Principles of Inorganic Chemistry

763 Pages·2015·59.97 MB·English

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PRINCIPLES OF
INORGANIC
CHEMISTRY
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PRINCIPLES OF
INORGANIC
CHEMISTRY
Brian W. Pfennig
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Copyright©2015byJohnWiley&Sons,Inc.Allrightsreserved
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LibraryofCongressCataloging-in-PublicationData:
Pfennig,BrianWilliam.
Principlesofinorganicchemistry/BrianW.Pfennig.
pagescm
Includesbibliographicalreferencesandindex.
ISBN978-1-118-85910-0(cloth)
1. Chemistry,Inorganic–Textbooks.2. Chemistry,Inorganic–Studyandteaching(Higher)3. Chemistry,
Inorganic–Studyandteaching(Graduate)I.Title.
QD151.3.P462015
546–dc23
2014043250
Coverimage:Courtesyoftheauthor
Typesetin10/12ptGillSansbyLaserwordsPrivateLimited,Chennai,India.
PrintedintheUnitedStatesofAmerica
10987654321
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1 2015
Contents
Preface xi
Acknowledgements xv
Chapter1 | TheCompositionofMatter 1
1.1 EarlyDescriptionsofMatter 1
1.2 VisualizingAtoms 6
1.3 ThePeriodicTable 8
1.4 TheStandardModel 9
Exercises 12
Bibliography 13
Chapter2 | TheStructureoftheNucleus 15
2.1 TheNucleus 15
2.2 NuclearBindingEnergies 16
2.3 NuclearReactions:FusionandFission 17
2.4 RadioactiveDecayandtheBandofStability 22
2.5 TheShellModeloftheNucleus 27
2.6 TheOriginoftheElements 30
Exercises 38
Bibliography 39
Chapter3 | ABriefReviewofQuantumTheory 41
3.1 TheWavelikePropertiesofLight 41
3.2 ProblemswiththeClassicalModeloftheAtom 48
3.3 TheBohrModeloftheAtom 55
3.4 ImplicationsofWave-ParticleDuality 58
3.5 PostulatesofQuantumMechanics 64
3.6 TheSchrödingerEquation 67
3.7 TheParticleinaBoxProblem 70
3.8 TheHarmonicOscillatorProblem 75
Exercises 78
Bibliography 79
Chapter4 | AtomicStructure 81
4.1 TheHydrogenAtom 81
4.1.1 TheRadialWaveFunctions 82
4.1.2 TheAngularWaveFunctions 86
4.2 PolyelectronicAtoms 91
4.3 ElectronSpinandthePauliPrinciple 93
4.4 ElectronConfigurationsandthePeriodicTable 96
4.5 AtomicTermSymbols 98
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vi CONTENTS
4.5.1 ExtractingTermSymbolsUsingRussell–SaundersCoupling 100
4.5.2 ExtractingTermSymbolsUsingjjCoupling 102
4.5.3 CorrelationBetweenRS(LS)CouplingandjjCoupling 104
4.6 ShieldingandEffectiveNuclearCharge 105
Exercises 107
Bibliography 108
Chapter5 | PeriodicPropertiesoftheElements 109
5.1 TheModernPeriodicTable 109
5.2 Radius 111
5.3 IonizationEnergy 118
5.4 ElectronAffinity 121
5.5 TheUniquenessPrinciple 122
5.6 DiagonalProperties 124
5.7 TheMetal–NonmetalLine 125
5.8 StandardReductionPotentials 126
5.9 TheInert-PairEffect 129
5.10 RelativisticEffects 130
5.11 Electronegativity 133
Exercises 136
Bibliography 137
Chapter6 | AnIntroductiontoChemicalBonding 139
6.1 TheBondinginMolecularHydrogen 139
6.2 LewisStructures 140
6.3 CovalentBondLengthsandBondDissociationEnergies 144
6.4 Resonance 146
6.5 PolarCovalentBonding 149
Exercises 153
Bibliography 154
Chapter7 | MolecularGeometry 155
7.1 TheVSEPRModel 155
7.2 TheLigandClose-PackingModel 170
7.3 AComparisonoftheVSEPRandLCPModels 175
Exercises 176
Bibliography 177
Chapter8 | MolecularSymmetry 179
8.1 SymmetryElementsandSymmetryOperations 179
8.1.1 Identity,E 180
8.1.2 ProperRotation,C 181
n
8.1.3 Reflection,𝜎 182
8.1.4 Inversion,i 183
8.1.5 ImproperRotation,S 183
n
8.2 SymmetryGroups 186
8.3 MolecularPointGroups 191
8.4 Representations 195
8.5 CharacterTables 202
8.6 DirectProducts 209
8.7 ReducibleRepresentations 214
Exercises 222
Bibliography 224
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CONTENTS vii
Chapter9 | VibrationalSpectroscopy 227
9.1 OverviewofVibrationalSpectroscopy 227
9.2 SelectionRulesforIRandRaman-ActiveVibrationalModes 231
9.3 DeterminingtheSymmetriesoftheNormalModesofVibration 235
9.4 GeneratingSymmetryCoordinatesUsingtheProjectionOperatorMethod 243
9.5 ResonanceRamanSpectroscopy 252
Exercises 256
Bibliography 258
Chapter10 |CovalentBonding 259
10.1 ValenceBondTheory 259
10.2 MolecularOrbitalTheory:Diatomics 278
10.3 MolecularOrbitalTheory:Polyatomics 292
10.4 MolecularOrbitalTheory:piOrbitals 305
10.5 MolecularOrbitalTheory:MoreComplexExamples 317
10.6 BoraneandCarboraneClusterCompounds 325
Exercises 334
Bibliography 336
Chapter11 |MetallicBonding 339
11.1 CrystallineLattices 339
11.2 X-RayDiffraction 345
11.3 Closest-PackedStructures 350
11.4 TheFreeElectronModelofMetallicBonding 355
11.5 BandTheoryofSolids 360
11.6 ConductivityinSolids 374
11.7 ConnectionsBetweenSolidsandDiscreteMolecules 383
Exercises 384
Bibliography 388
Chapter12 |IonicBonding 391
12.1 CommonTypesofIonicSolids 391
12.2 LatticeEnthalpiesandtheBorn–HaberCycle 398
12.3 IonicRadiiandPauling’sRules 404
12.4 TheSilicates 417
12.5 Zeolites 422
12.6 DefectsinCrystals 423
Exercises 426
Bibliography 428
Chapter13 |StructureandBonding 431
13.1 AReexaminationofCrystallineSolids 431
13.2 IntermediateTypesofBondinginSolids 434
13.3 QuantumTheoryofAtomsinMolecules(QTAIM) 443
Exercises 449
Bibliography 452
Chapter14 |StructureandReactivity 453
14.1 AnOverviewofChemicalReactivity 453
14.2 Acid–BaseReactions 455
14.3 FrontierMolecularOrbitalTheory 467
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viii CONTENTS
14.4 Oxidation–ReductionReactions 473
14.5 AGeneralizedViewofMolecularReactivity 475
Exercises 480
Bibliography 481
Chapter15 |AnIntroductiontoCoordinationCompounds 483
15.1 AHistoricalOverviewofCoordinationChemistry 483
15.2 TypesofLigandsandNomenclature 487
15.3 StabilityConstants 490
15.4 CoordinationNumbersandGeometries 492
15.5 Isomerism 498
15.6 TheMagneticPropertiesofCoordinationCompounds 501
Exercises 506
Bibliography 508
Chapter16 |Structure,Bonding,andSpectroscopyofCoordinationCompounds 509
16.1 ValenceBondModel 509
16.2 CrystalFieldTheory 512
16.3 LigandFieldTheory 525
16.4 TheAngularOverlapMethod 534
16.5 MolecularTermSymbols 541
16.5.1 Scenario1—AlltheOrbitalsareCompletelyOccupied 546
16.5.2 Scenario2—ThereisaSingleUnpairedElectroninOneoftheOrbitals 546
16.5.3 Scenario3—ThereareTwoUnpairedElectronsinTwoDifferentOrbitals 546
16.5.4 Scenario4—ADegenerateOrbitalisLackingaSingleElectron 547
16.5.5 Scenario5—ThereareTwoElectronsinaDegenerateOrbital 547
16.5.6 Scenario6—ThereareThreeElectronsinaTriplyDegenerateOrbital 547
16.6 Tanabe–SuganoDiagrams 549
16.7 ElectronicSpectroscopyofCoordinationCompounds 554
16.8 TheJahn–TellerEffect 564
Exercises 566
Bibliography 570
Chapter17 |ReactionsofCoordinationCompounds 573
17.1 KineticsOverview 573
17.2 OctahedralSubstitutionReactions 577
17.2.1 Associative(A)Mechanism 578
17.2.2 Interchange(I)Mechanism 579
17.2.3 Dissociative(D)Mechanism 580
17.3 SquarePlanarSubstitutionReactions 585
17.4 ElectronTransferReactions 593
17.5 InorganicPhotochemistry 606
17.5.1 PhotochemistryofChromium(III)AmmineCompounds 607
17.5.2 Light-InducedExcitedStateSpinTrappinginIron(II)Compounds 611
17.5.3 MLCTPhotochemistryinPentaammineruthenium(II)Compounds 615
17.5.4 PhotochemistryandPhotophysicsofRuthenium(II)PolypyridylCompounds 617
Exercises 622
Bibliography 624
Chapter18 |StructureandBondinginOrganometallicCompounds 627
18.1 IntroductiontoOrganometallicChemistry 627
18.2 ElectronCountingandthe18-ElectronRule 628
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