Electrochemistry of Metal Complexes: Applications from Electroplating to Oxide Layer Formation

306 Pages·2015·4.95 MB·English

by  Arvydas Survila

ArvydasSurvila
ElectrochemistryofMetal
Complexes
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ArvydasSurvila
Electrochemistry of Metal Complexes
ApplicationsfromElectroplatingtoOxideLayerFormation
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V
Contents
Preface IX
SymbolsandAbbreviations XIII
1 Introduction 1
1.1 EquilibriumPropertiesofComplexSystems 2
1.1.1 GeneralDefinitions 2
1.1.2 EquilibriumintheSolutionsofComplexCompounds 3
1.1.3 DistributionofComplexesandLigandsintheSolution 6
References 12
2 EquilibriumElectrodePotentials 13
2.1 ElectrodesoftheFirstKind 14
2.2 EquilibriaInvolvingIonsoftheIntermediateOxidationState 18
2.3 ElectrodesoftheSecondKind 22
2.4 Open-CircuitPotentials:ExamplesofExperimental
Investigations 25
2.4.1 SystemCu/Cu(I),CN− 25
2.4.2 SystemCu/Cu(II),β-Alanine 29
References 31
3 MassTransport 33
3.1 TwoModelsofLinearMassTransport 35
3.2 OtherCasesofDiffusionalMassTransport 39
3.3 MassTransportofChemicallyInteractingParticles 41
3.4 ConcentrationProfiles 44
3.4.1 ConcentrationProfilesinIdeallyLabileSystems 45
3.4.2 ConcentrationProfilesinSystemsofLimitedLability 52
References 58
4 PeculiaritiesofElectrochemicalProcessesInvolvingLabile
Complexes 61
4.1 Steady-StateVoltammograms 62
4.2 PotentialTransients 68
VI Contents
4.3 CurrentTransients 69
References 74
5 QuantitativeModelingofQuasi-ReversibleElectrochemicalProcesses
InvolvingLabileComplexesofMetals 75
5.1 KineticEquations 76
5.2 EmploymentofVoltammetricData 80
5.2.1 TafelPlotsNormalizedwithRespecttotheSurfaceConcentrationof
EAC 80
5.2.2 AnalysisofLPSCurrentMaxima 83
5.3 TechniquesBasedontheControloftheIntensityofForced
Convection 85
5.3.1 IsosurfaceConcentrationVoltammetry 85
5.3.2 DeterminationoftheExchangeCurrentDensityfromPolarization
Resistance 86
5.3.3 ElectrochemicalImpedanceSpectroscopy(EIS)underForced
ConvectionConditions 89
References 93
6 DeterminationofMechanismofElectrochemicalProcessesInvolving
MetalComplexes 97
6.1 DeterminationoftheMechanismbyReactionOrders 98
6.2 MethodofIsopotentialSolutions 100
References 102
7 Adsorption 105
7.1 ThermodynamicAspects 106
7.2 ModelAspects 108
References 112
8 ElectrochemicalProcessesinRealSystems 115
8.1 ExperimentalDetails 115
8.2 CyanideSystems 116
8.2.1 SystemCu|Cu(I),CN− 117
8.2.2 SystemAg|Ag(I),CN− 119
8.2.3 SystemAu|Au(I),CN− 125
8.3 EcologicalSystemsContainingHydroxyAcids 131
8.3.1 ElectroreductionofCu(II)Complexes 132
8.3.2 ElectroreductionofSn(II)Complexes 151
8.3.3 ElectroreductionofZn(II)Complexes 170
Appendix 174
References 174
9 ElectrochemicalDepositionofAlloys 183
9.1 MassTransportduringtheCodepositionofMetals 184
Contents VII
9.2 CodepositionofCobaltandTin 185
9.3 DepositionofBrassCoatings 194
9.4 DepositionofBronzeCoatings 205
9.4.1 SurfaceActivityofPolyethersonCopperandTinSubstrates 206
9.4.2 EffectofHalides.FormationofSurfaceComplexes 211
9.4.3 EffectofLengthoftheHydrocarbonChain 214
9.4.4 CodepositionofCopperandTin 217
9.4.5 RelatedPhenomena:CurrentOscillations 223
9.5 CodepositionofCobaltandMolybdenum 227
References 234
10 SpontaneousFormationofPhotosensitiveCuprousOxideLayers 241
10.1 TwoMechanismsofCu OFormation 242
2
10.2 CompositionofOxideLayers 243
10.3 KineticsofCu OFormation 244
2
10.4 ElectrochemicalReductionofOxideLayers 246
10.5 PhotoelectrochemicalPropertiesofOxideLayers 251
10.6 PhotoelectrochemicalStabilityofOxideLayers 255
10.7 InfluenceofOxideLayersonKineticsofCu(II)Reduction 258
References 263
11 HydrogenEvaluationInvolvingLigandsasProtonDonors 267
References 276
ConcludingRemarks 277
Index 283