Chemical Thermodynamics for Process Simulation

805 Pages·2019·16.687 MB·English

by  Bärbel Kolbe, Jürgen Gmehling, Jürgen Rarey, Michael Kleiber

ChemicalThermodynamicsforProcessSimulation

Chemical Thermodynamics
for Process Simulation
JürgenGmehling,MichaelKleiber,BärbelKolbe,and
JürgenRarey
Second,CompletelyRevisedandEnlargedEdition
Authors AllbookspublishedbyWiley-VCH
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v
Contents
Preface xiii
PrefacetotheSecondEdition xvii
ListofSymbols xix
AbouttheAuthors xxix
1 Introduction 1
2 PvTBehaviorofPureComponents 5
2.1 GeneralDescription 5
2.2 CaloricProperties 10
2.3 IdealGases 14
2.4 RealFluids 16
2.4.1 AuxiliaryFunctions 16
2.4.2 ResidualFunctions 17
2.4.3 FugacityandFugacityCoefficient 19
2.4.4 PhaseEquilibria 22
2.5 EquationsofState 25
2.5.1 VirialEquation 26
2.5.2 High-PrecisionEquationsofState 30
2.5.3 CubicEquationsofState 37
2.5.4 GeneralizedEquationsofStateandCorresponding-States
Principle 42
2.5.5 AdvancedCubicEquationsofState 49
Problems 57
References 60
3 CorrelationandEstimationofPureComponentProperties 63
3.1 Introduction 63
3.2 CharacteristicPhysicalPropertyConstants 63
3.2.1 CriticalData 64
3.2.2 AcentricFactor 69
3.2.3 NormalBoilingPoint 69
3.2.4 MeltingPointandEnthalpyofFusion 72
3.2.5 StandardEnthalpyandStandardGibbsEnergyofFormation 74
vi Contents
3.3 Temperature-DependentProperties 77
3.3.1 VaporPressure 78
3.3.2 LiquidDensity 90
3.3.3 EnthalpyofVaporization 94
3.3.4 IdealGasHeatCapacity 98
3.3.5 LiquidHeatCapacity 105
3.3.6 SpeedofSound 109
3.4 CorrelationandEstimationofTransportProperties 110
3.4.1 LiquidViscosity 110
3.4.2 VaporViscosity 115
3.4.3 LiquidThermalConductivity 120
3.4.4 VaporThermalConductivity 125
3.4.5 SurfaceTension 128
3.4.6 DiffusionCoefficients 131
Problems 135
References 138
4 PropertiesofMixtures 143
4.1 Introduction 143
4.2 PropertyChangesofMixing 144
4.3 PartialMolarProperties 145
4.4 Gibbs–DuhemEquation 148
4.5 IdealMixtureofIdealGases 150
4.6 IdealMixtureofRealFluids 152
4.7 ExcessProperties 153
4.8 FugacityinMixtures 154
4.8.1 FugacityofanIdealMixture 155
4.8.2 PhaseEquilibrium 155
4.9 ActivityandActivityCoefficient 156
4.10 ApplicationofEquationsofStatetoMixtures 157
4.10.1 VirialEquation 158
4.10.2 CubicEquationsofState 159
Problems 169
References 170
5 PhaseEquilibriainFluidSystems 173
5.1 Introduction 173
5.2 ThermodynamicFundamentals 185
5.3 ApplicationofActivityCoefficients 192
5.4 CalculationofVapor–LiquidEquilibriaUsinggEModels 195
5.5 FittingofgEModelParameters 212
5.5.1 CheckofVLEDataforThermodynamicConsistency 218
5.5.2 RecommendedgEModelParameters 227
5.6 CalculationofVapor–LiquidEquilibriaUsingEquationsofState 229
5.6.1 FittingofBinaryParametersofCubicEquationsofState 235
5.7 ConditionsfortheOccurrenceofAzeotropicBehavior 243
5.8 SolubilityofGasesinLiquids 252
Contents vii
5.8.1 CalculationofGasSolubilitiesUsingHenryConstants 254
5.8.2 CalculationofGasSolubilitiesUsingEquationsofState 262
5.8.3 PredictionofGasSolubilities 263
5.9 Liquid–LiquidEquilibria 266
5.9.1 TemperatureDependenceofTernaryLLE 277
5.9.2 PressureDependenceofLLE 279
5.10 PredictiveModels 280
5.10.1 RegularSolutionTheory 281
5.10.2 GroupContributionMethods 282
5.10.3 UNIFACMethod 284
5.10.3.1 ModifiedUNIFAC(Dortmund) 291
5.10.3.2 WeaknessesoftheGroupContributionMethodsUNIFACand
ModifiedUNIFAC 295
5.10.4 PredictiveSoave–Redlich–Kwong(PSRK)EquationofState 302
5.10.5 VTPRGroupContributionEquationofState 306
Problems 315
References 319
6 CaloricProperties 323
6.1 CaloricEquationsofState 323
6.1.1 InternalEnergyandEnthalpy 323
6.1.2 Entropy 326
6.1.3 HelmholtzEnergyandGibbsEnergy 327
6.2 EnthalpyDescriptioninProcessSimulationPrograms 329
6.2.1 RouteA:VaporasStartingPhase 330
6.2.2 RouteB:LiquidasStartingPhase 334
6.2.3 RouteC:EquationofState 335
6.3 CaloricPropertiesinChemicalReactions 343
Problems 349
References 350
7 ElectrolyteSolutions 351
7.1 Introduction 351
7.2 ThermodynamicsofElectrolyteSolutions 355
7.3 ActivityCoefficientModelsforElectrolyteSolutions 360
7.3.1 Debye–HückelLimitingLaw 360
7.3.2 BromleyExtension 361
7.3.3 PitzerModel 361
7.3.4 NRTLElectrolyteModelbyChen 364
7.3.5 LIQUACModel 372
7.3.6 MSAModel 380
7.4 DissociationEquilibria 381
7.5 InfluenceofSaltsontheVapor–LiquidEquilibriumBehavior 383
7.6 ComplexElectrolyteSystems 385
Problems 386
References 386
viii Contents
8 Solid–LiquidEquilibria 389
8.1 Introduction 389
8.2 ThermodynamicRelationsfortheCalculationofSolid–Liquid
Equilibria 392
8.2.1 Solid–LiquidEquilibriaofSimpleEutecticSystems 394
8.2.1.1 FreezingPointDepression 401
8.2.2 Solid–LiquidEquilibriaofSystemswithSolidSolutions 402
8.2.2.1 IdealSystems 402
8.2.2.2 Solid–LiquidEquilibriaforNonidealSystems 403
8.2.3 Solid–LiquidEquilibriawithIntermolecularCompoundFormationin
theSolidState 406
8.2.4 PressureDependenceofSolid–LiquidEquilibria 409
8.3 SaltSolubility 409
8.4 SolubilityofSolidsinSupercriticalFluids 414
Problems 416
References 419
9 MembraneProcesses 421
9.1 Osmosis 421
9.2 Pervaporation 424
Problems 425
References 426
10 PolymerThermodynamics 427
10.1 Introduction 427
10.2 gEModels 433
10.3 EquationsofState 444
10.4 InfluenceofPolydispersity 460
10.5 InfluenceofPolymerStructure 464
Problems 465
References 467
11 ApplicationsofThermodynamicsinSeparation
Technology 469
11.1 Introduction 469
11.2 VerificationofModelParametersPriortoProcess
Simulation 474
11.2.1 VerificationofPureComponentParameters 474
11.2.2 VerificationofgEModelParameters 475
11.3 InvestigationofAzeotropicPointsinMulticomponentSystems 483
11.4 ResidueCurves,DistillationBoundaries,andDistillationRegions 484
11.5 SelectionofEntrainersforAzeotropicandExtractiveDistillation 491
11.6 SelectionofSolventsforOtherSeparationProcesses 499
11.7 SelectionofSolvent-BasedSeparationProcesses 499
Problems 503
References 504