Housecroft Inorganic Chemistry 3e

by Housecroft, Catherine; Sharpe, Alan G.

• ISBN13: 9780130399137
• ISBN10: 0130399132
• Additional ISBN(s): 9780131755536, 9780582310803
• Edition: 2nd
• Format: Paperback
• Copyright: 2008-01-01
• Publisher: Pearson College Div
• More Book Details
• Purchase Benefits

Summary

Inorganic ChemistryCatherine E. Housecroft and Alan G. Sharpe This book has established itself as a leading textbook in the subject by offering a fresh and exciting approach to the teaching of modern inorganic chemistry. It gives a clear introduction to key principles with strong coverage of descriptive chemistry of the elements. Special selected topics chapters are included, covering inorganic kinetics and mechanism, catalysis, solid state chemistry and bioinorganic chemistry. A new full-colour text design and three-dimensional illustrations bring inorganic chemistry to life. Topic boxes have been used extensively throughout the book to relate the chemistry described in the text to everyday life, the chemical industry, environmental issues and legislation, and natural resources. Teaching aids throughout the text have been carefully designed to help students learn effectively. The many worked examples take students through each calculation or exercise step by step, and are followed by related self-study exercises tackling similar problems with answers to help develop their confidence. In addition, end-of-chapter problems reinforce learning and develop subject knowledge and skills. Definitions boxes and end-of-chapter checklists provide excellent revision aids, while further reading suggestions, from topical articles to recent literature papers, will encourage students to explore topics in more depth. New to this edition Many more self-study exercises have been introduced throughout the book with the aim of making stronger connections between descriptive chemistry and underlying principles. Additional 'overview problems' have been added to the end-of-chapter problem sets. The descriptive chemistry has been updated, with many new results from the literature being included. Chapter 4 Bonding in polyatomic molecules, has been rewritten with greater emphasis on the use of group theory for the derivation of ligand group orbitals and orbital symmetry labels. There is more coverage of supercritical fluids and 'green' chemistry. The new full-colour text design enhances the presentation of the many molecular structures and 3-D images. Supporting this edition Companion website featuring multiple-choice questions and rotatable 3-D molecular structures, available at www.rearsoned.co.uk/housecroft . For full information, including details of lecturer material, see the Contents list inside the book. ASolutions Manual, written by Catherine E. Housecroft, with detailed solutions to all end-of-chapter problems within the text is available for purchase separately ISBN 0131 39926 8. Catherine E. Housecroft is Professor of Chemistry at the University of Basel, Switzerland. She is the author of a number of textbooks and has extensive teaching experience in the UK, Switzerland, South Africa and the USA. Alan G. Sharpe is a Fellow of Jesus College, University of Cambridge, UK and has had many years of experience teaching inorganic chemistry to undergraduates

Table of Contents

Preface to the second edition	xxxi
Preface to the first edition	xxiii
Some basic concepts	1	(52)
Introduction	1	(1)
Inorganic chemistry: it is not an isolated branch of chemistry	1	(1)
The aims of Chapter 1	1	(1)
Fundamental particles of an atom	1	(1)
Atomic number, mass number and isotopes	2	(1)
Nuclides, atomic number and mass number	2	(1)
Relative atomic mass	2	(1)
Isotopes	2	(1)
Successes in early quantum theory	3	(3)
Some important successes of classical quantum theory	4	(1)
Bohr's theory of the atomic spectrum of hydrogen	5	(1)
An introduction to wave mechanics	6	(3)
The wave-nature of electrons	6	(1)
The uncertainty principle	6	(1)
The Schrodinger wave equation	6	(3)
Atomic orbitals	9	(7)
The quantum numbers n, l and ml	9	(1)
The radial part of the wavefunction, R(r)	10	(1)
The radial distribution function, 4πr2R(r)2	11	(1)
The angular part of the wavefunction, A(θ,φ)	12	(1)
Orbital energies in a hydrogen-like species	13	(1)
Size of orbitals	13	(2)
The spin quantum number and the magnetic spin quantum number	15	(1)
The ground state of the hydrogen atom	16	(1)
Many-electron atoms	16	(1)
The helium atom: two electrons	16	(1)
Ground state electronic configurations: experimental data	16	(1)
Penetration and shielding	17	(1)
The periodic table	17	(4)
The aufbau principle	21	(2)
Ground state electronic configurations	21	(1)
Valence and core electrons	22	(1)
Diagrammatic representations of electronic configurations	22	(1)
Ionization energies and electron affinities	23	(3)
Ionization energies	23	(2)
Electron affinities	25	(1)
Bonding models: an introduction	26	(1)
A historical overview	26	(1)
Lewis structures	26	(1)
Homonuclear diatomic molecules: valence bond (VB) theory	27	(2)
Uses of the term homonuclear	27	(1)
Covalent bond distance, covalent radius and van der Waals radius	27	(1)
The valence bond (VB) model of bonding in H2	27	(1)
The valence bond (VB) model applied to F2, O2 and N2	28	(1)
Homonuclear diatomic molecules: molecular orbital (MO) theory	29	(7)
An overview of the MO model	29	(1)
Molecular orbital theory applied to the bonding in H2	29	(2)
The bonding in He2, Li2 and Be2	31	(1)
The bonding in F2 and O2	32	(1)
What happens if the s--p separation is small?	33	(3)
The octet rule	36	(1)
Electronegativity values	36	(3)
Pauling electronegativity values, ΧP	37	(1)
Mulliken electronegativity values, ΧM	37	(1)
Allred--Rochow electronegativity values, ΧAR	38	(1)
Electronegativity: final remarks	38	(1)
Dipole moments	39	(2)
Polar diatomic molecules	39	(1)
Molecular dipole moments	40	(1)
MO theory: heteronuclear diatomic molecules	41	(2)
Which orbital interactions should be considered?	41	(1)
Hydrogen fluoride	42	(1)
Carbon monoxide	42	(1)
Isoelectronic molecules	43	(1)
Molecular shape and the VSEPR model	43	(5)
Valence-shell electron-pair repulsion theory	43	(4)
Structures derived from a trigonal bipyramid	47	(1)
Limitations of VSEPR theory	48	(1)
Molecular shape: geometrical isomerism	48	(5)
Square planar species	48	(1)
Octahedral species	48	(1)
Trigonal bipyramidal species	49	(1)
High coordination numbers	49	(1)
Double bonds	49	(4)
Nuclear properties	53	(26)
Introduction	53	(1)
Nuclear binding energy	53	(2)
Mass defect and binding energy	53	(1)
The average binding energy per nucleon	54	(1)
Radioactivity	55	(2)
Nuclear emissions	55	(1)
Nuclear transformations	55	(1)
The kinetics of radioactive decay	56	(1)
Units of radioactivity	57	(1)
Artificial isotopes	57	(1)
Bombardment of nuclei by high-energy α-particles and neutrons	57	(1)
Bombardment of nuclei by `slow' neutrons	57	(1)
Nuclear fission	58	(3)
The fission of uranium-235	58	(2)
The production of energy by nuclear fission	60	(1)
Nuclear reprocessing	61	(1)
Syntheses of transuranium elements	61	(1)
The separation of radioactive isotopes	62	(1)
Chemical separation	62	(1)
The Szilard--Chalmers effect	62	(1)
Nuclear fusion	62	(1)
Applications of isotopes	63	(2)
Infrared (IR) spectroscopy	63	(1)
Kinetic isotope effects	64	(1)
Radiocarbon dating	64	(1)
Analytical applications	65	(1)
Sources of 2H and 13C	65	(2)
Deuterium: electrolytic separation of isotopes	65	(1)
Carbon-13: chemical enrichment	65	(2)
Multinuclear NMR spectroscopy in inorganic chemistry	67	(6)
Which nuclei are suitable for NMR spectroscopic studies?	68	(1)
Chemical shift ranges	68	(1)
Spin--spin coupling	69	(3)
Stereochemically non-rigid species	72	(1)
Exchange processes in solution	73	(1)
Mossbauer spectroscopy in inorganic chemistry	73	(6)
The technique of Mossbauer spectroscopy	73	(2)
What can isomer shift data tell us?	75	(4)
An introduction to molecular symmetry	79	(21)
Introduction	79	(1)
Symmetry operations and symmetry elements	79	(5)
Rotation about an n-fold axis of symmetry	80	(1)
Reflection through a plane of symmetry (mirror plane)	80	(2)
Reflection through a centre of symmetry (inversion centre)	82	(1)
Rotation about an axis, followed by reflection through a plane perpendicular to this axis	82	(1)
Identity operator	82	(2)
Successive operations	84	(1)
Point groups	85	(4)
C1 point group	85	(1)
C∞v point group	85	(1)
D∞h point group	85	(1)
Td, Oh or Ih point groups	86	(1)
Determining the point group of a molecule or molecular ion	86	(3)
Character tables: an introduction	89	(1)
Why do we need to recognize symmetry elements?	90	(1)
Infrared spectroscopy	90	(5)
How many vibrational modes are there for a given molecular species?	90	(1)
Selection rule for an infrared active mode of vibration	91	(1)
Linear (D∞h or C∞v) and bent (C2v) triatomic molecules	92	(1)
XY3 molecules with D3h or C3v symmetry	92	(1)
XY4 molecules with Td or D4h symmetry	93	(1)
Observing IR spectroscopic absorptions: practical problems	94	(1)
Chiral molecules	95	(5)
Bonding in polyatomic molecules	100	(31)
Introduction	100	(1)
Valence bond theory: hybridization of atomic orbitals	100	(5)
What is orbital hybridization?	100	(1)
sp Hybridization: a scheme for linear species	101	(1)
sp2 Hybridization: a scheme for trigonal planar species	102	(1)
sp3 Hybridization: a scheme for tetrahedral and related species	103	(1)
Other hybridization schemes	104	(1)
Valence bond theory: multiple bonding in polyatomic molecules	105	(2)
C2H4	105	(1)
HCN	105	(1)
BF3	106	(1)
Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules	107	(5)
Molecular orbital diagrams: moving from a diatomic to polyatomic species	107	(1)
MO approach to the bonding in linear XH2: symmetry matching by inspection	107	(2)
MO approach to bonding in linear XH2: working from molecular symmetry	109	(1)
A bent triatomic: H2O	109	(3)
Molecular orbital theory applied to the polyatomic molecules BH3, NH3 and CH4	112	(5)
BH3	112	(1)
NH3	113	(2)
CH4	115	(1)
A comparison of the MO and VB bonding models	116	(1)
Molecular orbital theory: bonding analyses soon become complicated	117	(2)
Molecular orbital theory: learning to use the theory objectively	119	(12)
π-Bonding in CO2	119	(1)
[NO3]-	120	(1)
SF6	120	(3)
Three-centre two-electron interactions	123	(1)
A more advanced problem: B2H6	124	(7)
Structures and energetics of metallic and ionic solids	131	(31)
Introduction	131	(1)
Packing of spheres	131	(3)
Cubic and hexagonal close-packing	131	(1)
The unit cell: hexagonal and cubic close-packing	132	(1)
Interstitial holes: hexagonal and cubic close-packing	133	(1)
Non-close-packing: simple cubic and body-centred cubic arrays	134	(1)
The packing-of-spheres model applied to the structures of elements	134	(2)
Group 18 elements in the solid state	134	(1)
H2 and F2 in the solid state	134	(1)
Metallic elements in the solid state	134	(2)
Polymorphism in metals	136	(1)
Polymorphism: phase changes in the solid state	136	(1)
Phase diagrams	136	(1)
Metallic radii	136	(1)
Melting points and standard enthalpies of atomization of metals	137	(2)
Alloys and intermetallic compounds	139	(2)
Substitutional alloys	139	(1)
Interstitial alloys	139	(1)
Intermetallic compounds	140	(1)
Bonding in metals and semiconductors	141	(2)
Electrical conductivity and resistivity	141	(1)
Band theory of metals and insulators	141	(1)
The Fermi level	142	(1)
Band theory of semiconductors	143	(1)
Semiconductors	143	(1)
Intrinsic semiconductors	143	(1)
Extrinsic (n- and p-type) semiconductors	143	(1)
Sizes of ions	144	(2)
Ionic radii	144	(1)
Periodic trends in ionic radii	145	(1)
Ionic lattices	146	(6)
The rock salt (NaCl) lattice	148	(1)
The caesium chloride (CsCl) lattice	149	(1)
The fluorite (CaF2) lattice	149	(1)
The antifluorite lattice	149	(1)
The zinc blende (ZnS) lattice: a diamond-type network	149	(1)
The β-cristobalite (SiO2) lattice	150	(1)
The wurtzite (ZnS) structure	151	(1)
The rutile (TiO2) structure	151	(1)
The CdI2 and CdCl2 lattices: layer structures	151	(1)
The perovskite (CaTiO3) lattice: a double oxide	152	(1)
Crystal structures of semiconductors	152	(1)
Lattice energy: estimates from an electrostatic model	152	(3)
Coulombic attraction within an isolated ion-pair	152	(1)
Coulombic interactions in an ionic lattice	153	(1)
Born forces	153	(1)
The Born-Lande equation	154	(1)
Madelung constants	154	(1)
Refinements to the Born--Lande equation	155	(1)
Overview	155	(1)
Lattice energy: the Born--Haber cycle	155	(1)
Lattice energy: `calculated' versus `experimental' values	156	(1)
Applications of lattice energies	157	(1)
Estimation of electron affinities	157	(1)
Fluoride affinities	157	(1)
Estimation of standard enthalpies of formation and disproportionation	157	(1)
The Kapustinskii equation	158	(1)
Defects in solid state lattices: an introduction	158	(4)
Schottky defect	158	(1)
Frenkel defect	158	(1)
Experimental observation of Schottky and Frenkel defects	159	(3)
Acids, bases and ions in aqueous solution	162	(30)
Introduction	162	(1)
Properties of water	162	(3)
Structure and hydrogen bonding	162	(1)
The self-ionization of water	163	(1)
Water as a Bronsted acid or base	163	(2)
Definitions and units in aqueous solution	165	(1)
Molarity and molality	165	(1)
Standard state	165	(1)
Activity	165	(1)
Some Bronsted acids and bases	166	(3)
Carboxylic acids: examples of mono-, di- and polybasic acids	166	(1)
Inorganic acids	167	(1)
Inorganic bases: hydroxides	167	(1)
Inorganic bases: nitrogen bases	168	(1)
The energetics of acid dissociation in aqueous solution	169	(1)
Hydrogen halides	169	(1)
H2S, H2Se and H2Te	170	(1)
Trends within a series of oxoacids EOn(OH)m	170	(1)
Aquated cations: formation and acidic properties	171	(2)
Water as a Lewis base	171	(1)
Aquated cations as Bronsted acids	172	(1)
Amphoteric oxides and hydroxides	173	(1)
Amphoteric behaviour	173	(1)
Periodic trends in amphoteric properties	173	(1)
Solubilities of ionic salts	174	(4)
Solubility and saturated solutions	174	(1)
Sparingly soluble salts and solubility products	174	(1)
The energetics of the dissolution of an ionic salt: ΔsolGo	175	(1)
The energetics of the dissolution of an ionic salt: hydration of ions	176	(1)
Solubilities: some concluding remarks	177	(1)
Common-ion effect	178	(1)
Coordination complexes: an introduction	178	(2)
Definitions and terminology	178	(1)
Investigating coordination complex formation	179	(1)
Stability constants of coordination complexes	180	(6)
Determination of stability constants	182	(1)
Trends in stepwise stability constants	182	(1)
Thermodynamic considerations of complex formation: an introduction	182	(4)
Factors affecting the stabilities of complexes containing only monodentate ligands	186	(6)
Ionic size and charge	186	(1)
Hard and soft metal centres and ligands	187	(5)
Reduction and oxidation	192	(22)
Introduction	192	(1)
Oxidation and reduction	192	(1)
Oxidation states	192	(1)
Stock nomenclature	193	(1)
Standard reduction potentials, Eo, and relationships between Eo, ΔGo and K	193	(6)
Half-cells and galvanic cells	193	(2)
Defining and using standard reduction potentials, Eo	195	(2)
Dependence of reduction potentials on cell conditions	197	(2)
The effect of complex formation or precipitation on Mz+/M reduction potentials	199	(4)
Half-cells involving silver halides	199	(1)
Modifying the relative stabilities of different oxidation states of a metal	200	(3)
Disproportionation reactions	203	(1)
Disproportionation	203	(1)
Stabilizing species against disproportionation	203	(1)
Potential diagrams	203	(2)
Frost--Ebsworth diagrams	205	(3)
Frost-Ebsworth diagrams and their relationship to potential diagrams	205	(1)
Interpretation of Frost--Ebsworth diagrams	206	(2)
The relationships between standard reduction potentials and some other quantities	208	(2)
Factors influencing the magnitudes of standard reduction potentials	208	(1)
Values of ΔfGo for aqueous ions	209	(1)
Applications of redox reactions to the extraction of elements from their ores	210	(4)
Ellingham diagrams	210	(4)
Non-aqueous media	214	(22)
Introduction	214	(1)
Relative permittivity	214	(1)
Energetics of ionic salt transfer from water to an organic solvent	215	(1)
Acid--base behaviour in non-aqueous solvents	216	(1)
Strengths of acids and bases	216	(1)
Levelling and differentiating effects	217	(1)
`Acids' in acidic solvents	217	(1)
Acids and bases: a solvent-oriented definition	217	(1)
Self-ionizing and non-ionizing non-aqueous solvents	217	(1)
Liquid ammonia	218	(3)
Physical properties	218	(1)
Self-ionization	218	(1)
Reactions in liquid NH3	218	(1)
Solutions of s-block metals in liquid NH3	219	(2)
Redox reactions in liquid NH3	221	(1)
Liquid hydrogen fluoride	221	(1)
Physical properties	221	(1)
Acid--base behaviour in liquid HF	221	(1)
Electrolysis in liquid HF	222	(1)
Sulfuric acid	222	(1)
Physical properties	222	(1)
Acid--base behaviour in liquid H2SO4	223	(1)
Fluorosulfonic acid	223	(1)
Physical properties	223	(1)
Superacids	224	(1)
Bromine trifluoride	224	(1)
Physical properties	224	(1)
Behaviour of fluoride salts and molecular fluorides in BrF3	225	(1)
Reactions in BrF3	225	(1)
Dinitrogen tetraoxide	225	(2)
Physical properties	225	(1)
Reactions in N2O4	226	(1)
Ionic liquids	227	(3)
Molten salt solvent systems	227	(1)
Ionic liquids at ambient temperatures	227	(2)
Reactions in and applications of molten salt/ionic liquid media	229	(1)
Supercritical fluids	230	(6)
Properties of supercritical fluids and their uses as solvents	230	(2)
Supercritical fluids as media for inorganic chemistry	232	(4)
Hydrogen	236	(21)
Hydrogen: the simplest atom	236	(1)
The H+ and H- ions	236	(1)
The hydrogen ion (proton)	236	(1)
The hydride ion	237	(1)
Isotopes of hydrogen	237	(1)
Protium and deuterium	237	(1)
Deuterated compounds	237	(1)
Tritium	238	(1)
Dihydrogen	238	(6)
Occurrence	238	(1)
Physical properties	238	(1)
Synthesis and uses	238	(4)
Reactivity	242	(2)
Polar and non-polar E--H bonds	244	(1)
Hydrogen bonding	244	(7)
The hydrogen bond	244	(2)
Trends in boiling points, melting points and enthalpies of vaporization for p-block binary hydrides	246	(1)
Infrared spectroscopy	246	(1)
Solid state structures	247	(3)
Hydrogen bonding in biological systems	250	(1)
Binary hydrides: classification and general properties	251	(6)
Classification	251	(1)
Interstitial metal hydrides	251	(1)
Saline hydrides	251	(2)
Molecular hydrides and complexes derived from them	253	(1)
Polymeric hydrides	254	(1)
Intermediate hydrides	255	(2)
Group 1: the alkali metals	257	(18)
Introduction	257	(1)
Occurrence, extraction and uses	257	(2)
Occurrence	257	(1)
Extraction	257	(2)
Major uses of the alkali metals and their compounds	259	(1)
Physical properties	259	(2)
General properties	259	(1)
Atomic spectra and flame tests	260	(1)
Radioactive isotopes	261	(1)
NMR active nuclei	261	(1)
The metals	261	(2)
Appearance	261	(1)
Reactivity	261	(2)
Halides	263	(1)
Oxides and hydroxides	264	(1)
Oxides, peroxides, superoxides, suboxides and ozonides	264	(1)
Hydroxides	265	(1)
Salts of oxoacids: carbonates and hydrogencarbonates	265	(2)
Aqueous solution chemistry including macrocyclic complexes	267	(4)
Hydrated ions	267	(1)
Complex ions	268	(3)
Non-aqueous coordination chemistry	271	(4)
The group 2 metals	275	(18)
Introduction	275	(1)
Occurrence, extraction and uses	275	(3)
Occurrence	275	(1)
Extraction	276	(1)
Major uses of the group 2 metals and their compounds	277	(1)
Physical properties	278	(1)
General properties	278	(1)
Flame tests	279	(1)
Radioactive isotopes	279	(1)
The metals	279	(1)
Appearance	279	(1)
Reactivity	279	(1)
Halides	280	(3)
Beryllium halides	280	(2)
Halides of Mg, Ca, Sr and Ba	282	(1)
Oxides and hydroxides	283	(3)
Oxides and peroxides	283	(2)
Hydroxides	285	(1)
Salts of oxoacids	286	(1)
Complex ions in aqueous solution	287	(1)
Aqua species of beryllium	287	(1)
Aqua species of Mg2+, Ca2+, Sr2+ and Ba2+	288	(1)
Complexes with ligands other than water	288	(1)
Complexes with amido or alkoxy ligands	288	(1)
Diagonal relationships between Li and Mg, and between Be and Al	288	(5)
Lithium and magnesium	289	(1)
Beryllium and aluminium	290	(3)
The group 13 elements	293	(45)
Introduction	293	(1)
Occurrence, extraction and uses	293	(3)
Occurrence	293	(1)
Extraction	293	(2)
Major uses of the group 13 elements and their compounds	295	(1)
Physical properties	296	(3)
Electronic configurations and oxidation states	296	(3)
NMR active nuclei	299	(1)
The elements	299	(2)
Appearance	299	(1)
Structures of the elements	300	(1)
Reactivity	301	(1)
Simple hydrides	301	(6)
Neutral hydrides	301	(4)
The [MH4]- ions	305	(2)
Halides and complex halides	307	(6)
Boron halides: BX3 and B2X4	307	(2)
Al(III), Ga(III), In(III) and Tl(III) halides and their complexes	309	(2)
Lower oxidation state Al, Ga, In and Tl halides	311	(2)
Oxides, oxoacids, oxoanions and hydroxides	313	(4)
Boron oxides, oxoacids and oxoanions	313	(3)
Aluminium oxides, oxoacids, oxoanions and hydroxides	316	(1)
Oxides of Ga, In and Tl	317	(1)
Compounds containing nitrogen	317	(5)
Nitrides	317	(1)
Ternary boron nitrides	318	(1)
Molecular species containing B--N or B--P bonds	319	(2)
Molecular species containing group 13 metal--nitrogen bonds	321	(1)
Aluminium to thallium: salts of oxoacids, aqueous solution chemistry and complexes	322	(2)
Aluminium sulfate and alums	322	(1)
Aqua ions	322	(1)
Redox reactions in aqueous solution	322	(1)
Coordination complexes of the M3+ ions	323	(1)
Metal borides	324	(2)
Electron-deficient borane and carbaborane clusters: an introduction	326	(12)
Boron hydrides	326	(12)
The group 14 elements	338	(47)
Introduction	338	(1)
Occurrence, extraction and uses	338	(4)
Occurrence	338	(1)
Extraction and manufacture	339	(1)
Uses	339	(3)
Physical properties	342	(3)
Ionization energies and cation formation	342	(1)
Some energetic and bonding considerations	343	(1)
NMR active nuclei	344	(1)
Mossbauer spectroscopy	344	(1)
Allotropes of carbon	345	(8)
Graphite and diamond: structure and properties	345	(1)
Graphite: intercalation compounds	345	(3)
Fullerenes: synthesis and structure	348	(1)
Fullerenes: reactivity	349	(4)
Carbon nanotubes	353	(1)
Structural and chemical properties of silicon, germanium, tin and lead	353	(1)
Structures	353	(1)
Chemical properties	353	(1)
Hydrides	354	(3)
Binary hydrides	354	(2)
Halohydrides of silicon and germanium	356	(1)
Carbides, silicides, germides, stannides and plumbides	357	(4)
Carbides	357	(1)
Silicides	358	(1)
Germides, stannides and plumbides	358	(3)
Halides and complex halides	361	(4)
Carbon halides	361	(2)
Silicon halides	363	(1)
Halides of germanium, tin and lead	364	(1)
Oxides, oxoacids and hydroxides	365	(11)
Oxides and oxoacids of carbon	365	(4)
Silica, silicates and aluminosilicates	369	(4)
Oxides, hydroxides and oxoacids of germanium, tin and lead	373	(3)
Silicones	376	(1)
Sulfides	377	(2)
Cyanogen, silicon nitride and tin nitride	379	(2)
Cyanogen and its derivatives	379	(1)
Silicon nitride	380	(1)
Tin(IV) nitride	381	(1)
Aqueous solution chemistry and salts of oxoacids of germanium, tin and lead	381	(4)
The group 15 elements	385	(47)
Introduction	385	(1)
Occurrence, extraction and uses	386	(3)
Occurrence	386	(1)
Extraction	387	(1)
Uses	387	(2)
Physical properties	389	(3)
Bonding considerations	390	(1)
NMR active nuclei	391	(1)
Radioactive isotopes	391	(1)
The elements	392	(2)
Nitrogen	392	(1)
Phosphorus	392	(1)
Arsenic, antimony and bismuth	393	(1)
Hydrides	394	(7)
Trihydrides, EH3 (E = N, P, As, Sb and Bi)	394	(3)
Hydrides E2H4(E = N, P, As)	397	(1)
Chloramine and hydroxylamine	398	(1)
Hydrogen azide and azide salts	399	(2)
Nitrides, phosphides, arsenides, antimonides and bismuthides	401	(2)
Nitrides	401	(1)
Phosphides	402	(1)
Arsenides, antimonides and bismuthides	402	(1)
Halides, oxohalides and complex halides	403	(9)
Nitrogen halides	403	(2)
Oxofluorides and oxochlorides of nitrogen	405	(1)
Phosphorus halides	406	(2)
Phosphoryl trichloride, POCl3	408	(1)
Arsenic and antimony halides	409	(2)
Bismuth halides	411	(1)
Oxides of nitrogen	412	(3)
Dinitrogen monoxide, N2O	412	(1)
Nitrogen monoxide, NO	412	(1)
Dinitrogen trioxide, N2O3	413	(1)
Dinitrogen tetraoxide, N2O4, and nitrogen dioxide, NO2	414	(1)
Dinitrogen pentaoxide, N2O5	415	(1)
Oxoacids of nitrogen	415	(2)
Hyponitrous acid, H2N2O2	415	(1)
Nitrous acid, HNO2	415	(1)
Nitric acid, HNO3, and its derivatives	416	(1)
Oxides of phosphorus, arsenic, antimony and bismuth	417	(2)
Oxides of phosphorus	418	(1)
Oxides of arsenic, antimony and bismuth	419	(1)
Oxoacids of phosphorus	419	(3)
Phosphinic acid, H3PO2	419	(1)
Phosphonic acid, H3PO3	420	(1)
Hypophosphoric acid, H4P2O6	420	(1)
Phosphoric acid, H3PO4, and its derivatives	421	(1)
Oxoacids of arsenic, antimony and bismuth	422	(2)
Phosphazenes	424	(2)
Sulfides and selenides	426	(2)
Sulfides and selenides of phosphorus	426	(2)
Arsenic, antimony and bismuth sulfides	428	(1)
Aqueous solution chemistry	428	(4)
The group 16 elements	432	(36)
Introduction	432	(1)
Occurrence, extraction and uses	432	(2)
Occurrence	432	(1)
Extraction	433	(1)
Uses	433	(1)
Physical properties and bonding considerations	434	(3)
NMR active nuclei and isotopes as tracers	437	(1)
The elements	437	(5)
Dioxygen	437	(1)
Ozone	438	(1)
Sulfur: allotropes	439	(1)
Sulfur: reactivity	440	(1)
Selenium and tellurium	441	(1)
Hydrides	442	(4)
Water, H2O	442	(1)
Hydrogen peroxide, H2O2	442	(3)
Hydrides H2E (E = S, Se, Te)	445	(1)
Polysulfanes	445	(1)
Metal sulfides, polysulfides, polyselenides and polytellurides	446	(2)
Sulfides	446	(1)
Polysulfides	446	(1)
Polyselenides and polytellurides	447	(1)
Halides, oxohalides and complex halides	448	(5)
Oxygen fluorides	448	(1)
Sulfur fluorides and oxofluorides	448	(2)
Sulfur chlorides and oxochlorides	450	(1)
Halides of selenium and tellurium	451	(2)
Oxides	453	(4)
Oxides of sulfur	453	(3)
Oxides of selenium and tellurium	456	(1)
Oxoacids and their salts	457	(5)
Dithionous acid, H2S2O4	457	(1)
Sulfurous and disulfurous acids, H2SO3 and H2S2O5	457	(1)
Dithionic acid, H2S2O6	458	(1)
Sulfuric acid, H2SO4	459	(2)
Fluoro- and chlorosulfonic acids, HSO3F and HSO3Cl	461	(1)
Polyoxoacids with S--O--S units	461	(1)
Peroxosulfuric acids, H2S2O8 and H2SO5	461	(1)
Thiosulfuric acid, H2S2O3, and polythionates	461	(1)
Oxoacids of selenium and tellurium	462	(1)
Compounds of sulfur and selenium with nitrogen	462	(2)
Sulfur-nitrogen compounds	462	(2)
Tetraselenium tetranitride	464	(1)
Aqueous solution chemistry of sulfur, selenium and tellurium	464	(4)
The group 17 elements	468	(24)
Introduction	468	(1)
Fluorine, chlorine, bromine and iodine	468	(1)
Astatine	469	(1)
Occurrence, extraction and uses	469	(2)
Occurrence	469	(1)
Extraction	470	(1)
Uses	471	(1)
Physical properties and bonding considerations	471	(3)
NMR active nuclei and isotopes as tracers	473	(1)
The elements	474	(3)
Difluorine	474	(1)
Dichlorine, dibromine and diiodine	475	(1)
Charge transfer complexes	475	(2)
Clathrates	477	(1)
Hydrogen halides	477	(1)
Metal halides: structures and energetics	478	(1)
Interhalogen compounds and polyhalogen ions	479	(4)
Interhalogen compounds	479	(3)
Bonding in [XY2]- ions	482	(1)
Polyhalogen cations	482	(1)
Polyhalide anions	483	(1)
Oxides and oxofluorides of chlorine, bromine and iodine	483	(2)
Oxides	483	(1)
Oxofluorides	484	(1)
Oxoacids and their salts	485	(3)
Hypofluorous acid, HOF	485	(1)
Oxoacids of chlorine, bromine and iodine	485	(3)
Aqueous solution chemistry	488	(4)
The group 18 elements	492	(11)
Introduction	492	(1)
Occurrence, extraction and uses	493	(1)
Occurrence	493	(1)
Extraction	493	(1)
Uses	493	(1)
Physical properties	494	(2)
NMR active nuclei	495	(1)
Compounds of xenon	496	(5)
Fluorides	496	(2)
Chlorides	498	(1)
Oxides	499	(1)
Oxofluorides	499	(1)
Other compounds of xenon	499	(2)
Compounds of krypton and radon	501	(2)
Organometallic compounds of s- and p-block elements	503	(32)
Introduction	503	(1)
Group 1: alkali metal organometallics	504	(3)
Group 2 organometallics	507	(4)
Beryllium	507	(2)
Magnesium	509	(1)
Calcium, strontium and barium	510	(1)
Group 13	511	(7)
Boron	511	(1)
Aluminium	511	(3)
Gallium, indium and thallium	514	(4)
Group 14	518	(9)
Silicon	518	(2)
Germanium	520	(1)
Tin	521	(3)
Lead	524	(2)
Coparallel and tilted C5-rings in group 14 metallocenes	526	(1)
Group 15	527	(3)
Bonding aspects and E=E bond formation	527	(1)
Arsenic, antimony and bismuth	527	(3)
Group 16	530	(5)
Selenium and tellurium	530	(5)
d-Block chemistry: general considerations	535	(20)
Topic overview	535	(1)
Ground state electronic configurations	535	(1)
d-Block metals versus transition elements	535	(1)
Electronic configurations	536	(1)
Physical properties	536	(2)
The reactivity of the metals	538	(1)
Characteristic properties: a general perspective	538	(1)
Colour	538	(1)
Paramagnetism	539	(1)
Complex formation	539	(1)
Variable oxidation states	539	(1)
Electroneutrality principle	539	(2)
Coordination numbers	541	(6)
The Kepert model	541	(2)
Coordination number 2	543	(1)
Coordination number 3	543	(1)
Coordination number 4	543	(1)
Coordination number 5	544	(1)
Coordination number 6	544	(1)
Coordination number 7	545	(1)
Coordination number 8	546	(1)
Coordination number 9	547	(1)
Coordination numbers of 10 and above	547	(1)
Isomerism in d-block metal complexes	547	(8)
Structural isomerism: ionization isomers	548	(1)
Structural isomerism: hydration isomers	548	(1)
Structural isomerism: coordination isomerism	549	(1)
Structural isomerism: linkage isomerism	549	(1)
Structural isomerism: polymerization isomerism	549	(1)
Stereoisomerism: geometrical isomers	549	(1)
Stereoisomerism: optical isomers	549	(6)
d-Block chemistry: coordination complexes	555	(38)
Introduction	555	(1)
High- and low-spin states	555	(1)
Bonding in d-block metal complexes: valence bond theory	555	(2)
Hybridization schemes	555	(1)
Applying VB theory	556	(1)
Crystal field theory	557	(7)
The octahedral crystal field	558	(2)
Crystal field stabilization energy: high- and low-spin octahedral complexes	560	(1)
Jahn--Teller distortions	561	(1)
The tetrahedral crystal field	562	(1)
The square planar crystal field	562	(2)
Other crystal fields	564	(1)
Crystal field theory: uses and limitations	564	(1)
Molecular orbital theory: octahedral complexes	564	(6)
Complexes with no metal--ligand π-bonding	564	(2)
Complexes with metal--ligand π-bonding	566	(4)
Ligand field theory	570	(1)
Electronic spectra	570	(8)
Spectral features	570	(1)
Selection rules	571	(3)
Electronic spectra of octahedral and tetrahedral complexes	574	(2)
Microstates	576	(1)
Tanabe--Sugano diagrams	577	(1)
Evidence for metal--ligand covalent bonding	578	(1)
The nephelauxetic effect	578	(1)
ESR spectroscopy	579	(1)
Magnetic properties	579	(6)
Magnetic susceptibility and the spin-only formula	579	(2)
Spin and orbital contributions to the magnetic moment	581	(2)
The effects of temperature on μeff	583	(1)
Spin crossover	584	(1)
Ferromagnetism, antiferromagnetism and ferrimagnetism	584	(1)
Thermodynamic aspects: ligand field stabilization energies (LFSE)	585	(2)
Trends in LFSE	585	(1)
Lattice energies and hydration energies of Mn+ ions	586	(1)
Octahedral versus tetrahedral coordination: spinels	587	(1)
Thermodynamic aspects: the Irving--Williams series	587	(1)
Thermodynamic aspects: oxidation states in aqueous solution	588	(5)
d-Block metal chemistry: the first row metals	593	(52)
Introduction	593	(1)
Occurrence, extraction and uses	593	(4)
Physical properties: an overview	597	(1)
Group 3: scandium	597	(1)
The metal	597	(1)
Scandium(III)	598	(1)
Group 4: titanium	598	(4)
The metal	598	(1)
Titanium(IV)	598	(3)
Titanium(III)	601	(1)
Low oxidation states	601	(1)
Group 5: vanadium	602	(4)
The metal	602	(1)
Vanadium(V)	602	(2)
Vanadium(IV)	604	(1)
Vanadium(III)	605	(1)
Vanadium(II)	605	(1)
Group 6: chromium	606	(5)
The metal	606	(1)
Chromium(VI)	606	(1)
Chromium(V) and chromium(IV)	607	(1)
Chromium(III)	608	(1)
Chromium(II)	609	(1)
Chromium-chromium multiple bonds	610	(1)
Group 7: manganese	611	(6)
The metal	611	(1)
Manganese(VII)	612	(1)
Manganese(VI)	613	(1)
Manganese(V)	613	(1)
Manganese(IV)	613	(1)
Manganese(III)	614	(2)
Manganese(II)	616	(1)
Group 8: iron	617	(7)
The metal	617	(1)
Iron(VI), iron(V) and iron(IV)	617	(1)
Iron(III)	618	(4)
Iron(II)	622	(2)
Group 9: cobalt	624	(6)
The metal	624	(1)
Cobalt(IV)	624	(1)
Cobalt(III)	624	(3)
Cobalt(II)	627	(3)
Group 10: nickel	630	(4)
The metal	630	(1)
Nickel(IV) and nickel(III)	630	(1)
Nickel(II)	631	(3)
Nickel(I)	634	(1)
Group 11: copper	634	(5)
The metal	634	(1)
Copper(IV) and (III)	634	(1)
Copper(II)	635	(2)
Copper(I)	637	(2)
Group 12: zinc	639	(6)
The metal	639	(1)
Zinc(II)	640	(5)
d-Block metal chemistry: the second and third row metals	645	(55)
Introduction	645	(1)
Occurrence, extraction and uses	645	(4)
Physical properties	649	(2)
Effects of the lanthanoid contraction	649	(1)
Coordination numbers	649	(1)
NMR active nuclei	649	(2)
Group 3: yttrium	651	(1)
The metal	651	(1)
Yttrium(III)	651	(1)
Group 4: zirconium and hafnium	652	(2)
The metals	652	(1)
Zirconium(IV) and hafnium(IV)	652	(1)
Lower oxidation states of zirconium and hafnium	652	(1)
Zirconium clusters	653	(1)
Group 5: niobium and tantalum	654	(4)
The metals	654	(1)
Niobium(V) and tantalum(V)	654	(2)
Niobium(IV) and tantalum(IV)	656	(1)
Lower oxidation state halides	656	(2)
Group 6: molybdenum and tungsten	658	(8)
The metals	658	(1)
Molybdenum(VI) and tungsten(VI)	659	(3)
Molybdenum(V) and tungsten(V)	662	(1)
Molybdenum(IV) and tungsten(IV)	663	(1)
Molybdenum(III) and tungsten(III)	663	(2)
Molybdenum(II) and tungsten(II)	665	(1)
Group 7: technetium and rhenium	666	(5)
The metals	666	(1)
High oxidation states of technetium and rhenium: M(VII), M(VI) and M(V)	667	(2)
Technetium(IV) and rhenium(IV)	669	(1)
Technetium(III) and rhenium(III)	669	(2)
Group 8: ruthenium and osmium	671	(8)
The metals	671	(1)
High oxidation states of ruthenium and osmium: M(VIII), M(VII) and M(VI)	671	(2)
Ruthenium(V), (IV) and osmium(V), (IV)	673	(2)
Ruthenium(III) and osmium(III)	675	(1)
Ruthenium(II) and osmium(II)	676	(2)
Mixed-valence ruthenium complexes	678	(1)
Group 9: rhodium and iridium	679	(5)
The metals	679	(1)
High oxidation states of rhodium and iridium: M(VI) and M(V)	679	(1)
Rhodium(IV) and iridium(IV)	680	(1)
Rhodium(III) and iridium(III)	680	(2)
Rhodium(II) and iridium(II)	682	(1)
Rhodium(I) and iridium(I)	683	(1)
Group 10: palladium and platinum	684	(5)
The metals	684	(1)
The highest oxidation states: M(VI) and M(V)	684	(1)
Palladium(IV) and platinum(IV)	684	(1)
Palladium(III), platinum(III) and mixed-valence complexes	685	(1)
Palladium(II) and platinum(II)	686	(3)
Group 11: silver and gold	689	(5)
The metals	689	(1)
Gold(V) and silver(V)	690	(1)
Gold(III) and silver(III)	690	(1)
Gold(II) and silver(II)	691	(1)
Gold(I) and silver(I)	692	(2)
Gold(--I) and silver(--I)	694	(1)
Group 12: cadmium and mercury	694	(6)
The metals	694	(1)
Cadmium(II)	695	(1)
Mercury(II)	695	(1)
Mercury(I)	696	(4)
Organometallic compounds of d-block elements	700	(41)
Introduction	700	(1)
Hapticity of a ligand	700	(1)
Common types of ligand: bonding and spectroscopy	700	(7)
σ-Bonded alkyl, aryl and related ligands	700	(1)
Carbonyl ligands	701	(1)
Hydride ligands	702	(1)
Phosphine and related ligands	703	(1)
π-Bonded organic ligands	704	(2)
Dinitrogen	706	(1)
Dihydrogen	707	(1)
The 18-electron rule	707	(2)
Metal carbonyls: synthesis, physical properties and structure	709	(5)
Synthesis and physical properties	710	(1)
Structures	711	(3)
The isolobal principle and application of Wade's rules	714	(2)
Total valence electron counts in d-block organometallic clusters	716	(3)
Single cage structures	717	(1)
Condensed cages	718	(1)
Limitations of total valence counting schemes	719	(1)
Types of organometallic reactions	719	(3)
Substitution of CO ligands	719	(1)
Oxidative addition	719	(1)
Alkyl and hydrogen migrations	720	(1)
β-Hydrogen elimination	721	(1)
α-Hydrogen abstraction	721	(1)
Summary	722	(1)
Metal carbonyls: selected reactions	722	(1)
Metal carbonyl hydrides and halides	723	(1)
Alkyl, aryl, alkene and alkyne complexes	724	(3)
σ-Bonded alkyl and aryl ligands	724	(1)
Alkene ligands	725	(1)
Alkyne ligands	726	(1)
Allyl and buta-1,3-diene complexes	727	(2)
Allyl and related ligands	727	(1)
Buta-1,3-diene and related ligands	728	(1)
Carbene and carbyne complexes	729	(1)
Complexes containing η5-cyclopentadienyl ligands	730	(4)
Ferrocene and other metallocenes	731	(1)
(η5-Cp)2Fe2(CO)4 and derivatives	732	(2)
Complexes containing η6 - and η7-ligands	734	(3)
η6-Arene ligands	734	(1)
Cycloheptatriene and derived ligands	735	(2)
Complexes containing the η4-cyclobutadiene ligand	737	(4)
The f-block metals: lanthanoids and actinoids	741	(23)
Introduction	741	(1)
f-Orbitals and oxidation states	742	(1)
Atom and ion sizes	743	(1)
The lanthanoid contraction	743	(1)
Coordination numbers	743	(1)
Spectroscopic and magnetic properties	744	(3)
Electronic spectra and magnetic moments: lanthanoids	744	(2)
Luminescence of lanthanoid complexes	746	(1)
Electronic spectra and magnetic moments: actinoids	746	(1)
Sources of the lanthanoids and actinoids	747	(1)
Occurrence and separation of the lanthanoids	747	(1)
The actinoids	748	(1)
Lanthanoid metals	748	(1)
Inorganic compounds and coordination complexes of the lanthanoids	749	(2)
Halides	749	(1)
Hydroxides and oxides	750	(1)
Complexes of Ln(III)	750	(1)
Organometallic complexes of the lanthanoids	751	(4)
σ-Bonded complexes	751	(2)
Cyclopentadienyl complexes	753	(2)
Bis(arene) derivatives	755	(1)
Complexes containing the η8-cyclooctatetraenyl ligand	755	(1)
The actinoid metals	755	(1)
Inorganic compounds and coordination complexes of thorium, uranium and plutonium	756	(3)
Thorium	756	(1)
Uranium	757	(1)
Plutonium	758	(1)
Organometallic complexes of thorium and uranium	759	(5)
σ-Bonded complexes	759	(1)
Cyclopentadienyl derivatives	760	(1)
Complexes containing the η8-cyclooctatetraenyl ligand	761	(3)
d-Block metal complexes: reaction mechanisms	764	(22)
Introduction	764	(1)
Ligand substitutions: some general points	764	(2)
Kinetically inert and labile complexes	764	(1)
Stoichiometric equations say nothing about mechanism	764	(1)
Types of substitution mechanism	765	(1)
Activation parameters	765	(1)
Substitution in square planar complexes	766	(3)
Rate equations, mechanism and the trans-effect	766	(3)
Ligand nucleophilicity	769	(1)
Substitution and racemization in octahedral complexes	769	(8)
Water exchange	770	(2)
The Eigen--Wilkins mechanism	772	(2)
Stereochemistry of substitution	774	(1)
Base-catalysed hydrolysis	774	(2)
Isomerization and racemization of octahedral complexes	776	(1)
Electron-transfer processes	777	(9)
Inner-sphere mechanism	777	(2)
Outer-sphere mechanism	779	(7)
Homogeneous and heterogeneous catalysis	786	(27)
Introduction and definitions	786	(1)
Catalysis: introductory concepts	786	(3)
Energy profiles for a reaction: catalysed versus non-catalysed	786	(1)
Catalytic cycles	787	(1)
Choosing a catalyst	788	(1)
Homogeneous catalysis: alkene (olefin) metathesis	789	(2)
Homogeneous catalysis: industrial applications	791	(6)
Alkene hydrogenation	791	(2)
Monsanto acetic acid synthesis	793	(1)
Tennessee--Eastman acetic anhydride process	794	(1)
Hydroformylation (Oxo-process)	795	(2)
Alkene oligomerization	797	(1)
Homogeneous catalyst development	797	(2)
Polymer-supported catalysts	797	(1)
Biphasic catalysis	798	(1)
d-Block organometallic clusters as homogeneous catalysts	799	(1)
Heterogeneous catalysis: surfaces and interactions with adsorbates	799	(3)
Heterogeneous catalysis: commercial applications	802	(5)
Alkene polymerization: Ziegler--Natta catalysis	802	(1)
Fischer--Tropsch carbon chain growth	803	(1)
Haber process	804	(1)
Production of SO3 in the Contact process	805	(1)
Catalytic converters	805	(1)
Zeolites as catalysts for organic transformations: uses of ZSM-5	806	(1)
Heterogeneous catalysis: organometallic cluster models	807	(6)
Some aspects of solid state chemistry	813	(17)
Introduction	813	(1)
Defects in solid state lattices	813	(2)
Types of defect: stoichiometric and non-stoichiometric compounds	813	(1)
Colour centres (F-centres)	814	(1)
Thermodynamic effects of crystal defects	814	(1)
Electrical conductivity in ionic solids	815	(2)
Sodium and lithium ion conductors	815	(1)
d-Block metal(II) oxides	816	(1)
Superconductivity	817	(2)
Superconductors: early examples and basic theory	817	(1)
High-temperature superconductors	817	(2)
Superconducting properties of MgB2	819	(1)
Applications of superconductors	819	(1)
Ceramic materials: colour pigments	819	(1)
White pigments (opacifiers)	820	(1)
Adding colour	820	(1)
Chemical vapour deposition (CVD)	820	(6)
High-purity silicon for semiconductors	821	(1)
α-Boron nitride	821	(1)
Silicon nitride and carbide	821	(1)
III-V Semiconductors	822	(1)
Metal deposition	823	(1)
Ceramic coatings	824	(1)
Perovskites and cuprate superconductors	824	(2)
Inorganic fibres	826	(4)
Boron fibres	826	(1)
Carbon fibres	826	(1)
Silicon carbide fibres	827	(1)
Alumina fibres	827	(3)
The trace metals of life	830	(33)
Introduction	830	(2)
Amino acids, peptides and proteins: some terminology	830	(2)
Metal storage and transport: Fe, Cu, Zn and V	832	(5)
Iron storage and transport	832	(3)
Metallothioneins: transporting some toxic metals	835	(2)
Dealing with O2	837	(6)
Haemoglobin and myoglobin	837	(2)
Haemocyanin	839	(2)
Haemerythrin	841	(2)
Cytochromes P-450	843	(1)
Biological redox processes	843	(11)
Blue copper proteins	844	(1)
The mitochondrial electron-transfer chain	845	(2)
Iron--sulfur proteins	847	(4)
Cytochromes	851	(3)
The Zn2+ ion: Nature's Lewis acid	854	(9)
Carbonic anhydrase II	854	(1)
Carboxypeptidase A	855	(3)
Carboxypeptidase G2	858	(1)
Cobalt-for-zinc ion substitution	859	(4)
Appendices	863	(25)
1 Greek letters with pronunciations	864	(1)
2 Abbreviations and symbols for quantities and units	865	(4)
3 Selected character tables	869	(4)
4 The electromagnetic spectrum	873	(2)
5 Naturally occurring isotopes and their abundances	875	(2)
6 Van der Waals, metallic, covalent and ionic radii for the s-, p- and first row d-block elements	877	(2)
7 Pauling electronegativity values (ΧP) for selected elements of the periodic table	879	(1)
8 Ground state electronic configurations of the elements and ionization energies for the first five ionizations	880	(3)
9 Electron affinities	883	(1)
10 Standard enthalpies of atomization (ΔaHo) of the elements at 298K	884	(1)
11 Selected standard reduction potentials (298 K)	885	(3)
Answers to non-descriptive problems	888	(17)
Index	905