Inorganic Chemistry

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

• ISBN13: 9780582310803
• ISBN10: 0582310806
• Edition: 1st
• Format: Paperback
• Copyright: 2001-01-01
• Publisher: Prentice Hall

Summary

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.

Author Biography

Catherine E. Housecroft is Professor of Inorganic Chemistry at the University of Birmingham, UK, Executive Editor of Polyhedron, a former Associate Editor of Coordination Chemistry Reviews.

Table of Contents

Preface	xxxi
Some basic concepts	1	(49)
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	(1)
The wave-nature of electrons	6	(1)
The uncertainty principle	6	(1)
The Schrodinger wave equation	6	(1)
Atomic orbitals	7	(8)
The quantum numbers n, l and ml	7	(3)
The radial part of the wavefunction, R(r)	10	(1)
The radial distribution function, 4πr2 R(r)2	11	(1)
The angular part of the wavefunction, A(&thetas;,&phis;)	11	(2)
Orbital energies in a hydrogen-like species	13	(1)
Size of orbitals	14	(1)
The spin quantum number and the magnetic spin quantum number	14	(1)
The ground state of the hydrogen atom	14	(1)
Many-electron atoms	15	(3)
The helium atom: two electrons	15	(1)
Ground state electronic configurations: experimental data	16	(1)
Penetration and shielding	16	(2)
The periodic table	18	(1)
The aufbau principle	18	(4)
Ground state electronic configurations	18	(3)
Valence and core electrons	21	(1)
Diagrammatic representations of electronic configurations	22	(1)
Ionization energies and electron affinities	22	(3)
Ionization energies	22	(2)
Eleotron affinities	24	(1)
Bonding models: an introduction	25	(1)
A historical overview	25	(1)
Lewis structures	25	(1)
Homonuclear diatomic molecules: valence bond (VB) theory	25	(3)
Uses of the term homonuclear	25	(1)
Covalent bond distance, covalent radius and van der Waals radius	26	(1)
The valence bond (VB) model of bonding in H2	26	(1)
The valence bond (VB) model applied to F2, O2 and N2	27	(1)
Homonuclear diatomic molecules: molecular orbital (MO) theory	28	(6)
An overview of the MO model	28	(1)
Molecular orbital theory applied to the bonding in H2	28	(2)
The bonding in He2, Li2 and Be2	30	(1)
The bonding in F2 and O2	31	(1)
What happens if the s-p separation is small?	31	(3)
The octet rule	34	(1)
Electronegativity values	35	(3)
Pauling electronegativity values, XP	35	(1)
Mulliken electronegativity values, XM	36	(1)
Allred-Rochow electronegativity values, XAR	36	(1)
Electronegativity: final remarks	37	(1)
Dipole moments	38	(1)
Polar diatomic molecules	38	(1)
Molecular dipole moments	39	(1)
MO theory: heteronuclear diatomic molecules	39	(2)
Which orbital interactions should be considered?	39	(1)
Hydrogen fluoride	40	(1)
Carbon monoxide	41	(1)
Isoelectronic molecules	41	(1)
Molecular shape and the VSEPR model	41	(5)
Valence-shell electron-pair repulsion theory	41	(2)
Limitations of VSEPR theory	43	(3)
Molecular shape: geometrical isomerism	46	(4)
Square planar species	46	(1)
Octahedral species	46	(1)
Trigonal bipyramidal species	47	(1)
High coordination numbers	47	(1)
Double bonds	47	(3)
Nuclear properties	50	(24)
Introduction	50	(1)
Nuclear binding energy	50	(2)
Mass defect and binding energy	50	(1)
The average binding energy per nucleon	51	(1)
Radioactivity	52	(2)
Nuclear emissions	52	(1)
Nuclear transformations	52	(1)
The kinetics of radioative decay	53	(1)
Units of radioactivity	54	(1)
Artificial isotopes	54	(1)
Bombardment of nuclei by high-energy &alpha-particles and neutrons	54	(1)
Bombardment of nuclei by `slow' neutrons	54	(1)
Nuclear fission	55	(3)
The fission of uranium-235	55	(2)
The production of energy by nuclear fission	57	(1)
Nuclear reprocessing	57	(1)
Syntheses of transuranium elements	58	(1)
The separation of radioactive isotopes	58	(1)
Chemical separation	58	(1)
The Szilard-Chalmers effect	58	(1)
Nuclear fusion	59	(1)
Applications of isotopes	59	(3)
Infrared (IR) spectroscopy	60	(1)
Kinetic isotope effects	60	(1)
Radiocarbon dating	61	(1)
Analytical applications	62	(1)
Sources of 2H and 13C	62	(1)
Deuterium: electrolytic separation of isotopes	62	(1)
Carbon-13: chemical enrichment	62	(1)
Multinuclear NMR spectroscopy in inorganic chemistry	62	(8)
Which nuclei are suitable for NMR spectroscopic studies?	63	(1)
Chemical shift ranges	63	(1)
Spin-spin coupling	63	(4)
Stereochemically non-rigid species	67	(1)
Exchange processes in solution	68	(2)
Mossbauer spectroscopy in inorganic chemistry	70	(4)
The technique of Mossbauer spectroscopy	70	(1)
What can isomer shift data tell us?	70	(4)
An introduction to molecular symmetry	74	(17)
Introduction	74	(1)
Symmetry operations and symmetry elements	74	(4)
Rotation about an n-fold axis of symmetry	75	(1)
Reflection through a plane of symmetry (mirror plane)	75	(1)
Reflection through a centre of symmetry (inversion centre)	75	(1)
Rotation about an axis, followed by reflection through a plane perpendicular to this axis	76	(1)
Identity operator	76	(2)
Successive operations	78	(1)
Point groups	78	(4)
C1 point group	78	(1)
C∞v point group	78	(1)
D∞h point group	79	(1)
Td, Oh or Ih point groups	79	(1)
Determining the point group of a molecule or molecular ion	79	(3)
Character tables: an introduction	82	(1)
Why do we need to recognize symmetry elements?	82	(1)
Infrared spectroscopy	83	(3)
How many vibrational modes are there for a given molecular species?	83	(1)
Selection rule for an infrared active mode of vibration	84	(1)
Linear and bent triatomic molecules	84	(1)
Trigonal planar and trigonal pyramidal molecules	84	(1)
Tetrahedral and square planar species	85	(1)
Observing IR spectroscopic absorptions: practical problems	86	(1)
Chiral molecules	86	(5)
Bonding in polyatomic molecules	91	(25)
Introduction	91	(1)
Valence bond theory: hybridization of atomic orbitals	91	(5)
What is orbital hybridization?	91	(1)
sp Hybridization: a scheme for linear species	92	(1)
sp2 Hybridization: a scheme for trigonal planar species	92	(2)
sp3 Hybridization: a scheme for tetrahedral species	94	(1)
Other hybridization schemes	95	(1)
Valence bond theory: multiple bonding in polyatomic molecules	96	(2)
C2H4	96	(1)
HCN	96	(1)
BF3	97	(1)
π-Bond formation between different types of orbitals	98	(1)
Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules	98	(2)
Molecular orbital diagrams: moving from a diatomic to polyatomic species	98	(1)
Ligand group orbitals: MO approach to the bonding in linear XH2	99	(1)
A bent triatomic: H2O	99	(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