Inorganic Chemistry This page intentionally left blank Inorganic Chemistry Second Edition James E. House Illinois Wesleyan University and Illinois State University AMSTERDAM(cid:1)BOSTON(cid:1)HEIDELBERG(cid:1)LONDON(cid:1)NEWYORK(cid:1)OXFORD PARIS(cid:1)SANDIEGO(cid:1)SANFRANCISCO(cid:1)SINGAPORE(cid:1)SYDNEY(cid:1)TOKYO AcademicPressisImprintofElsevier Elsevier 225WymanStreet,Waltham,MA02451,USA TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UK Firstedition2008 Secondedition2013 Copyright(cid:1)2013,2008ElsevierInc.Allrightsreserved. Nopartofthispublicationmaybereproduced,storedinaretrievalsystemortransmittedinanyformorby anymeanselectronic,mechanical,photocopying,recordingorotherwisewithoutthepriorwrittenpermission ofthepublisher PermissionsmaybesoughtdirectlyfromElsevier’sScience&TechnologyRightsDepartmentinOxford, UK:phone(+44)(0)1865843830;fax(+44)(0)1865853333;email:[email protected] youcansubmityourrequestonlinebyvisitingtheElsevierwebsiteathttp://elsevier.com/locate/permissions, andselectingObtainingpermissiontouseElseviermaterial Notice Noresponsibilityisassumedbythepublisherforanyinjuryand/ordamagetopersonsorpropertyasamatter ofproductsliability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products,instructions orideascontainedinthematerialherein.Becauseofrapidadvancesinthemedicalsciences,inparticular, independentverificationofdiagnosesanddrugdosagesshouldbemade LibraryofCongressCataloging-in-PublicationData AcatalogrecordforthisbookisavailablefromtheLibraryofCongress LibraryofCongressCataloging-in-PublicationData House,J.E. Inorganicchemistry/JamesHouse.e2nded. p.cm. Includesbibliographicalreferencesandindex. 1.Chemistry,InorganiceTextbooks.I.Title. QD151.5.H682013 546–dc23 2012017867 ISBN:978-0-12-385110-9 ForinformationonallElsevierpublications visitourwebsiteatwww.store.elsevier.com PrintedandboundinChina 1213 111098765432 Contents PREFACE TO THE SECOND EDITION............................................................................................xi PREFACE TO THE FIRSTEDITION................................................................................................xii PART 1 Structure of Atoms and Molecules.......................................................1 CHAPTER 1 Light,Electrons, andNuclei......................................................................................3 1.1 SomeEarlyExperimentsinAtomicPhysics...................................................................3 1.2 TheNatureofLight...........................................................................................................7 1.3 TheBohrModel................................................................................................................11 1.4 ParticleeWaveDuality.....................................................................................................14 1.5 ElectronicPropertiesofAtoms.......................................................................................16 1.6 NuclearBindingEnergy..................................................................................................21 1.7 NuclearStability...............................................................................................................23 1.8 TypesofNuclearDecay..................................................................................................25 1.9 PredictingDecayModes.................................................................................................28 CHAPTER 2 Basic Quantum Mechanicsand Atomic Structure................................................33 2.1 ThePostulates..................................................................................................................33 2.2 TheHydrogenAtom........................................................................................................40 2.3 TheHeliumAtom.............................................................................................................45 2.4 SlaterWaveFunctions.....................................................................................................47 2.5 ElectronConfigurations..................................................................................................49 2.6 SpectroscopicStates........................................................................................................54 CHAPTER 3 Covalent BondinginDiatomic Molecules..............................................................61 3.1 TheBasicIdeasofMolecularOrbitalMethods............................................................61 3.2 TheHþ andH Molecules...............................................................................................69 2 2 3.3 DiatomicMoleculesofSecond-RowElements..............................................................71 3.4 PhotoelectronSpectroscopy............................................................................................77 3.5 HeteronuclearDiatomicMolecules................................................................................79 3.6 Electronegativity..............................................................................................................82 3.7 SpectroscopicStatesforMolecules................................................................................85 v vi Contents CHAPTER 4 ASurvey ofInorganic Structures andBonding.....................................................89 4.1 StructuresofMoleculesHavingSingleBonds..............................................................89 4.2 ResonanceandFormalCharge......................................................................................99 4.3 ComplexStructures:APreviewofComingAttractions...........................................111 4.4 Electron-DeficientMolecules........................................................................................119 4.5 StructuresHavingUnsaturatedRings.........................................................................121 4.6 BondEnergies................................................................................................................123 CHAPTER 5 Symmetry and Molecular Orbitals........................................................................129 5.1 SymmetryElements.......................................................................................................129 5.2 OrbitalSymmetry...........................................................................................................137 5.3 ABriefLookatGroupTheory......................................................................................139 5.4 ConstructionofMolecularOrbitals..............................................................................144 5.5 OrbitalsandAngles.......................................................................................................150 5.6 SimpleCalculationsUsingtheHückelMethod..........................................................152 PART 2 Condensed Phases...............................................................................167 CHAPTER 6 Dipole Momentsand Intermolecular Interactions...............................................169 6.1 DipoleMoments.............................................................................................................169 6.2 DipoleeDipoleForces....................................................................................................174 6.3 Dipole-InducedDipoleForces.......................................................................................176 6.4 London(Dispersion)Forces..........................................................................................177 6.5 ThevanderWaalsEquation........................................................................................181 6.6 HydrogenBonding.........................................................................................................183 6.7 CohesionEnergyandSolubilityParameters..............................................................192 6.8 Solvatochromism............................................................................................................196 CHAPTER 7 Ionic Bondingand Structures of Solids................................................................201 7.1 EnergeticsofCrystalFormation................................................................................201 7.2 MadelungConstants...................................................................................................205 7.3 TheKapustinskiiEquation.........................................................................................209 7.4 IonicSizesandCrystalEnvironments.......................................................................210 7.5 CrystalStructures........................................................................................................213 7.6 SolubilityofIonicCompounds....................................................................................219 7.7 ProtonandElectronAffinities....................................................................................224 7.8 StructuresofMetals.....................................................................................................227 7.9 DefectsinCrystals.......................................................................................................230 7.10 PhaseTransitionsinSolids.........................................................................................233 7.11 HeatCapacity...............................................................................................................234 7.12 HardnessofSolids.......................................................................................................237 Contents vii CHAPTER 8 Dynamic Processesin InorganicSolids................................................................243 8.1 CharacteristicsofSolid-StateReactions....................................................................243 8.2 KineticModelsforReactionsinSolids......................................................................245 8.3 ThermalMethodsofAnalysis....................................................................................253 8.4 EffectsofPressure.......................................................................................................254 8.5 ReactionsinSomeSolidInorganicCompounds.......................................................256 8.6 PhaseTransitions........................................................................................................258 8.7 ReactionsatInterfaces................................................................................................262 8.8 DiffusioninSolids........................................................................................................263 8.9 Sintering........................................................................................................................265 8.10 DriftandConductivity.................................................................................................267 PART 3 Acids, Bases, and Solvents ................................................................271 CHAPTER 9 AcideBase Chemistry............................................................................................273 9.1 ArrheniusTheory.........................................................................................................273 9.2 BrønstedeLowryTheory.............................................................................................276 9.3 FactorsAffectingtheStrengthofAcidsandBases.................................................279 9.4 AcideBaseCharacterofOxides.................................................................................284 9.5 ProtonAffinities...........................................................................................................286 9.6 LewisTheory................................................................................................................288 9.7 CatalyticBehaviorofAcidsandBases......................................................................292 9.8 TheHardeSoftInteractionPrinciple(HSIP)..............................................................296 9.9 ElectronicPolarizabilities............................................................................................305 9.10 TheDragoFour-ParameterEquation.........................................................................306 CHAPTER 10 Chemistry inNonaqueous Solvents....................................................................313 10.1 SomeCommonNonaqueousSolvents.....................................................................313 10.2 TheSolventConcept.................................................................................................314 10.3 AmphotericBehavior.................................................................................................316 10.4 TheCoordinationModel...........................................................................................317 10.5 ChemistryinLiquidAmmonia.................................................................................318 10.6 LiquidHydrogenFluoride.........................................................................................324 10.7 LiquidSulfurDioxide.................................................................................................326 10.8 Superacids..................................................................................................................330 PART 4 Chemistry of the Elements................................................................335 CHAPTER 11 Chemistry of Metallic Elements..........................................................................337 11.1 TheMetallicElements............................................................................................337 11.2 BandTheory.............................................................................................................338 viii Contents 11.3 GroupsIAandIIAMetals.......................................................................................341 11.4 ZintlPhases..............................................................................................................349 11.5 AluminumandBeryllium........................................................................................351 11.6 TheFirst-RowTransitionMetals...........................................................................353 11.7 Second-andThird-RowTransitionMetals...........................................................355 11.8 Alloys.........................................................................................................................357 11.9 ChemistryofTransitionMetals.............................................................................360 11.10 TheLanthanides......................................................................................................367 CHAPTER 12 Organometallic Compounds ofthe Main Group Elements..............................375 12.1 PreparationofOrganometallicCompounds...........................................................376 12.2 OrganometallicCompoundsofGroupIAMetals...................................................378 12.3 OrganometallicCompoundsofGroupIIAMetals..................................................380 12.4 OrganometallicCompoundsofGroupIIIAMetals................................................383 12.5 OrganometallicCompoundsofGroupIVAMetals................................................387 12.6 OrganometallicCompoundsofGroupVAElements.............................................388 12.7 OrganometallicCompoundsofZn,Cd,andHg.....................................................389 CHAPTER 13 Chemistry of Nonmetallic Elements I.Hydrogen, Boron, Oxygen, and Carbon....................................................................................................................393 13.1 Hydrogen....................................................................................................................393 13.2 Boron...........................................................................................................................400 13.3 Oxygen........................................................................................................................411 13.4 Carbon.........................................................................................................................420 CHAPTER 14 Chemistry of Nonmetallic Elements II. Groups IVAand VA...........................439 14.1 TheGroupIVAElements..........................................................................................439 14.2 Nitrogen......................................................................................................................456 14.3 Phosphorus,Arsenic,Antimony,andBismuth......................................................471 CHAPTER 15 Chemistry of Nonmetallic Elements III. Groups VIAeVIIIA............................499 15.1 Sulfur,Selenium,andTellurium...............................................................................499 15.2 TheHalogens.............................................................................................................520 15.3 TheNobleGases........................................................................................................538 PART 5 Chemistry of Coordination Compounds..........................................551 CHAPTER 16 Introduction to Coordination Chemistry............................................................553 16.1 StructuresofCoordinationCompounds................................................................553 16.2 MetaleLigandBonds...............................................................................................557 16.3 NamingCoordinationCompounds........................................................................559 16.4 Isomerism.................................................................................................................561 16.5 ASimpleValenceBondDescriptionofCoordinateBonds.................................568
Description: