

(3)

How many vibrational modes are there for a given molecular species?

(1)

Selection rule for an infrared active mode of vibration

(1)

Linear and bent triatomic molecules

(1)

Trigonal planar and trigonal pyramidal molecules

(1)

Tetrahedral and square planar species

(1)

Observing IR spectroscopic absorptions: practical problems

(1)

Chiral molecules

(5)

Bonding in polyatomic molecules

(25)

Introduction

(1)

Valence bond theory: hybridization of atomic orbitals

(5)

What is orbital hybridization?

(1)

sp Hybridization: a scheme for linear species

(1)

sp2 Hybridization: a scheme for trigonal planar species

(2)

sp3 Hybridization: a scheme for tetrahedral species

(1)

Other hybridization schemes

(1)

Valence bond theory: multiple bonding in polyatomic molecules

(2)

C2H4

(1)

HCN

(1)

BF3

(1)

π-Bond formation between different types of orbitals

(1)

Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules

(2)

Molecular orbital diagrams: moving from a diatomic to polyatomic species

(1)

Ligand group orbitals: MO approach to the bonding in linear XH2

(1)

A bent triatomic: H2O

(1)

Molecular orbital theory applied to the polyatomic molecules BH3, NH3 and CH4

100

(5)

BH3

102

(1)

NH3

103

(1)

CH4

103

(1)

A comparison of the MO and VB bonding models

104

(1)

Molecular orbital theory: bonding analyses soon become complicated

105

(1)

Molecular orbital theory: learning to use the theory objectively

106

(10)

CO2

107

(1)

XeF2

108

(1)

[NO3]-

108

(1)

SF6

109

(2)

A more advanced problem: B2H6

111

(3)

Role of d-orbitals in main group compounds

114

(2)

Structures and energetics of metallic and ionic solids

116

(28)

Introduction

116

(1)

Packing of spheres

116

(3)

Cubic and hexagonal close-packing

116

(1)

The unit cell: hexagonal and cubic close-packing

117

(1)

Interstitial holes: hexagonal and cubic close-packing

118

(1)

Non-close-packing: simple cubic and body-centred cubic arrays

118

(1)

The packing-of-spheres model applied to the structures of elements

119

(2)

Group 18 elements in the solid state

119

(1)

H2 and F2 in the solid state

119

(1)

Metallic elements in the solid state

119

(2)

Polymorphism in metals

121

(1)

Polymorphism: phase changes in the solid state

121

(1)

Phase diagrams

121

(1)

Metallic radii

121

(1)

Melting points and standard enthalpies of atomization of metals

122

(1)

Alloys and intermetallic compounds

122

(3)

Substitutional alloys

123

(1)

Interstitial alloys

123

(1)

Intermetallic compounds

123

(2)

Bonding in metals and semiconductors

125

(2)

Electrical conductivity and resistivity

125

(1)

Band theory of metals and insulators

125

(1)

The Fermi level

126

(1)

Band theory of semiconductors

127

(1)

Semiconductors

127

(1)

Intrinsic semiconductors

127

(1)

Extrinsic (n- and p- type) semiconductors

127

(1)

Sizes of ions

128

(1)

Ionic radii

128

(1)

Periodic trends in ionic radii

129

(1)

Ionic lattices

129

(5)

The rock salt (NaCl) lattice

130

(1)

The caesium chloride (CsCl) lattice

131

(1)

The fluorite (CaF2) lattice

132

(1)

The antifluorite lattice

132

(1)

The zinc blende (ZnS) lattice: a diamond-type network

132

(1)

The β-cristobalite (SiO2) lattice

133

(1)

The wurtzite (ZnS) structure

133

(1)

The rutile (TiO2) structure

133

(1)

The CdI2 and CdCl2 lattices: layer structures

134

(1)

The perovskite (CaTiO3) lattice: a double oxide

134

(1)

Crystal structures of semiconductors

134

(1)

Lattice energy: estimates from an electrostatic model

135

(3)

Coulombic attraction within an isolated ion-pair

135

(1)

Coulombic interactions in an ionic lattice

135

(1)

Born forces

136

(1)

The Born-Lande equation

136

(1)

Madelung constants

137

(1)

Refinements to the Born-Lande equation

137

(1)

Overview

138

(1)

Lattice energy: the Born-Haber cycle

138

(1)

Lattice energy: `calculated' versus `experimental' values

139

(1)

Applications of lattice energies

139

(2)

Estimation of electron affinities

139

(1)

Fluoride affinities

140

(1)

Estimation of standard enthalpies of formation and disproportionation

140

(1)

The Kapustinskii equation

141

(1)

Defects in solid state lattices: an introduction

141

(3)

Schottky defect

141

(1)

Frenkel defect

141

(1)

Experimental observation of Schottky and Frenkel defects

142

(2)

Acids, bases and ions in aqueous solution

144

(26)

Introduction

144

(1)

Properties of water

144

(3)

Structure and hydrogen bonding

144

(1)

The self-ionization of water

145

(1)

Water as a Bronsted acid or base

145

(2)

Definitions and units in aqueous solution

147

(1)

Molarity and molality

147

(1)

Standard state

147

(1)

Activity

147

(1)

Bronsted acids and bases

147

(3)

Carboxylic acids: examples of mono-, di- and polybasic acids

147

(1)

Inorganic acids

148

(2)

Inorganic bases: hydroxides

150

(1)

Inorganic bases: nitrogen bases

150

(1)

The energetics of acid dissociation in aqueous solution

150

(2)

Hydrogen halides

150

(2)

H2S, H2Se and H2 Te

152

(1)

Trends within a series of oxoacids EOn (OH)m

152

(1)

Aquated cations: formation and acidic properties

152

(2)

Water as a Lewis base

152

(1)

Aquated cations as Bronsted acids

153

(1)

Amphoteric oxides and hydroxides

154

(1)

Amphoteric behaviour

154

(1)

Periodic trends in amphoteric properties

155

(1)

Solubilities of ionic salts

155

(4)

Solubility and saturated solutions

155

(1)

Sparingly soluble salts and solubility products

155

(1)

The energetics of the dissolution of an ionic salt: ΔsolGo

156

(1)

The energetics of the dissolution of an ionic salt: hydration of ions

157

(1)

Solubilities: some concluding remarks

158

(1)

Common-ion effect

159

(1)

Coordination complexes: an introduction

159

(3)

Definitions and terminology

159

(1)

Investigating coordination complex formation

160

(2)

Stability constants of coordination complexes

162

(4)

Determination of stability constants

163

(1)

Trends in stepwise stability constants

163

(1)

Thermodynamic considerations of complex formation: an introduction

163

(3)

Factors affecting the stabilities of complexes containing only monodentate ligands

166

(4)

Ionic size and charge

166

(1)

Hard and soft metal centres and ligands

166

(4)

Reduction and oxidation

170

(17)

Introduction

170

(1)

Oxidation and reduction

170

(1)

Oxidation states

170

(1)

Stock nomenclature

171

(1)

Standard reduction potentials, E°, and relationships between E°, ΔG° and K

171

(5)

Half-cells and galvanic cells

171

(1)

Defining and using standard reduction potentials, E°

172

(2)

Dependence of reduction potentials on cell conditions

174

(2)

The effect of complex formation or precipitation on Mz+ /M reduction potentials

176

(3)

Half-cells involving silver halides

176

(1)

Modifying the relative stabilities of different oxidation states of a metal

177

(2)

Disproportionation reactions

179

(1)

Disproportionation

179

(1)

Stabilizing species against disproportionation

180

(1)

Potential diagrams

180

(1)

The relationships between standard reduction potentials and some other quantities

181

(2)

Factors influencing the magnitudes of standard reduction potentials

181

(1)

Values of ΔfG° for aqueous ions

182

(1)

Applications of redox reactions to the extraction of elements from their ores

183

(4)

Ellingham diagrams

183

(4)

Non-aqueous media

187

(17)

Introduction

187

(1)

Relative permittivity

187

(1)

Energetics of ionic salt transfer from water to an organic solvent

188

(1)

Acid-base behaviour in non-aqueous solvents

189

(1)

Strengths of acids and bases

189

(1)

Levelling and differentiating effects

190

(1)

`Acids' in acidic solvents

190

(1)

Acids and bases: a solvent-oriented definition

190

(1)

Self-ionizing and non-ionizing non-aqueous solvents

190

(2)

Liquid ammonia

192

(2)

Physical properties

192

(1)

Self-ionization

192

(1)

Reactions in liquid NH3

192

(1)

Solutions of s-block metals in liquid NH3

193

(1)

Redox reactions in liquid NH3

194

(1)

Liquid hydrogen fluoride

194

(2)

Physical properties

194

(1)

Acid-base behaviour in liquid HF

195

(1)

Electrolysis in liquid HF

196

(1)

Sulfuric acid

196

(1)

Physical properties

196

(1)

Acid-base behaviour in liquid H2SO4

196

(1)

Fluorosulfonic acid

197

(1)

Physical properties

197

(1)

Superacids

197

(1)

Bromine trifluoride

198

(1)

Physical properties

198

(1)

Behaviour of fluoride salts and molecular fluorides in BrF3

198

(1)

Reactions in BrF3

198

(1)

Dinitrogen tetraoxide

199

(1)

Physical properties

199

(1)

Reactions in N2O4

199

(1)

Ionic liquids

200

(4)

Molten salt solvent systems

201

(1)

Ionic salts at ambient temperatures

201

(1)

Reactions in and applications of molten salt media

201

(3)

Hydrogen

204

(15)

Hydrogen: the simplest atom

204

(1)

The H+ and H- ions

204

(1)

The hydrogen ion (proton)

204

(1)

The hydride ion

204

(1)

Isotopes of hydrogen

205

(1)

Protium and deuterium

205

(1)

Deuterated compounds

205

(1)

Tritium

205

(1)

Dihydrogen

206

(3)

Occurrence

206

(1)

Physical properties

206

(1)

Synthesis and uses

206

(1)

Reactivity

207

(2)

Polar and non-polar E--H bonds

209

(1)

Hydrogen bonding

210

(4)

The hydrogen bond

210

(1)

Trends in boiling points, melting points and enthalpies of vaporization for p-block binary hydrides

211

(1)

Infrared spectroscopy

211

(2)

Solid state structures

213

(1)

Hydrogen bonding in biological systems

214

(1)

Binary hydrides: classification and general properties

214

(5)

Classification

214

(1)

Interstitial metal hydrides

214

(1)

Saline hydrides

214

(2)

Molecular hydrides

216

(1)

Polymeric hydrides

217

(1)

Intermediate hydrides

217

(2)

Group 1: the alkali metals

219

(14)

Introduction

219

(1)

Occurrence, extraction and uses

219

(2)

Occurrence

219

(1)

Extraction

219

(2)

Major uses of the alkali metals and their compounds

221

(1)

Physical properties

221

(2)

General properties

221

(1)

Atomic spectra and flame tests

222

(1)

Radioactive isotopes

223

(1)

NMR active nuclei

223

(1)

The metals

223

(1)

Appearance

223

(1)

Reactivity

223

(1)

Halides

224

(1)

Oxides and hydroxides

225

(1)

Oxides, peroxides, superoxides, suboxides and ozonides

225

(1)

Hydroxides

226

(1)

Salts of oxoacids: carbonates and hydrogencarbonates

226

(1)

Aqueous solution chemistry

227

(2)

Hydrated ions

227

(1)

Complex ions

228

(1)

Non-aqueous coordination chemistry

229

(4)

The group 2 metals

233

(14)

Introduction

233

(1)

Occurrence, extraction and uses

233

(3)

Occurrence

233

(1)

Extraction

234

(1)

Major uses of the group 2 metals and their compounds

235

(1)

Physical properties

236

(1)

General properties

236

(1)

Flame tests

236

(1)

Radioactive isotopes

236

(1)

The metals

237

(1)

Appearance

237

(1)

Reactivity

237

(1)

Halides

238

(2)

Beryllium halides

238

(1)

Halides of Mg, Ca, Sr and Ba

239

(1)

Oxides and hydroxides

240

(2)

Oxides and peroxides

240

(1)

Hydroxides

241

(1)

Salts of oxoacids

242

(1)

Complex ions in aqueous solution

243

(1)

Aqua species of beryllium

243

(1)

Aqua species of Mg2+, Ca2+, Sr2+ and Ba2+

243

(1)

Complexes with ligands other than water

243

(1)

Complexes with amido or alkoxy ligands

244

(3)

The group 13 elements

247

(34)

Introduction

247

(1)

Occurrence, extraction and uses

247

(2)

Occurrence

247

(1)

Extraction

247

(1)

Major uses of the group 13 elements and their compounds

248

(1)

Physical properties

249

(2)

Electronic configurations and oxidation states

250

(1)

NMR active nuclei

251

(1)

The elements

251

(2)

Appearance

251

(1)

Structures of the elements

252

(1)

Reactivity

253

(1)

Simple hydrides

253

(4)

Neutral hydrides

253

(3)

The [MH4]- ions

256

(1)

Halides and complex halides

257

(4)

Boron halides: BX3 and B2X4

257

(2)

Al(III), Ga(III), In(III) and Tl(III) halides and their complexes

259

(1)

Lower oxidation state Al, Ga, In and Tl halides

260

(1)

Oxides, oxoacids, oxoanions and hydroxides

261

(4)

Boron oxides, oxoacids and oxoanions

261

(2)

Aluminium oxides, oxoacids, oxoanions and hydroxides

263

(2)

Oxides of Ga, In and Tl

265

(1)

Compounds containing nitrogen

265

(4)

Nitrides

265

(1)

Molecular species containing boron-nitrogen bonds

266

(2)

Molecular species containing group 13 metal-nitrogen bonds

268

(1)

Aluminium to thallium: salts of oxoacids, aqueous solution chemistry and complexes

269

(1)

Aluminium sulfate and alums

269

(1)

Aqua ions

269

(1)

Redox reactions in aqueous solution

269

(1)

Coordination complexes of the M3+ ions

270

(1)

Metal borides

270

(2)

Electron-deficient borane clusters: an introduction

272

(9)

Boron hydrides

272

(9)

The group 14 elements

281

(34)

Introduction

281

(1)

Occurrence, extraction and uses

281

(3)

Occurrence

281

(1)

Extraction and manufacture

282

(1)

Uses

282

(2)

Physical properties

284

(2)

Ionization energies and cation formation

284

(1)

Some energetic and bonding considerations

284

(2)

NMR active nuclei

286

(1)

Mossbauer spectroscopy

286

(1)

Allotropes of carbon

286

(6)

Graphite and diamond: structure and properties

286

(1)

Graphite: intercalation compounds

287

(1)

Fullerenes: synthesis and structure

288

(1)

Fullerenes: reactivity

289

(3)

Carbon nanotubes

292

(1)

Structural and chemical properties of silicon, gemanium, tin and lead

292

(1)

Structures

292

(1)

Chemical properties

292

(1)

Hydrides

292

(3)

Binary hydrides

293

(1)

Halohydrides of silicon and germanium

294

(1)

Carbides, silicides, germides, stannides and plumbides

295

(2)

Carbides

295

(1)

Silicides

295

(1)

Germides, stannides and plumbides

296

(1)

Halides and complex halides

297

(3)

Carbon halides

297

(2)

Silicon halides

299

(1)

Halides of germanium, tin and lead

299

(1)

Oxides, oxoacids and hydroxides

300

(8)

Oxides and oxoacids of carbon

300

(2)

Silica, silicates and aluminosilicates

302

(4)

Oxides, hydroxides and oxoacids of germanium, tin and lead

306

(2)

Silicones

308

(1)

Sulfides

309

(1)

Cyanogen and silicon nitride

310

(2)

Cyanogen and its derivatives

310

(2)

Silicon nitride

312

(1)

Aqueous solution chemistry and salts of oxoacids of tin and lead

312

(3)

The group 15 elements

315

(36)

Introduction

315

(1)

Occurrence, extraction and uses

315

(2)

Occurrence

315

(1)

Extraction

316

(1)

Uses

316

(1)

Physical properties

317

(2)

Bonding considerations

317

(2)

NMR active nuclei

319

(1)

Radioactive isotopes

319

(1)

The elements

319

(2)

Nitrogen

319

(1)

Phosphorus

320

(1)

Arsenic, antimony and bismuth

321

(1)

Hydrides

321

(5)

Trihydrides, EH3 (E = N, P, As, Sb and Bi)

321

(2)

Hydrides E2H4 (E = N, P, As)

323

(1)

Chloramine and hydroxylamine

324

(1)

Hydrogen azide and azide salts

325

(1)

Nitrides, phosphides, arsenides, antimonides and bismuthides

326

(1)

Nitrides

326

(1)

Phosphides

326

(1)

Arsenides, antimonides and bismuthides

327

(1)

Halides, oxohalides and complex halides

327

(5)

Nitrogen halides

327

(2)

Oxofluorides and oxochlorides of nitrogen

329

(1)

Phosphorus halides

329

(1)

Phosphoryl trichloride, POCI3

330

(1)

Arsenic and antimony halides

330

(2)

Bismuth halides

332

(1)

Oxides of nitrogen

332

(3)

Dinitrogen monoxide, N2O

332

(1)

Nitrogen monoxide, NO

333

(1)

Dinitrogen trioxide, N2O3

334

(1)

Dinitrogen tetraoxide, N2O4, and nitrogen dioxide, NO2

334

(1)

Dinitrogen pentaoxide, N2O5

335

(1)

Oxoacids of nitrogen

335

(3)

Hyponitrous acid, H2N2O2

335

(1)

Nitrous acid, HNO2

336

(1)

Nitric acid, HNO3, and its derivatives

336

(2)

Oxides of phosphorus, arsenic, antimony and bismuth

338

(1)

Oxides of phosphorus

338

(1)

Oxides of arsenic, antimony and bismuth

339

(1)

Oxoacids of phosphorus

339

(4)

Phosphinic acid, H3PO2

339

(1)

Phosphonic acid, H3PO3

340

(1)

Hypophosphoric acid, H4P2O6

341

(1)

Phosphoric acid, H3PO4, and its derivatives

341

(2)

Oxoacids of arsenic, antimony and bismuth

343

(1)

Phosphazenes

344

(2)

Sulfides and selenides

346

(2)

Sulfides and selenides of phosphorus

346

(1)

Arsenic, antimony and bismuth sulfides

347

(1)

Aqueous solution chemistry

348

(3)

The group 16 elements

351

(30)

Introduction

351

(1)

Occurrence, extraction and uses

351

(2)

Occurrence

351

(1)

Extraction

352

(1)

Uses

353

(1)

Physical properties and bonding considerations

353

(1)

NMR active nuclei and isotopes as tracers

354

(1)

The elements

354

(4)

Dioxygen

354

(1)

Ozone

355

(1)

Sulfur: allotropes

356

(1)

Sulfur: reactivity

357

(1)

Selenium and tellurium

357

(1)

Hydrides

358

(4)

Water, H2O

358

(1)

Hydrogen peroxide, H2O2

359

(1)

Hydrides H2E (E = S, Se, Te)

360

(1)

Polysufanes

361

(1)

Metal sulfides, polysulfides, polyselenides and polytellurides

362

(2)

Sulfides

362

(1)

Polysulfides

362

(1)

Polyselenides and polytellurides

363

(1)

Haildes, oxohalides andcomplex halides

364

(5)

Oxygen flurides

364

(1)

Sulfur fluorides and oxofluorides

364

(2)

Sulfur chlorides and oxochlorides

366

(1)

Halides of selenium and tellurium

367

(2)

Oxides

369

(3)

Oxides of sulfur

369

(2)

Oxides of selenium and tellurium

371

(1)

Oxoacids and their salts

372

(4)

Dithionous acid, H2S2O4

372

(1)

Sulfurous and disulfurous acids, H2SO3 and H2S2O5

373

(1)

Dithionic acid, H2S2O6

374

(1)

Sulfuric acid, H2SO4

374

(1)

Fluoro- and chlorosulfonic acids, HSO3F and HSO3 Cl

374

(1)

Polyoxoacids with S-O-S units

374

(1)

Peroxosulfuric acids, H2S2O8, and H2SO5

375

(1)

Thiosulfuric acid, H2S2O3, and polythionates

375

(1)

Oxoacids of selenium and tellurium

375

(1)

Compounds of sulfur and selenium with nitrogen

376

(2)

Sulfur-nitrogen compounds

376

(2)

Tetraselenium tetranitride

378

(1)

Aqueous solution chemistry of sulfur, selenium and tellurium

378

(3)

The group 17 elements

381

(20)

Introduction

381

(1)

Fluorine, chlorine, bromine and iodine

381

(1)

Astatine

382

(1)

Occurrence, extraction and uses

382

(2)

Occurrence

382

(1)

Extraction

383

(1)

Uses

383

(1)

Physical properties and bonding considerations

384

(2)

NMR active nuclei and isotopes as tracers

385

(1)

The elements

386

(2)

Difluorine

386

(1)

Dichlorine, dibromine and diiodine

386

(1)

Charge transfer complexes

387

(1)

Clathrates

388

(1)

Hydrogen halides

388

(1)

Metal halides: structures and energetics

389

(1)

Interhalogen compounds and polyhalogen ions

390

(4)

Interhalogen compounds

390

(2)

Bonding in [XY2]- ions

392

(1)

Polyhalogen cations

393

(1)

Polyhalide anions

393

(1)

Oxides and oxoflurides of chlorine, bromine and iodine

394

(1)

Oxides

394

(1)

Oxofluorides

395

(1)

Oxoacids and their salts

395

(3)

Hypoflurous acid, HOF

395

(1)

Oxoacids of chlorine, bromine and iodine

395

(3)

Aqueous solution chemistry

398

(3)

The group 18 elements

401

(9)

Introduction

401

(1)

Occurrence, extraction and uses

402

(1)

Occurrence

402

(1)

Extraction

402

(1)

Uses

402

(1)

Physical properties

403

(1)

NMR active nuclei

404

(1)

Compounds of xenon

404

(3)

Fluorides

404

(2)

Oxides

406

(1)

Oxofluorides

407

(1)

Other compounds of xenon

407

(1)

Compounds of krypton and radon

407

(3)

Organometallic compounds of s-and p-block elements

410

(24)

Introduction

410

(1)

Group 1: alkali metal organometallics

411

(2)

Group 2 organometallics

413

(3)

Beryllium

415

(1)

Magnesium

415

(1)

Group 13

416

(6)

Boron

416

(1)

Aluminium

417

(2)

Gallium, indium and thallium

419

(3)

Group 14

422

(6)

Silicon

422

(1)

Germanium

423

(1)

Tin

424

(2)

Lead

426

(2)

Group 15

428

(3)

Bonding aspects

428

(1)

Arsenic, antimony and bismuth

428

(3)

Group 16

431

(3)

Selenium and tellurium

431

(3)

d-Block chemistry: general considerations

434

(18)

Topic overview

434

(1)

Ground state electronic configurations

434

(1)

d-Block metals versus transition elements

434

(1)

Electronic configurations

435

(1)

Physical properties

435

(1)

The reactivity of the metals

436

(1)

Characteristic properties: a general perspective

437

(1)

Colour

437

(1)

Paramagnetism

437

(1)

Complex formation

437

(1)

Variable oxidation states

438

(1)

Electroneutrality principle

438

(1)

Coordination numbers

439

(7)

The Kepert model

440

(1)

Coordination number two

441

(1)

Coordination number three

441

(1)

Coordination number four

441

(1)

Coordination number five

442

(1)

Coordination number six

443

(1)

Coordination number seven

443

(1)

Coordination number eight

444

(1)

Coordination number nine

445

(1)

Coordination numbers of ten and above

445

(1)

Isomerism in d-block metal complexes

446

(6)

Structural isomerism: ionization isomers

446

(1)

Structural isomerism: hydration isomers

446

(1)

Structural isomerism: coordination isomerism

447

(1)

Structural isomerism: linkage isomerism

447

(1)

Structural isomerism: polymerization isomerism

447

(1)

Stereoisomerism: geometrical isomers

447

(1)

Stereoisomerism: optical isomers

447

(5)

d-Block chemistry: coordination complexes

452

(36)

Introduction

452

(1)

High - and low-spin states

452

(1)

Bonding in d-block metal complexes: valence bond theory

452

(2)

Hybridization schemes

452

(1)

Applying VB theory

453

(1)

Crystal field theory

454

(7)

The octahedral crystal field

455

(2)

Crystal field stablization energy: high - and low-spin octahedral complexes

457

(1)

Jahn-Teller distortions

457

(2)

The tetrahedral crystal field

459

(1)

The square planar crystal field

459

(2)

Other crystal fields

461

(1)

Crystal field theory: uses and limitations

461

(1)

Molecular orbital theory: octahedral complexes

461

(4)

Complexes with no metal-ligand π-bonding

461

(1)

Complexes with metal-ligand π-bonding

461

(4)

Ligand field theory

465

(1)

Electronic spectra

466

(7)

Spectral features

466

(1)

Selection rules

466

(1)

Electronic spectra of octahedral and tetrahedral complexes

467

(5)

Microstates

472

(1)

Tanabe-Sugano diagrams

473

(1)

Evidence for metal-ligand covalent bonding

473

(1)

The nephelauxetic effect

473

(1)

ESR spectroscopy

474

(1)

Magnetic properties

474

(7)

Magnetic susceptibility and the spin-only formula

474

(3)

Spin and orbital contributions to the magnetic moment

477

(2)

The effects of temperature on μeff

479

(1)

Spin crossover

479

(1)

Ferromagnetism, antiferromagnetism and ferrimagnetism

480

(1)

Thermodynamic aspects: ligand field stabilization energies (LFSE)

481

(2)

Trends in LFSE

481

(1)

Lattice energies and hydration energies of Mn+ ions

481

(1)

Octahedral versus tetrahedral coordination: spinels

482

(1)

Thermodynamic aspects: the Irving-Williams series

483

(1)

Thermodynamic aspects: Oxidation states in aqueous solution

484

(4)

d-Block metal chemistry: the first row metals

488

(46)

Introduction

488

(1)

Occurrence, extraction and uses

488

(3)

Physical properties: an overview

491

(1)

Group 3: scandium

491

(1)

The metal

491

(1)

Scandium(III)

491

(1)

Group 4: titanium

492

(4)

The metal

492

(1)

Titanium(IV)

493

(2)

Titanium(III)

495

(1)

Low oxidation states

495

(1)

Group 5: vanadium

496

(3)

The metal

496

(1)

Vanadium(V)

496

(2)

Vanadium(IV)

498

(1)

Vandadium(III)

498

(1)

Vanadadium(II)

499

(1)

Group 6: chromium

499

(5)

The metal

499

(1)

Chromium(IV)

499

(2)

Chromium(V) and chromium(IV)

501

(1)

Chromium(III)

501

Chromium(II)

492

(11)

Chromium-chromium multiple bonds

503

(1)

Group 7: manganese

504

(5)

The metal

504

(1)

Manganese(VII)

504

(2)

Manganese(VI)

506

(1)

Manganese(V)

506

(1)

Manganese(IV)

506

(1)

Manganese(III)

507

(1)

Manganese(II)

508

(1)

Group 8: iron

509

(6)

The metal

509

(1)

Iron(VI), iron(V) and iron(IV)

509

(1)

Iron(III)

510

(3)

Iron(II)

513

(2)

Group 9: cobalt

515

(6)

The metal

515

(1)

Cobalt(IV)

515

(1)

Cobalt(III)

515

(3)

Cobalt(II)

518

(3)

Group 10: nickel

521

(3)

The metal

521

(1)

Nickel(IV) and nickel(III)

521

(1)

Nickel(II)

522

(2)

Nickel(I)

524

(1)

Group 11: copper

524

(5)

The metal

524

(1)

Copper(IV) and (III)

525

(1)

Copper(II)

525

(3)

Copper(I)

528

(1)

Group 12: zinc

529

(5)

The metal

529

(1)

Zinc(II)

530

(4)

d-Block metal chemistry: the second and third row metals

534

(50)

Introduction

534

(1)

Occurrence, extraction and uses

534

(3)

Physical properties

537

(3)

Effects of the lanthanoid contraction

539

(1)

Coordination numbers

540

(1)

NMR active nuclei

540

(1)

Group 3: yttrium

540

(1)

The metal

540

(1)

Yttrium(III)

540

(1)

Group 4: zirconium and hafnium

540

(3)

The metals

540

(1)

Zirconium(IV) and hafnium(IV)

541

(1)

Lower oxidation states of zirconium and hafnium

542

(1)

Zirconium clusters

542

(1)

Group 5: niobium and tantalum

543

(3)

The metals

543

(1)

Niobium(V) and tantalum(V)

543

(2)

Niobium(IV) and tantalum(IV)

545

(1)

Lower oxidation state halides

545

(1)

Group 6: molybdenum and tungsten

546

(8)

The metals

546

(1)

Molybdenum(VI) and tungsten(VI)

547

(3)

Molybdenum(V) and tungsten(V)

550

(1)

Molybdenum(IV) and tungsten(IV)

551

(1)

Molybdenum(III) and tungsten(III)

551

(1)

Molybdenum(II) and tungsten(II)

552

(2)

Group 7: technetium and rhenium

554

(4)

The metals

554

(1)

High oxidation states of technetium and rhenium: M(VII), M(VI) and M(V)

554

(2)

Technetium(IV) and rhenium(IV)

556

(1)

Technetium(III) and rhenium(III)

557

(1)

Group 8: ruthenium and osmium

558

(8)

The metals

558

(1)

High oxidation states of ruthenium and osmium: M(VIII), M(VII) and M(VI)

558

(2)

Ruthenium(V), (IV) and osmium(V), (IV)

560

(1)

Ruthenium(III) and osmium(III)

561

(2)

Ruthenium(II) and osmium(II)

563

(2)

Mixed-valence ruthenium complexes

565

(1)

Group 9: rhodium and iridium

566

(4)

The metals

566

(1)

High oxidation states of rhodium and iridium: M(VI) and M(V)

566

(1)

Rhodium(IV) and iridium(IV)

566

(1)

Rhodium(III) and iridium(III)

566

(2)

Rhodium(II) and iridium(II)

568

(1)

Rhodium(I) and iridium(I)

569

(1)

Group 10: palladium and platinum

570

(5)

The metals

570

(1)

The highest oxidation states: M(VI) and M(V)

570

(1)

Palladium(IV) and platinum(IV)

570

(1)

Palladium(III), platinum(III) and mixed valence complexes

571

(1)

Palladium(II) and platinum(II)

572

(3)

Group 11: silver and gold

575

(4)

The metals

575

(1)

Gold(V) and silver (V)

576

(1)

Gold(III) and silver (III)

576

(1)

Silver(II)

577

(1)

Gold(I) and silver(I)

577

(2)

Group 12: cadimium and mercury

579

(5)

The metals

579

(1)

Cadmium(II)

580

(1)

Mercury(II)

580

(1)

Mercury(I)

581

(3)

Organometallic compounds of d-block elements

584

(38)

Introduction

584

(1)

Hapticity of a ligand

584

(1)

Common types of ligand: bonding and spectroscopy

584

(6)

σ-Bonded alkyl, aryl and related ligands

584

(1)

Carbonyl ligands

585

(1)

Hydride ligands

586

(1)

Phosphine and related ligands

587

(1)

π-Bonded organic ligands

587

(3)

Dinitrogen

590

(1)

Dihydrogen

590

(1)

The 18-electron rule

590

(2)

Metal carbonyls: synthesis, physical properties and structure

592

(5)

Synthesis and physical properties

593

(1)

Structures

594

(3)

The isolobal principle and application of Wade's rules

597

(2)

Total valence electron counts in d-block organometallic clusters

599

(2)

Single cage structures

599

(1)

Condensed cages

600

(1)

Limitations of total valence counting schemes

601

(1)

Types of organometallic reactions

601

(4)

Substitution of CO ligands

601

(1)

Oxidative addition

602

(1)

Alkyl and hydrogen migrations

602

(1)

β-Hydrogen elimination

603

(1)

α-Hydrogen abstraction

604

(1)

Metal carbonyls: selected reactions

605

(1)

Metal carbonyl hydrides and halides

606

(1)

Alkyl, aryl, alkene and alkyne complexes

606

(3)

σ-Bonded alkyl and aryl ligands

606

(1)

Alkene ligands

607

(1)

Alkyne ligands

608

(1)

Allyl and buta-1,3-diene complexes

609

(2)

Allyl and related ligands

609

(1)

Buta-1,3-diene and related ligands

610

(1)

Carbene and carbyne complexes

611

(1)

Complexes containing η5-cyclopentadienyl ligands

612

(3)

Ferrocene and other metallocenes

612

(1)

(η5-Cp)2Fe2(CO)4 and derivatives

613

(2)

Complexes containing η6- and η7-ligands

615

(3)

η6-Arene ligands

615

(2)

Cycloheptatriene and derived ligands

617

(1)

Complexes containing the η4-cyclobutadiene ligand

618

(4)

The f-block metals: lanthanoids and actinoids

622

(19)

Introduction

622

(1)

f-Orbitals and oxidation states

623

(1)

Atom and ion sizes

624

(1)

The lanthanoid contraction

624

(1)

Coordination numbers

624

(1)

Spectroscopic and magnetic properties

625

(1)

Electronic spectra and magnetic moments: lanthanoids

625

(1)

Luminescence of lanthanoid complexes

626

(1)

Electronic spectra and magnetic moments: actinoids

626

(1)

Sources of the lanthanoids and actinoids

626

(2)

Occurrence and separation of the lanthanoids

626

(2)

The actinoids

628

(1)

Lanthanoid metals

628

(1)

Inorganic compounds and coordination complexes of the lanthanoids

629

(2)

Halides

629

(1)

Hydroxides and oxides

629

(1)

Complexes of Ln(III)

629

(2)

Organometallic complexes of the lanthanoids

631

(2)

σ-Bonded complexes

631

(1)

Cyclopentadienyl complexes

631

(2)

Bis(arene) derivatives

633

(1)

Complexes containing the η8-cyclooctatetraenyl ligand

633

(1)

The actinoid metals

633

(1)

Inorganic compounds and coordination complexes of thorium and uranium

634

(2)

Thorium

634

(1)

Uranium

635

(1)

Organometallic complexes of thorium and uranium

636

(5)

σ-Bonded complexes

636

(1)

Cyclopentadienyl derivatives

637

(1)

Complexes containing the η8-cyclooctatetraenyl ligand

638

(3)

d-Block metal complexes: reaction mechanisms

641

(21)

Introduction

641

(1)

Ligand substitutions: some general points

641

(2)

Kinetically inert and labile complexes

641

(1)

Stoichiometric equations say nothing about mechanism

641

(1)

Types of substitution mechanism

642

(1)

Activation parameters

642

(1)

Substitution in square planar complexes

643

(3)

Rate equations, mechanism and the trans-effect

643

(3)

Ligand nucleophilicity

646

(1)

Substitution and racemization in octahedral complexes

646

(8)

Water exchange

647

(1)

The Eigen--Wilkins mechanism

648

(2)

Stereochemistry of substitution

650

(2)

Base-catalyzed hydrolysis

652

(1)

Isomerization and racemization of octahedral complexes

652

(2)

Electron-transfer processes

654

(8)

Inner-sphere mechanism

654

(2)

Outer-sphere mechanism

656

(6)

Homogeneous and heterogeneous catalysis

662

(23)

Introduction and definitions

662

(1)

Catalysis: introductory concepts

662

(3)

Free energy profiles for a reaction: catalyzed versus non-catalyzed

662

(1)

Catalytic cycles

663

(1)

Choosing a catalyst

664

(1)

Homogeneous catalysis: industrial applications

665

(6)

Alkene hydrogenation

665

(2)

Monsanto acetic acid synthesis

667

(1)

Tennessee--Eastman acetic anhydride process

668

(1)

Hydroformylation (Oxo-process)

669

(2)

Alkene oligomerization

671

(1)

Homogeneous catalyst development

671

(2)

Polymer-supported catalysts

671

(1)

Biphasic catalysis

672

(1)

d-Block organometallic clusters as homogeneous catalysts

672

(1)

Heterogeneous catalysis: surfaces and interactions with adsorbates

673

(2)

Heterogeneous catalysis: commercial applications

675

(5)

Alkene polymerization: Ziegler-Natta catalysis

675

(1)

Fischer-Tropsch carbon chain growth

676

(1)

Haber process

677

(1)

Production of SO3 in the Contact process

678

(1)

Catalytic converters

678

(1)

Zeolites as catalysts for organic transformations: uses of ZSM-5

679

(1)

Heterogeneous catalysis: organometallic cluster models

680

(5)

Some aspects of solid state chemistry

685

(16)

Introduction

685

(1)

Defects in solid state lattices

685

(2)

Types of defect: stoichiometric and non-stoichiometric compounds

685

(1)

Colour centres (F-centres)

686

(1)

Thermodynamic effects of crystal defects

686

(1)

Electrical conductivity in ionic solids

687

(2)

Sodium and lithium ion conductors

687

(1)

d-Block metal(II) oxides

688

(1)

Superconductivity

689

(2)

Superconductors: early examples and basic theory

689

(1)

High-temperature superconductors

689

(2)

Applications of superconductors

691

(1)

Ceramic materials: colour pigments

691

(1)

White pigments (opacifiers)

691

(1)

Adding colour

691

(1)

Chemical vapour deposition (CVD)

692

(5)

High-purity silicon for semiconductors

692

(1)

α-Boron nitride

693

(1)

Silicon nitride and carbide

693

(1)

III-V Semiconductors

694

(1)

Metal deposition

695

(1)

Ceramic coatings

695

(1)

Perovskites and cuprate superconductors

695

(2)

Inorganic fibres

697

(4)

Boron fibres

697

(1)

Carbon fibres

698

(1)

Silicon carbide fibres

698

(1)

Alumina fibres

698

(3)

The trace metals of life

701

(31)

Introduction

701

(2)

Amino acids, peptides and proteins: some terminology

701

(2)

Metal storage and transport: Fe, Cu, Zn and V

703

(4)

Iron storage and transport

703

(3)

Metallothioneins: transporting some toxic metals

706

(1)

Dealing with O2

707

(7)

Haemoglobin and myoglobin

707

(3)

Haemocyanin

710

(1)

Haemerythrin

711

(3)

Cytochromes P-450

714

(1)

Biological redox processes

714

(10)

Blue copper proteins

714

(3)

The mitochondrial electron-transfer chain

717

(1)

Iron-sulfur proteins

717

(5)

Cytochromes

722

(2)

The Zn2+ ion: Nature's Lewis acid

724

(8)

Carbonic anhydrase II

724

(1)

Carboxypeptidase A

725

(3)

Carboxypeptidase G2

728

(1)

Cobalt-for-zinc ion substitution

728

(4)

Appendices

732

(23)

1 Greek letters with pronunciations

733

(1)

2 Abbreviations and symbols for quantities and units

734

(4)

3 Selected character tables

738

(2)

4 The electromagnetic spectrum

740

(2)

5 Naturally occurring isotopes and their abundances

742

(2)

6 Van der Waals, metallic, covalent and ionic radii for the s-, p- and first row d-block elements

744

(2)

7 Pauling electronegativity values (χp) for selected elements of the periodic table

746

(1)

8 Ground state electronic configurations of the elements and ionization energies for the first five ionizations

747

(3)

9 Electron affinities

750

(1)

10 Standard enthalpies of atomization (ΔaHo) of the elements at 298 K

751

(1)

11 Selected standard reduction potentials (298 K)

752

(3)

Answers to non-descriptive problems

755

(16)

Index

771

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Inorganic Chemistry

Summary

Author Biography

Table of Contents

Supplemental Materials