This must-read for advanced students and professionals alike is the first book to demonstrate how chemical thermodynamics work in the real world by applying them to actual engineering examples. It also discusses the advantages and disadvantages of the particular models and procedures, and explains the most important models that are applied in process industry. All the topics are illustrated with examples that are closely related to practical process simulation problems. At the end of each chapter, additional calculation examples are given to enable readers to extend their comprehension.
Chemical Thermodynamics for Process Simulation instructs on the behavior of fluids for pure fluids, describing the main types of equations of state and their abilities. It discusses the various quantities of interest in process simulation, their correlation, and prediction in detail. Chapters look at the important terms for the description of the thermodynamics of mixtures; the most important models and routes for phase equilibrium calculation; models which are applicable to a wide variety of non-electrolyte systems; membrane processes; polymer thermodynamics; enthalpy of reaction; chemical equilibria, and more.
-Explains thermodynamic fundamentals used in process simulation with solved examples
-Includes new chapters about modern measurement techniques, retrograde condensation, and simultaneous description of chemical equilibrium
-Comprises numerous solved examples, which simplify the understanding of the often complex calculation procedures, and discusses advantages and disadvantages of models and procedures
-Includes estimation methods for thermophysical properties and phase equilibria thermodynamics of alternative separation processes
-Supplemented with MathCAD-sheets and DDBST programs for readers to reproduce the examples
Chemical Thermodynamics for Process Simulation is an ideal resource for those working in the fields of process development, process synthesis, or process optimization, and an excellent book for students in the engineering sciences.
Table of Contents
Preface xiii
Preface to the Second Edition xvii
List of Symbols xix
About the Authors xxix
1 Introduction 1
2 PvT Behavior of Pure Components 5
2.1 General Description 5
2.2 Caloric Properties 10
2.3 Ideal Gases 14
2.4 Real Fluids 16
2.4.1 Auxiliary Functions 16
2.4.2 Residual Functions 17
2.4.3 Fugacity and Fugacity Coefficient 19
2.4.4 Phase Equilibria 22
2.5 Equations of State 25
2.5.1 Virial Equation 26
2.5.2 High-Precision Equations of State 30
2.5.3 Cubic Equations of State 37
2.5.4 Generalized Equations of State and Corresponding-States Principle 42
2.5.5 Advanced Cubic Equations of State 49
Problems 57
References 60
3 Correlation and Estimation of Pure Component Properties 63
3.1 Introduction 63
3.2 Characteristic Physical Property Constants 63
3.2.1 Critical Data 64
3.2.2 Acentric Factor 69
3.2.3 Normal Boiling Point 69
3.2.4 Melting Point and Enthalpy of Fusion 72
3.2.5 Standard Enthalpy and Standard Gibbs Energy of Formation 74
3.3 Temperature-Dependent Properties 77
3.3.1 Vapor Pressure 78
3.3.2 Liquid Density 90
3.3.3 Enthalpy of Vaporization 94
3.3.4 Ideal Gas Heat Capacity 98
3.3.5 Liquid Heat Capacity 105
3.3.6 Speed of Sound 109
3.4 Correlation and Estimation of Transport Properties 110
3.4.1 Liquid Viscosity 110
3.4.2 Vapor Viscosity 115
3.4.3 Liquid Thermal Conductivity 120
3.4.4 Vapor Thermal Conductivity 125
3.4.5 Surface Tension 128
3.4.6 Diffusion Coefficients 131
Problems 135
References 138
4 Properties of Mixtures 143
4.1 Introduction 143
4.2 Property Changes of Mixing 144
4.3 Partial Molar Properties 145
4.4 Gibbs-Duhem Equation 148
4.5 Ideal Mixture of Ideal Gases 150
4.6 Ideal Mixture of Real Fluids 152
4.7 Excess Properties 153
4.8 Fugacity in Mixtures 154
4.8.1 Fugacity of an Ideal Mixture 155
4.8.2 Phase Equilibrium 155
4.9 Activity and Activity Coefficient 156
4.10 Application of Equations of State to Mixtures 157
4.10.1 Virial Equation 158
4.10.2 Cubic Equations of State 159
Problems 169
References 170
5 Phase Equilibria in Fluid Systems 173
5.1 Introduction 173
5.2 Thermodynamic Fundamentals 185
5.3 Application of Activity Coefficients 192
5.4 Calculation of Vapor-Liquid Equilibria Using gE Models 195
5.5 Fitting of gE Model Parameters 212
5.5.1 Check of VLE Data for Thermodynamic Consistency 218
5.5.2 Recommended gE Model Parameters 227
5.6 Calculation of Vapor-Liquid Equilibria Using Equations of State 229
5.6.1 Fitting of Binary Parameters of Cubic Equations of State 235
5.7 Conditions for the Occurrence of Azeotropic Behavior 243
5.8 Solubility of Gases in Liquids 252
5.8.1 Calculation of Gas Solubilities Using Henry Constants 254
5.8.2 Calculation of Gas Solubilities Using Equations of State 262
5.8.3 Prediction of Gas Solubilities 263
5.9 Liquid-Liquid Equilibria 266
5.9.1 Temperature Dependence of Ternary LLE 277
5.9.2 Pressure Dependence of LLE 279
5.10 Predictive Models 280
5.10.1 Regular Solution Theory 281
5.10.2 Group Contribution Methods 282
5.10.3 UNIFAC Method 284
5.10.3.1 Modified UNIFAC (Dortmund) 291
5.10.3.2 Weaknesses of the Group Contribution Methods UNIFAC and Modified UNIFAC 295
5.10.4 Predictive Soave-Redlich-Kwong (PSRK) Equation of State 302
5.10.5 VTPR Group Contribution Equation of State 306
Problems 315
References 319
6 Caloric Properties 323
6.1 Caloric Equations of State 323
6.1.1 Internal Energy and Enthalpy 323
6.1.2 Entropy 326
6.1.3 Helmholtz Energy and Gibbs Energy 327
6.2 Enthalpy Description in Process Simulation Programs 329
6.2.1 Route A: Vapor as Starting Phase 330
6.2.2 Route B: Liquid as Starting Phase 334
6.2.3 Route C: Equation of State 335
6.3 Caloric Properties in Chemical Reactions 343
Problems 349
References 350
7 Electrolyte Solutions 351
7.1 Introduction 351
7.2 Thermodynamics of Electrolyte Solutions 355
7.3 Activity Coefficient Models for Electrolyte Solutions 360
7.3.1 Debye-Hรผckel Limiting Law 360
7.3.2 Bromley Extension 361
7.3.3 Pitzer Model 361
7.3.4 NRTL Electrolyte Model by Chen 364
7.3.5 LIQUAC Model 372
7.3.6 MSA Model 380
7.4 Dissociation Equilibria 381
7.5 Influence of Salts on the Vapor-Liquid Equilibrium Behavior 383
7.6 Complex Electrolyte Systems 385
Problems 386
References 386
8 Solid-Liquid Equilibria 389
8.1 Introduction 389
8.2 Thermodynamic Relations for the Calculation of Solid-Liquid Equilibria 392
8.2.1 Solid-Liquid Equilibria of Simple Eutectic Systems 394
8.2.1.1 Freezing Point Depression 401
8.2.2 Solid-Liquid Equilibria of Systems with Solid Solutions 402
8.2.2.1 Ideal Systems 402
8.2.2.2 Solid-Liquid Equilibria for Nonideal Systems 403
8.2.3 Solid-Liquid Equilibria with Intermolecular Compound Formation in the Solid State 406
8.2.4 Pressure Dependence of Solid-Liquid Equilibria 409
8.3 Salt Solubility 409
8.4 Solubility of Solids in Supercritical Fluids 414
Problems 416
References 419
9 Membrane Processes 421
9.1 Osmosis 421
9.2 Pervaporation 424
Problems 425
References 426
10 Polymer Thermodynamics 427
10.1 Introduction 427
10.2 gE Models 433
10.3 Equations of State 444
10.4 Influence of Polydispersity 460
10.5 Influence of Polymer Structure 464
Problems 465
References 467
11 Applications of Thermodynamics in Separation Technology 469
11.1 Introduction 469
11.2 Verification of Model Parameters Prior to Process Simulation 474
11.2.1 Verification of Pure Component Parameters 474
11.2.2 Verification of gE Model Parameters 475
11.3 Investigation of Azeotropic Points in Multicomponent Systems 483
11.4 Residue Curves, Distillation Boundaries, and Distillation Regions 484
11.5 Selection of Entrainers for Azeotropic and Extractive Distillation 491
11.6 Selection of Solvents for Other Separation Processes 499
11.7 Selection of Solvent-Based Separation Processes 499
Problems 503
References 504
12 Enthalpy of Reaction and Chemical Equilibria 505
12.1 Introduction 505
12.2 Enthalpy of Reaction 506
12.2.1 Temperature Dependence 507
12.2.2 Consideration of the Real Gas Behavior on the Enthalpy of Reaction 509
12.3 Chemical Equilibrium 511
12.4 Multiple Chemical Reaction Equilibria 530
12.4.1 Relaxation Method 531
12.4.2 Gibbs Energy Minimization 535
Problems 544
References 547
13 Examples for Complex Systems 549
13.1 Introduction 549
13.2 Formaldehyde Solutions 549
13.3 Vapor Phase Association 555
Problems 568
References 570
14 Practical Applications 573
14.1 Introduction 573
14.2 Flash 573
14.3 Joule-Thomson Effect 575
14.4 Adiabatic Compression and Expansion 577
14.5 Pressure Relief 581
14.6 Limitations of Equilibrium Thermodynamics 586
Problems 589
References 591
15 Experimental Determination of Pure Component and Mixture Properties 593
15.1 Introduction 593
15.2 Pure Component Vapor Pressure and Boiling Temperature 594
15.3 Enthalpy of Vaporization 598
15.4 Critical Data 599
15.5 Vapor-Liquid Equilibria 599
15.5.1 Dynamic VLE Stills 601
15.5.2 Static Techniques 604
15.5.3 Degassing 611
15.5.4 Headspace Gas Chromatography (HSGC) 613
15.5.5 High-Pressure VLE 614
15.5.6 Inline True Component Analysis in Reactive Mixtures 616
15.6 Activity Coefficients at Infinite Dilution 617
15.6.1 Gas Chromatographic Retention Time Measurement 618
15.6.2 Inert Gas Stripping (Dilutor) 620
15.6.3 Limiting Activity Coefficients of High Boilers in Low Boilers 622
15.7 Liquid-Liquid Equilibria (LLE) 622
15.8 Gas Solubility 623
15.9 Excess Enthalpy 624
Problems 626
References 626
16 Introduction to the Collection of Example Problems 631
16.1 Introduction 631
16.2 Mathcad Examples 631
16.3 Examples Using the Dortmund Data Bank (DDB) and the Integrated Software Package DDBSP 633
16.4 Examples Using Microsoft Excel and Microsoft Office VBA 634
Appendix A Pure Component Parameters 635
Appendix B Coefficients for High-Precision Equations of State 663
References 668
Appendix C Useful Derivations 669
A1 Relationship Between (๐s/๐T)P and (๐s/๐T)v 670
A2 Expressions for (๐u/๐v)T and (๐s/๐v)T 670
A3 cP and cv as Derivatives of the Specific Entropy 671
A4 Relationship Between cP and cv 672
A5 Expression for (๐h/๐P)T 673
A6 Expression for (๐s/๐P)T 674
A7 Expression for [๐(g/RT)/๐T]P and vanโt Hoff Equation 674
A8 General Expression for cv 675
A9 Expression for (๐P/๐v)T 676
A10 Cardanoโs Formula 676
B1 Derivation of the Kelvin Equation 677
B2 Equivalence of Chemical Potential ฮผ and Gibbs Energy g for a Pure Substance 678
B3 Phase Equilibrium Condition for a Pure Substance 679
B4 Relationship Between Partial Molar Property and State Variable (Euler Theorem) 681
B5 Chemical Potential in Mixtures 681
B6 Relationship Between Second Virial Coefficients of Leiden and Berlin Form 682
B7 Derivation of Expressions for the Speed of Sound for Ideal and Real Gases 683
B8 Activity of the Solvent in an Electrolyte Solution 685
B9 Temperature Dependence of the Azeotropic Composition 686
B10 Konovalov Equations 688
C1 (s-sid)T,P 691
C2 (h-hid)T,P 692
C3 (g-gid)T,P 692
C4 Relationship Between Excess Enthalpy and Activity Coefficient 692
D1 Fugacity Coefficient for a Pressure-Explicit Equation of State 692
D2 Fugacity Coefficient of the Virial Equation (Leiden Form) 694
D3 Fugacity Coefficient of the Virial Equation (Berlin Form) 695
D4 Fugacity Coefficient of the Soave-Redlich-Kwong Equation of State 696
D5 Fugacity Coefficient of the PSRK Equation of State 698
D6 Fugacity Coefficient of the VTPR Equation of State 702
E1 Derivation of the Wilson Equation 707
E2 Notation of the Wilson, NRTL, and UNIQUAC Equations in Process Simulation Programs 710
E3 Inability of the Wilson Equation to Describe a Miscibility Gap 711
F1 (h-hid) for Soave-Redlich-Kwong Equation of State 713
F2 (s-sid) for Soave-Redlich-Kwong Equation of State 715
F3 (g-gid) for Soave-Redlich-Kwong Equation of State 715
F4 Antiderivatives of cid P Correlations 715
G1 Speed of Sound as Maximum Velocity in an Adiabatic Pipe with Constant Cross-Flow Area 717
G2 Maximum Mass Flux of an Ideal Gas 717
References 719
Appendix D Standard Thermodynamic Properties for Selected Electrolyte Compounds 721
Reference 722
Appendix E Regression Technique for Pure Component Data 723
Appendix F Regression Techniques for Binary Parameters 727
References 741
Appendix G Ideal Gas Heat Capacity Polynomial Coefficients for Selected Compounds 743
Reference 744
Appendix H UNIFAC Parameters 745
Further Reading 746
Appendix I Modified UNIFAC Parameters 747
Further Reading 751
Appendix J PSRK Parameters 753
Further Reading 755
Appendix K VTPR Parameters 757
References 759
Further Readings 760
Index 761
