Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications

456 Pages·2016·4.789 MB·English

by  George W. Luther III

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Inorganic Chemistry for Geochemistry and
Environmental Sciences
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Inorganic Chemistry for
Geochemistry and
Environmental Sciences
Fundamentals and Applications
GEORGE W. LUTHER, III
(cid:2) School of Marine Science & Policy, (cid:2)
University of Delaware, USA
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Thiseditionfirstpublished2016
©2016JohnWiley&SonsLtd
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LibraryofCongressCataloging-in-PublicationData
Names:LutherIII,GeorgeW.
Title:Inorganicchemistryforgeochemistryandenvironmentalsciences:
fundamentalsandapplications/GeorgeW.Luther,III.
Description:Chichester,WestSussex:JohnWiley&Sons,Inc.,2016.|
Includesbibliographicalreferencesandindex.
Identifiers:LCCN2015047266|ISBN9781118851371(cloth)|ISBN9781118851401(epdf)|ISBN9781118851418(epub)
Subjects:LCSH:Chemistry,Inorganic.|Geochemistry.|
Bioinorganicchemistry.|Transitionmetals–Environmentalaspects.|
Sulfides–Environmentalaspects.|Chemicalecology.
Classification:LCCQH541.15.C44L882016|DDC577/.14–dc23LCrecordavailableathttp://lccn.loc.gov/2015047266
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
Setin9/11pt,TimesLTStdbySPiGlobal,Chennai,India.
1 2016
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ToB.J.,GregoryandStephanie
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Contents
AbouttheAuthor xv
Preface xvii
CompanionWebsite xix
1. InorganicChemistryandtheEnvironment 1
1.1 Introduction 1
1.1.1 EnergeticsofProcesses 1
1.2 Neutron–ProtonConversion 3
1.3 ElementBurningReactions – BuildupofLargerElements 4
1.4 NuclearStabilityandBindingEnergy 5
1.4.1 The“r”and“s”Processes 6
1.5 NuclearStability(RadioactiveDecay) 8
1.6 AtmosphericSynthesisofElements 8
1.7 AbundanceoftheElements 8
1.7.1 TheCosmosandtheEarth’sLithosphere 8
(cid:2) 1.7.2 ElementalAbundance(Atmosphere,Oceans,andHumanBody) 10 (cid:2)
1.8 ScopeofInorganicChemistryinGeochemistryandtheEnvironment 17
1.8.1 ElementalDistributionBasedonPhotosynthesisandChemosynthesis 17
1.8.2 StratifiedWatersandSediments – theDegradationofOrganicMatterby
AlternateElectronAcceptors 19
1.9 Summary 21
1.9.1 EnvironmentalInorganicChemistry 22
References 22
2. Oxidation–ReductionReactions(Redox) 24
2.1 Introduction 24
2.1.1 EnergeticsofHalfReactions 24
2.1.2 StandardPotentialandtheStabilityofaChemicalSpeciesofanElement 26
2.2 VariationofStandardPotentialwithpH(theNernstEquation) 29
2.3 ThermodynamicCalculationsandpHDependence 29
2.4 StabilityFieldofAqueousChemicalSpecies 31
2.5 NaturalEnvironments 32
2.6 CalculationstoPredictFavorableChemicalReactions 32
2.6.1 CouplingHalf-Reactions 34
2.6.2 One-ElectronOxygenTransformationswithFe2+ andMn2+toFormO − 35
2
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viii Contents
2.7 HighlyOxidizingConditions 38
2.7.1 OzonolysisReactions 38
2.7.2 AtmosphericRedoxReactions 39
Appendix2.1GibbsFreeEnergiesofFormation 43
References 43
3. AtomicStructure 45
3.1 History 45
3.2 TheBohrAtom 46
3.3 TheSchrodingerWaveEquation 47
3.4 ComponentsoftheWaveFunction 50
3.4.1 RadialPartoftheWaveFunction,R(r) 50
3.4.2 AngularPartoftheWavefunctionY (𝜃,𝜙)andAtomicOrbitals 54
lml
3.5 TheFourQuantumNumbers 56
3.6 ThePolyelectronicAtomsandtheFillingofOrbitalsfortheAtomsof
theElements 58
3.7 AufbauPrinciple 61
3.8 AtomicProperties 62
3.8.1 OrbitalsEnergiesandShielding 62
3.8.2 TermSymbols:CouplingofSpinandOrbitalAngularMomentum 63
3.8.3 PeriodicProperties – AtomicRadius 67
3.8.4 PeriodicProperties – IonizationPotential(IP) 67
3.8.5 PeriodicProperties – ElectronAffinity(EA) 71
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3.8.6 PeriodicProperties – Electronegativity(𝜒) 74
3.8.7 PeriodicProperties – Hardness(𝜂) 75
References 77
4. Symmetry 79
4.1 Introduction 79
4.2 SymmetryConcepts 79
4.2.1 SymmetryOperation 79
4.2.2 SymmetryElement 79
4.2.3 SymmetryElementsandOperations 80
4.3 PointGroups 84
4.3.1 SpecialGroupsandPlatonicSolids/Polyhedra 85
4.3.2 ExamplesoftheUseoftheSchemeforDeterminingPointGroups 88
4.4 OpticalIsomerismandSymmetry 92
4.4.1 Dichloro-AlleneDerivatives(C H Cl ) 92
3 2 2
4.4.2 TartaricAcid 93
4.4.3 CylindricalHelixMolecules 93
4.5 FundamentalsofGroupTheory 93
4.5.1 C PointGroup 95
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4.5.2 ExplanationoftheCharacterTable 96
4.5.3 GenerationoftheIrreducibleRepresentations(C Case) 97
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4.5.4 NotationforIrreducibleRepresentations 97
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