Nonequilibrium Thermodynamics (eBook)

Front cover 1
Nonequilibrium Thermodynamics 4
Copyright page 5
Table of Contents 8
Preface 18
Preface to First Edition 20
List of Symbols 22
Chapter 1. Fundamentals of Equilibrium Thermodynamics 26
1.1 Introduction 26
1.2 Basic Definitions 26
1.3 Reversible and Irreversible Processes 31
1.4 Equilibrium 33
1.5 The Fundamental Equations 35
1.6 The Thermodynamic Laws 36
1.7 Balance Equations 39
1.8 Entropy and Entropy Production 41
1.9 The Gibbs Equation 45
1.10 Equations of State 47
1.11 Thermodynamic Potentials 71
1.12 Cross Relations 72
1.13 Extremum Principles 73
Problems 74
References 77
References for Further Reading 77
Chapter 2. Transport and Rate Processes 78
2.1 Introduction 78
2.2 Nonequilibrium Systems 78
2.3 Kinetic Approach 80
2.4 Transport Phenomena 81
2.5 The Maxwell–Stefan Equations 111
2.6 Transport Coefficients 112
2.7 Electric Charge Flow 112
2.8 The Relaxation Theory 114
2.9 Chemical Reactions 114
2.10 Coupled Processes 115
Problems 117
References 121
References for Further Reading 121
Chapter 3. Fundamentals of Nonequilibrium Thermodynamics 122
3.1 Introduction 122
3.2 Local Thermodynamic Equilibrium 122
3.3 The Second Law of Thermodynamics 123
3.4 Balance Equations and Entropy Production 137
3.5 Entropy Production Equation 146
3.6 Phenomenological Equations 152
3.7 Onsager’s Relations 157
3.8 Transformation of Forces and Flows 158
3.9 Chemical Reactions 164
3.10 Heat Conduction 164
3.11 Diffusion 166
3.12 Validity of Linear Phenomenological Equations 167
3.13 Curie–Prigogine Principle 168
3.14 Time Variation of Entropy Production 169
3.15 Minimum Entropy Production 171
Problems 177
References 179
References for Further Reading 179
Chapter 4. Using the Second Law: Thermodynamic Analysis 180
4.1 Introduction 180
4.2 Second-Law Analysis 180
4.3 Equipartition Principle 201
4.4 Exergy Analysis 209
4.5 Applications of Exergy Analysis 217
4.6 Chemical Exergy 268
4.7 Depletion Number 269
4.8 Optimization Problem 270
4.9 Information Capacity and Exergy 270
4.10 Pinch Analysis 271
Problems 289
References 298
References for Further Reading 299
Chapter 5. Thermoeconomics 300
5.1 Introduction 300
5.2 Thermodynamic Cost 300
5.3 Ecological Cost 310
5.4 Availability 311
5.5 Thermodynamic Optimum 312
5.6 Equipartition and Optimization in Separation Systems 314
5.7 Thermoeconomics of Latent Heat Storage 332
Problems 340
References 343
References for Further Reading 343
Chapter 6. Diffusion 344
6.1 Introduction 344
6.2 Maxwell–Stefan Equation 344
6.3 Diffusion in Nonelectrolyte Systems 360
6.4 Diffusion in Electrolyte Systems 361
6.5 Diffusion Without Shear Forces 369
6.6 Statistical Rate Theory 376
Problems 385
References 387
References for Further Reading 387
Chapter 7. Heat and Mass Transfer 388
7.1 Introduction 388
7.2 Coupled Heat and Mass Transfer 388
7.3 Heat of Transport 394
7.4 Degree of Coupling 396
7.5 Coupling in Liquid Mixtures 397
7.6 Coupled Mass and Energy Balances 409
7.7 Separation by Thermal Diffusion 412
7.8 Nonlinear Approach 419
7.9 Heat and Mass Transfer in Discontinuous System 426
7.10 Thermoelectric Effects 431
Problems 435
References 438
References for Further Reading 438
Chapter 8. Chemical Reactions 440
8.1 Introduction 440
8.2 Chemical Reaction Equilibrium Constant 440
8.3 The Principle of Detailed Balance 444
8.4 Dissipation for Chemical Reactions 448
8.5 Reaction Velocity (Flow) 450
8.6 Multiple Chemical Reactions 451
8.7 Stationary States 455
8.8 Michaelis–Menten Kinetics 468
8.9 Coupled Chemical Reactions 472
Problems 474
References 476
Chapter 9. Coupled Systems of Chemical Reactions and Transport Processes 478
9.1 Introduction 478
9.2 Nonisothermal Reaction–Diffusion Systems 478
9.3 Chemical Reaction with Coupled Heat and Mass Flows 490
9.4 Coupled System of Chemical Reaction and Transport Processes 495
9.5 Evolution of Coupled Systems 509
9.6 Facilitated Transport 510
9.7 Active Transport 520
9.8 Nonlinear Macrokinetics in a Reaction–Diffusion System 525
Problems 526
References 528
References for Further Reading 529
Chapter 10. Membrane Transport 530
10.1 Introduction 530
10.2 Membrane Equilibrium 530
10.3 Passive Transport 533
10.4 Facilitated and Active Transports in Membranes 550
10.5 Biomembranes 551
Problems 563
References 564
References for Further Reading 565
Chapter 11. Thermodynamics and Biological Systems 566
11.1 Introduction 566
11.2 Simplified Analysis in Living Systems 566
11.3 Bioenergetics 573
11.4 Proper Pathways 582
11.5 Coupling in Mitochondria 592
11.6 Regulation in Bioenergetics 599
11.7 Exergy use in Bioenergetics 606
11.8 Molecular Evolution 618
11.9 Molecular Machines 618
11.10. Evolutionary Criterion 620
Problems 621
References 622
References for Further Reading 623
Chapter 12. Stability Analysis 624
12.1 Introduction 624
12.2 The Gibbs Stability Theory 624
12.3 Stability and Entropy Production 629
12.4 Thermodynamic Fluctuations 632
12.5 Stability in Nonequilibrium Systems 633
12.6 Linear Stability Analysis 639
12.7 Oscillating Systems 641
Problems 653
References 654
References for Further Reading 654
Chapter 13. Organized Structures 656
13.1 Introduction 656
13.2 Equilibrium and Nonequilibrium Structures 656
13.3 Bifurcation 657
13.4 Limit Cycle 658
13.5 Order in Physical Structures 659
13.6 Order in Chemical Systems 663
13.7 Biological Structures 675
Problems 688
References 693
References for Further Reading 694
Chapter 14. Nonequilibrium Thermodynamics Approaches 696
14.1 Introduction 696
14.2 Network Thermodynamics with Bond Graph Methodology 696
14.3. Mosaic Nonequilibrium Thermodynamics 703
14.4 Rational Thermodynamics 704
14.5 Extended Nonequilibrium Thermodynamics 705
14.6 Generic Formulations 708
14.7 Matrix Model 709
14.8 Internal Variables 710
References 711
References for Further Reading 711
Appendix 712
Appendix A 712
Appendix B 713
Appendix C 720
Appendix D 721
Appendix E 729
Appendix F 738
Subject Index 752