Hydrolysis of metal ions

945 Pages·2016·18.113 MB·English

by  Paul L. Brown, Christian Ekberg

PaulL.Brown
ChristianEkberg
HydrolysisofMetalIons
Volume1
PaulL.Brown
ChristianEkberg
HydrolysisofMetalIons
Volume2

PaulL.Brown
ChristianEkberg
Hydrolysis of Metal Ions
Volume1
PaulL.Brown
ChristianEkberg
Hydrolysis of Metal Ions
Volume2
Authors AllbookspublishedbyWiley-VCHare
carefullyproduced.Nevertheless,authors,
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Dr.PaulL.Brown
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GeochemAustralia
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Readersareadvisedtokeepinmindthat
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Prof.ChristianEkberg inaccurate.
ChalmersUniversityofTechnology
NuclearChemistry/IndustrialMaterials
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V
Contents
Volume1
Preface XIII
1 Introduction 1
References 4
2 Theory 7
2.1 HydrolysisReactionsandStability/SolubilityConstants 7
2.2 Debye–HückelTheory 9
2.3 OsmoticCoefficient 12
2.4 SpecificIonInteractionTheory 14
2.5 DeterminationofTemperature-DependentParameters 17
2.6 DeterminationofIonInteractionParametersfromActivity
andOsmoticCoefficientData 18
2.7 DeterminationofIonInteractionParametersforKOH
∘
atTemperaturesOtherthan25 C 22
2.8 ActivityofWater 23
2.9 EnthalpyandEntropy 24
2.10 EstimationofStabilityandSolubilityConstants 26
References 28
3 MethodologiesforDeterminingStability/SolubilityConstants 31
3.1 Introduction 31
3.2 Potentiometry 31
3.2.1 ConsiderationsandLimitations 37
3.3 Liquid–LiquidExtraction 37
3.3.1 ConsiderationsandLimitations 41
3.4 Solid–LiquidExtraction 42
3.4.1 ConsiderationsandLimitations 43
3.5 Solubility 44
3.5.1 ConsiderationsandLimitations 45
VI Contents
3.6 Spectrophotometry 46
3.6.1 ConsiderationsandLimitations 48
3.7 ExperimentalUncertainties 49
3.7.1 UncertaintiesinDataPoints 49
3.7.2 UncertaintiesinFittedParameters 51
3.7.3 Correlations 52
References 53
4 StatisticalAnalysisandSelectionCriteria 55
4.1 UncertaintyAssessment 55
4.1.1 UncertaintyAssignmentBasedonNumberofAvailableData 55
4.1.2 PropagationofUncertainties 56
4.2 SelectionofStabilityandSolubilityConstants 57
References 60
5 Water 61
5.1 PhysicalPropertiesofWater 61
5.2 ProtolysisofWateratZeroIonicStrength 65
∘
5.3 ProtolysisofWaterinMediaofFixedIonicStrengthat25 C 68
5.4 ProtolysisofWaterinMediaofFixedIonicStrengthatOther
Temperatures 72
5.5 Enthalpy,EntropyandHeatCapacity 73
5.6 CollationandAssessmentofLiteratureData 77
5.6.1 ZeroIonicStrength 77
5.6.2 IonicStrengthDependence 86
5.6.2.1 CesiumChloride 86
5.6.2.2 TetramethylammoniumChloride 89
5.6.2.3 SodiumChloride 89
5.6.2.4 PotassiumChloride 102
5.6.2.5 LithiumChloride 107
5.6.2.6 BariumChloride 111
5.6.2.7 SodiumPerchlorate 113
5.6.2.8 LithiumPerchlorate 115
5.6.2.9 PotassiumIodide 118
5.6.2.10 PotassiumNitrate 118
5.6.2.11 SodiumNitrate 119
5.6.2.12 SodiumTriflate 122
5.6.2.13 SodiumSulfate 126
5.7 ZeroIonicStrengthDataatHighPressure 128
5.8 ComparativeStrengthoftheProtolysisConstantofWater 128
References 130
6 AlkaliMetals 135
6.1 Introduction 135
6.2 Lithium 136