Inorganic chemistry

Cover......Page 1
Inorganic Chemistry......Page 4
Summary of Contents......Page 6
Contents......Page 8
Preface......Page 37
Acknowledgements......Page 39
Fundamental particles of an atom......Page 40
Atomic number, mass number and isotopes......Page 41
Successes in early quantum theory......Page 42
An introduction to wave mechanics......Page 45
Atomic orbitals......Page 48
Many-electron atoms......Page 56
The periodic table......Page 59
The aufbau principle......Page 61
Ionization energies and electron affinities......Page 63
Bonding models: an introduction......Page 69
Homonuclear diatomic molecules: valence bond (VB) theory......Page 70
Homonuclear diatomic molecules: molecular orbital (MO) theory......Page 72
The octet rule and isoelectronic species......Page 79
Electronegativity values......Page 81
Dipole moments......Page 83
MO theory: heteronuclear diatomic molecules......Page 85
Molecular shape and the VSEPR model......Page 87
Molecular shape: stereoisomerism......Page 93
Nuclear binding energy......Page 97
Radioactivity......Page 99
Artificial isotopes......Page 101
Nuclear fission......Page 102
Syntheses of transuranium elements......Page 103
Nuclear fusion......Page 106
Applications of isotopes......Page 108
Multinuclear NMR spectroscopy ininorganic chemistry......Page 111
Mo¨ ssbauer spectroscopy in inorganic chemistry......Page 121
Symmetry operations and symmetry elements......Page 127
Successive operations......Page 132
Point groups......Page 133
Character tables: an introduction......Page 137
Why do we need to recognize symmetry elements?......Page 138
Vibrational spectroscopy......Page 139
Chiral molecules......Page 149
Valence bond theory: hybridization of atomic orbitals......Page 154
Valence bond theory: multiple bonding in polyatomic molecules......Page 159
Molecular orbital theory: the ligand group orbital approach and application to triatomic molecules......Page 161
Molecular orbital theory applied to the polyatomic molecules BH3, NH3 and CH4......Page 166
Molecular orbital theory: bonding analyses soon become complicated......Page 172
Molecular orbital theory: learning to use the theory objectively......Page 174
Packing of spheres......Page 187
The packing-of-spheres model applied to the structures of elements......Page 190
Polymorphism in metals......Page 192
Metallic radii......Page 193
Alloys and intermetallic compounds......Page 194
Bonding in metals and semiconductors......Page 197
Semiconductors......Page 200
Sizes of ions......Page 201
Ionic lattices......Page 203
Lattice energy: estimates from an electrostatic model......Page 210
Lattice energy: the Born--Haber cycle......Page 213
Applications of lattice energies......Page 214
Defects in solid state lattices: an introduction......Page 216
Properties of water......Page 220
Definitions and units in aqueous solution......Page 223
Some Brønsted acids and bases......Page 224
The energetics of acid dissociation in aqueous solution......Page 226
Trends within a series of oxoacids EOn(OH)m......Page 229
Aquated cations: formation and acidic properties......Page 230
Solubilities of ionic salts......Page 232
Common-ion effect......Page 236
Coordination complexes: an introduction......Page 237
Stability constants of coordination complexes......Page 240
Factors affecting the stabilities of complexes containing only monodentate ligands......Page 245
Introduction......Page 251
Standard reduction potentials, Eo, and relationships between Eo, Go and K......Page 252
The effect of complex formation or precipitation on Mzþ/M reduction potentials......Page 260
Disproportionation reactions......Page 264
Potential diagrams......Page 265
Frost--Ebsworth diagrams......Page 266
The relationships between standard reduction potentials and some other quantities......Page 269
Applications of redox reactions to the extraction of elements from their ores......Page 271
Introduction......Page 275
Relative permittivity......Page 276
Energetics of ionic salt transfer from water to an organic solvent......Page 277
Acid--base behaviour in non-aqueous solvents......Page 278
Liquid ammonia......Page 279
Liquid hydrogen fluoride......Page 283
Sulfuric acid and fluorosulfonic acid......Page 284
Superacids......Page 286
Bromine trifluoride......Page 287
Dinitrogen tetraoxide......Page 288
Ionic liquids......Page 290
Supercritical fluids......Page 294
The Hþ and H ions......Page 300
Isotopes of hydrogen......Page 301
Dihydrogen......Page 302
Polar and non-polar EH bonds......Page 308
Hydrogen bonding......Page 309
Binary hydrides: classification and general properties......Page 317
Occurrence, extraction and uses......Page 323
Physical properties......Page 325
The metals......Page 328
Halides......Page 331
Oxides and hydroxides......Page 332
Salts of oxoacids: carbonates and hydrogencarbonates......Page 333
Aqueous solution chemistry including macrocyclic complexes......Page 335
Non-aqueous coordination chemistry......Page 340
Occurrence, extraction and uses......Page 344
Physical properties......Page 347
The metals......Page 348
Halides......Page 350
Oxides and hydroxides......Page 353
Salts of oxoacids......Page 356
Complex ions in aqueous solution......Page 357
Complexes with amido or alkoxy ligands......Page 359
Diagonal relationships between Li and Mg, and between Be and Al......Page 360
Occurrence, extraction and uses......Page 364
Physical properties......Page 368
The elements......Page 370
Simple hydrides......Page 373
Halides and complex halides......Page 379
Oxides, oxoacids, oxoanions and hydroxides......Page 386
Compounds containing nitrogen......Page 391
Aluminium to thallium: salts of oxoacids, aqueous solution chemistry and complexes......Page 396
Metal borides......Page 399
Electron-deficient borane and carbaborane clusters: an introduction......Page 401
Occurrence, extraction and uses......Page 415
Physical properties......Page 419
Allotropes of carbon......Page 423
Structural and chemical properties of silicon, germanium, tin and lead......Page 433
Hydrides......Page 434
Carbides, silicides, germides, stannides and plumbides......Page 438
Halides and complex halides......Page 442
Oxides, oxoacids and hydroxides......Page 448
Siloxanes and polysiloxanes (silicones)......Page 461
Sulfides......Page 462
Cyanogen, silicon nitride and tin nitride......Page 465
Aqueous solution chemistry and salts of oxoacids of germanium, tin and lead......Page 467
Introduction......Page 472
Occurrence, extraction and uses......Page 474
Physical properties......Page 476
The elements......Page 480
Hydrides......Page 482
Nitrides, phosphides, arsenides, antimonides and bismuthides......Page 490
Halides, oxohalides and complex halides......Page 494
Oxides of nitrogen......Page 502
Oxoacids of nitrogen......Page 507
Oxides of phosphorus, arsenic, antimony and bismuth......Page 511
Oxoacids of phosphorus......Page 513
Oxoacids of arsenic, antimony and bismuth......Page 519
Phosphazenes......Page 520
Sulfides and selenides......Page 523
Aqueous solution chemistry and complexes......Page 524
Occurrence, extraction and uses......Page 529
Physical properties and bonding considerations......Page 531
The elements......Page 534
Hydrides......Page 540
Metal sulfides, polysulfides, polyselenides and polytellurides......Page 544
Halides, oxohalides and complex halides......Page 547
Oxides......Page 554
Oxoacids and their salts......Page 559
Compounds of sulfur and selenium with nitrogen......Page 565
Aqueous solution chemistry of sulfur, selenium and tellurium......Page 567
Introduction......Page 571
Occurrence, extraction and uses......Page 572
Physical properties and bonding considerations......Page 576
The elements......Page 579
Hydrogen halides......Page 582
Metal halides: structures and energetics......Page 583
Interhalogen compounds and polyhalogen ions......Page 584
Oxides and oxofluorides of chlorine, bromine and iodine......Page 589
Oxoacids and their salts......Page 592
Aqueous solution chemistry......Page 595
Introduction......Page 600
Occurrence, extraction and uses......Page 601
Physical properties......Page 603
Compounds of xenon......Page 604
Compounds of argon, krypton and radon......Page 611
Introduction......Page 613
Group 1: alkali metal organometallics......Page 614
Group 2 organometallics......Page 617
Group 13......Page 621
Group 14......Page 629
Group 15......Page 641
Group 16......Page 644
Ground state electronic configurations......Page 650
Physical properties......Page 651
Characteristic properties: a general perspective......Page 653
Coordination numbers and geometries......Page 658
Isomerism in d-block metal complexes......Page 666
Introduction......Page 676
Bonding in d-block metal complexes: valence bond theory......Page 677
Crystal field theory......Page 679
Molecular orbital theory: octahedral complexes......Page 687
Describing electrons in multi electronsystems......Page 693
Electronic spectra......Page 699
Evidence for metal--ligand covalent bonding......Page 708
Magnetic properties......Page 709
Thermodynamic aspects: ligand field stabilization energies (LFSE)......Page 717
Thermodynamic aspects: oxidation states in aqueous solution......Page 719
Occurrence, extraction and uses......Page 725
Group 3: scandium......Page 729
Group 4: titanium......Page 730
Group 5: vanadium......Page 734
Group 6: chromium......Page 738
Group 7: manganese......Page 746
Group 8: iron......Page 753
Group 9: cobalt......Page 761
Group 10: nickel......Page 768
Group 11: copper......Page 771
Group 12: zinc......Page 778
Occurrence, extraction and uses......Page 783
Physical properties......Page 788
Group 3: yttrium......Page 790
Group 4: zirconium and hafnium......Page 791
Group 5: niobium and tantalum......Page 793
Group 6: molybdenum and tungsten......Page 798
Group 7: technetium and rhenium......Page 808
Group 8: ruthenium and osmium......Page 813
Group 9: rhodium and iridium......Page 822
Group 10: palladium and platinum......Page 827
Group 11: silver and gold......Page 833
Group 12: cadmium and mercury......Page 839
Common types of ligand: bonding and spectroscopy......Page 845
The 18-electron rule......Page 854
Metal carbonyls: synthesis, physical properties and structure......Page 855
The isolobal principle and application of Wade’s rules......Page 860
Total valence electron counts in d-block organometallic clusters......Page 863
Types of organometallic reactions......Page 866
Metal carbonyls: selected reactions......Page 870
Metal carbonyl hydrides and halides......Page 871
Alkyl, aryl, alkene and alkyne complexes......Page 872
Allyl and buta-1,3-diene complexes......Page 876
Carbene and carbyne complexes......Page 878
Complexes containingZ5-cyclopentadienyl ligands......Page 880
Complexes containing Z6- and Z7-ligands......Page 885
Complexes containing the Z4-cyclobutadiene ligand......Page 888
Introduction......Page 893
f-Orbitals and oxidation states......Page 894
Atom and ion sizes......Page 895
Spectroscopic and magnetic properties......Page 897
Sources of the lanthanoids and actinoids......Page 899
Lanthanoid metals......Page 901
Inorganic compounds and coordination complexes of the lanthanoids......Page 902
Organometallic complexes of the lanthanoids......Page 905
The actinoid metals......Page 910
Inorganic compounds and coordination complexes of thorium, uranium and plutonium......Page 911
Organometallic complexes of thorium and uranium......Page 914
Ligand substitutions: some general points......Page 919
Substitution in square planar complexes......Page 922
Substitution and racemization in octahedral complexes......Page 927
Electron-transfer processes......Page 934
Catalysis: introductory concepts......Page 944
Homogeneous catalysis: alkene (olefin) and alkyne metathesis......Page 947
Homogeneous catalytic reduction of N2 to NH3......Page 950
Homogeneous catalysis: industrial applications......Page 951
Homogeneous catalyst development......Page 958
Heterogeneous catalysis: surfaces and interactions with adsorbates......Page 962
Heterogeneous catalysis: commercial applications......Page 964
Heterogeneous catalysis: organometallic cluster models......Page 970
Defects in solid state lattices......Page 977
Electrical conductivity in ionic solids......Page 979
Superconductivity......Page 982
Chemical vapour deposition (CVD)......Page 986
Inorganic fibres......Page 992
Carbon nanotubes......Page 996
Introduction......Page 1001
Metal storage and transport: Fe, Cu, Zn and V......Page 1002
Dealing with O2......Page 1010
Biological redox processes......Page 1017
The Zn2+ ion: Nature’s Lewis acid......Page 1028
Appendices......Page 1038
Greek letters with pronunciations......Page 1039
Abbreviations and symbols for quantities and units......Page 1040
Selected character tables......Page 1044
The electromagnetic spectrum......Page 1048
Naturally occurring isotopes and their abundances......Page 1050
Van der Waals, metallic, covalent and ionic radii......Page 1052
Pauling electronegativity values (P) for selected elements of the periodic table......Page 1054
Ground state electronic configurations of the elements and ionization energies......Page 1055
Electron affinities......Page 1058
Standard enthalpies of atomization (aHo) of the elements at 298 K......Page 1059
Selected standard reduction potentials (298 K)......Page 1060
Answers to non-descriptive problems......Page 1063
Index......Page 1081