Chemical Thermodynamics for Process Simulation

Jürgen Gmehling, PhD, is Professor of Chemical Engineering at the University of Oldenburg, Germany. He is also president and CEO of DDBST GmbH, Oldenburg, as well as cofounder of LTP GmbH, part of the Carl von Ossietzky University of Oldenburg. Michael Kleiber, PhD, works as a Chief Development Engineer for ThyssenKrupp Uhde, Germany. Bärbel Kolbe, PhD, is a senior process engineer for ThyssenKrupp Uhde, Germany. Jürgen Rarey, PhD, is a professor at the University of Oldenburg, Germany, and cofounded DDBST GmbH, Oldenburg. He is also an honorary professor in Durban, South Africa.

• Preface xiiiPreface to the Second Edition xviiList of Symbols xixAbout the Authors xxix1 Introduction 12 PvT Behavior of Pure Components 52.1 General Description 52.2 Caloric Properties 102.3 Ideal Gases 142.4 Real Fluids 162.4.1 Auxiliary Functions 162.4.2 Residual Functions 172.4.3 Fugacity and Fugacity Coefficient 192.4.4 Phase Equilibria 222.5 Equations of State 252.5.1 Virial Equation 262.5.2 High-Precision Equations of State 302.5.3 Cubic Equations of State 372.5.4 Generalized Equations of State and Corresponding-States Principle 422.5.5 Advanced Cubic Equations of State 49Problems 57References 603 Correlation and Estimation of Pure Component Properties 633.1 Introduction 633.2 Characteristic Physical Property Constants 633.2.1 Critical Data 643.2.2 Acentric Factor 693.2.3 Normal Boiling Point 693.2.4 Melting Point and Enthalpy of Fusion 723.2.5 Standard Enthalpy and Standard Gibbs Energy of Formation 743.3 Temperature-Dependent Properties 773.3.1 Vapor Pressure 783.3.2 Liquid Density 903.3.3 Enthalpy of Vaporization 943.3.4 Ideal Gas Heat Capacity 983.3.5 Liquid Heat Capacity 1053.3.6 Speed of Sound 1093.4 Correlation and Estimation of Transport Properties 1103.4.1 Liquid Viscosity 1103.4.2 Vapor Viscosity 1153.4.3 Liquid Thermal Conductivity 1203.4.4 Vapor Thermal Conductivity 1253.4.5 Surface Tension 1283.4.6 Diffusion Coefficients 131Problems 135References 1384 Properties of Mixtures 1434.1 Introduction 1434.2 Property Changes of Mixing 1444.3 Partial Molar Properties 1454.4 Gibbs–Duhem Equation 1484.5 Ideal Mixture of Ideal Gases 1504.6 Ideal Mixture of Real Fluids 1524.7 Excess Properties 1534.8 Fugacity in Mixtures 1544.8.1 Fugacity of an Ideal Mixture 1554.8.2 Phase Equilibrium 1554.9 Activity and Activity Coefficient 1564.10 Application of Equations of State to Mixtures 1574.10.1 Virial Equation 1584.10.2 Cubic Equations of State 159Problems 169References 1705 Phase Equilibria in Fluid Systems 1735.1 Introduction 1735.2 Thermodynamic Fundamentals 1855.3 Application of Activity Coefficients 1925.4 Calculation of Vapor–Liquid Equilibria Using gE Models 1955.5 Fitting of gE Model Parameters 2125.5.1 Check of VLE Data for Thermodynamic Consistency 2185.5.2 Recommended gE Model Parameters 2275.6 Calculation of Vapor–Liquid Equilibria Using Equations of State 2295.6.1 Fitting of Binary Parameters of Cubic Equations of State 2355.7 Conditions for the Occurrence of Azeotropic Behavior 2435.8 Solubility of Gases in Liquids 2525.8.1 Calculation of Gas Solubilities Using Henry Constants 2545.8.2 Calculation of Gas Solubilities Using Equations of State 2625.8.3 Prediction of Gas Solubilities 2635.9 Liquid–Liquid Equilibria 2665.9.1 Temperature Dependence of Ternary LLE 2775.9.2 Pressure Dependence of LLE 2795.10 Predictive Models 2805.10.1 Regular Solution Theory 2815.10.2 Group Contribution Methods 2825.10.3 UNIFAC Method 2845.10.3.1 Modified UNIFAC (Dortmund) 2915.10.3.2 Weaknesses of the Group Contribution Methods UNIFAC and Modified UNIFAC 2955.10.4 Predictive Soave–Redlich–Kwong (PSRK) Equation of State 3025.10.5 VTPR Group Contribution Equation of State 306Problems 315References 3196 Caloric Properties 3236.1 Caloric Equations of State 3236.1.1 Internal Energy and Enthalpy 3236.1.2 Entropy 3266.1.3 Helmholtz Energy and Gibbs Energy 3276.2 Enthalpy Description in Process Simulation Programs 3296.2.1 Route A: Vapor as Starting Phase 3306.2.2 Route B: Liquid as Starting Phase 3346.2.3 Route C: Equation of State 3356.3 Caloric Properties in Chemical Reactions 343Problems 349References 3507 Electrolyte Solutions 3517.1 Introduction 3517.2 Thermodynamics of Electrolyte Solutions 3557.3 Activity Coefficient Models for Electrolyte Solutions 3607.3.1 Debye–Hückel Limiting Law 3607.3.2 Bromley Extension 3617.3.3 Pitzer Model 3617.3.4 NRTL Electrolyte Model by Chen 3647.3.5 LIQUAC Model 3727.3.6 MSA Model 3807.4 Dissociation Equilibria 3817.5 Influence of Salts on the Vapor–Liquid Equilibrium Behavior 3837.6 Complex Electrolyte Systems 385Problems 386References 3868 Solid–Liquid Equilibria 3898.1 Introduction 3898.2 Thermodynamic Relations for the Calculation of Solid–Liquid Equilibria 3928.2.1 Solid–Liquid Equilibria of Simple Eutectic Systems 3948.2.1.1 Freezing Point Depression 4018.2.2 Solid–Liquid Equilibria of Systems with Solid Solutions 4028.2.2.1 Ideal Systems 4028.2.2.2 Solid–Liquid Equilibria for Nonideal Systems 4038.2.3 Solid–Liquid Equilibria with Intermolecular Compound Formation in the Solid State 4068.2.4 Pressure Dependence of Solid–Liquid Equilibria 4098.3 Salt Solubility 4098.4 Solubility of Solids in Supercritical Fluids 414Problems 416References 4199 Membrane Processes 4219.1 Osmosis 4219.2 Pervaporation 424Problems 425References 42610 Polymer Thermodynamics 42710.1 Introduction 42710.2 gE Models 43310.3 Equations of State 44410.4 Influence of Polydispersity 46010.5 Influence of Polymer Structure 464Problems 465References 46711 Applications of Thermodynamics in Separation Technology 46911.1 Introduction 46911.2 Verification of Model Parameters Prior to Process Simulation 47411.2.1 Verification of Pure Component Parameters 47411.2.2 Verification of gE Model Parameters 47511.3 Investigation of Azeotropic Points in Multicomponent Systems 48311.4 Residue Curves, Distillation Boundaries, and Distillation Regions 48411.5 Selection of Entrainers for Azeotropic and Extractive Distillation 49111.6 Selection of Solvents for Other Separation Processes 49911.7 Selection of Solvent-Based Separation Processes 499Problems 503References 50412 Enthalpy of Reaction and Chemical Equilibria 50512.1 Introduction 50512.2 Enthalpy of Reaction 50612.2.1 Temperature Dependence 50712.2.2 Consideration of the Real Gas Behavior on the Enthalpy of Reaction 50912.3 Chemical Equilibrium 51112.4 Multiple Chemical Reaction Equilibria 53012.4.1 Relaxation Method 53112.4.2 Gibbs Energy Minimization 535Problems 544References 54713 Examples for Complex Systems 54913.1 Introduction 54913.2 Formaldehyde Solutions 54913.3 Vapor Phase Association 555Problems 568References 57014 Practical Applications 57314.1 Introduction 57314.2 Flash 57314.3 Joule–Thomson Effect 57514.4 Adiabatic Compression and Expansion 57714.5 Pressure Relief 58114.6 Limitations of Equilibrium Thermodynamics 586Problems 589References 59115 Experimental Determination of Pure Component and Mixture Properties 59315.1 Introduction 59315.2 Pure Component Vapor Pressure and Boiling Temperature 59415.3 Enthalpy of Vaporization 59815.4 Critical Data 59915.5 Vapor–Liquid Equilibria 59915.5.1 Dynamic VLE Stills 60115.5.2 Static Techniques 60415.5.3 Degassing 61115.5.4 Headspace Gas Chromatography (HSGC) 61315.5.5 High-Pressure VLE 61415.5.6 Inline True Component Analysis in Reactive Mixtures 61615.6 Activity Coefficients at Infinite Dilution 61715.6.1 Gas Chromatographic Retention Time Measurement 61815.6.2 Inert Gas Stripping (Dilutor) 62015.6.3 Limiting Activity Coefficients of High Boilers in Low Boilers 62215.7 Liquid–Liquid Equilibria (LLE) 62215.8 Gas Solubility 62315.9 Excess Enthalpy 624Problems 626References 62616 Introduction to the Collection of Example Problems 63116.1 Introduction 63116.2 Mathcad Examples 63116.3 Examples Using the Dortmund Data Bank (DDB) and the Integrated Software Package DDBSP 63316.4 Examples Using Microsoft Excel and Microsoft Office VBA 634Appendix A Pure Component Parameters 635Appendix B Coefficients for High-Precision Equations of State 663References 668Appendix C Useful Derivations 669A1 Relationship Between (;;s/;;T)P and (;;s/;;T)v 670A2 Expressions for (;;u/;;v)T and (;;s/;;v)T 670A3 cP and cv as Derivatives of the Specific Entropy 671A4 Relationship Between cP and cv 672A5 Expression for (;;h/;;P)T 673A6 Expression for (;;s/;;P)T 674A7 Expression for [;;(g/RT)/;;T]P and van’t Hoff Equation 674A8 General Expression for cv 675A9 Expression for (;;P/;;v)T 676A10 Cardano’s Formula 676B1 Derivation of the Kelvin Equation 677B2 Equivalence of Chemical Potential μ and Gibbs Energy g for a Pure Substance 678B3 Phase Equilibrium Condition for a Pure Substance 679B4 Relationship Between Partial Molar Property and State Variable (Euler Theorem) 681B5 Chemical Potential in Mixtures 681B6 Relationship Between Second Virial Coefficients of Leiden and Berlin Form 682B7 Derivation of Expressions for the Speed of Sound for Ideal and Real Gases 683B8 Activity of the Solvent in an Electrolyte Solution 685B9 Temperature Dependence of the Azeotropic Composition 686B10 Konovalov Equations 688C1 (s–sid)T,P 691C2 (h–hid)T,P 692C3 (g–gid)T,P 692C4 Relationship Between Excess Enthalpy and Activity Coefficient 692D1 Fugacity Coefficient for a Pressure-Explicit Equation of State 692D2 Fugacity Coefficient of the Virial Equation (Leiden Form) 694D3 Fugacity Coefficient of the Virial Equation (Berlin Form) 695D4 Fugacity Coefficient of the Soave–Redlich–Kwong Equation of State 696D5 Fugacity Coefficient of the PSRK Equation of State 698D6 Fugacity Coefficient of the VTPR Equation of State 702E1 Derivation of the Wilson Equation 707E2 Notation of the Wilson, NRTL, and UNIQUAC Equations in Process Simulation Programs 710E3 Inability of the Wilson Equation to Describe a Miscibility Gap 711F1 (h–hid) for Soave–Redlich–Kwong Equation of State 713F2 (s–sid) for Soave–Redlich–Kwong Equation of State 715F3 (g–gid) for Soave–Redlich–Kwong Equation of State 715F4 Antiderivatives of cid P Correlations 715G1 Speed of Sound as Maximum Velocity in an Adiabatic Pipe with Constant Cross-Flow Area 717G2 Maximum Mass Flux of an Ideal Gas 717References 719Appendix D Standard Thermodynamic Properties for Selected Electrolyte Compounds 721Reference 722Appendix E Regression Technique for Pure Component Data 723Appendix F Regression Techniques for Binary Parameters 727References 741Appendix G Ideal Gas Heat Capacity Polynomial Coefficients for Selected Compounds 743Reference 744Appendix H UNIFAC Parameters 745Further Reading 746Appendix I Modified UNIFAC Parameters 747Further Reading 751Appendix J PSRK Parameters 753Further Reading 755Appendix K VTPR Parameters 757References 759Further Readings 760Index 761