Preface to the First Edition xvii
Preface to the Second Edition xxi
Preface to The Third Edition xxv
Preface xxix
Acknowledgments xxxvii
1 The First Law 1
1.1 Terminology 1
1.2 Closed Systems 4
1.3 Work Transfer 7
1.4 Heat Transfer 12
1.5 Energy Change 16
1.6 Open Systems 18
1.7 History 23
References 31
Problems 33
2 The Second Law 39
2.1 Closed Systems 39
2.1.1 Cycle in Contact with One Temperature Reservoir 39
2.1.2 Cycle in Contact with Two Temperature Reservoirs 41
2.1.3 Cycle in Contact with Any Number of Temperature Reservoirs 49
2.1.4 Process in Contact with Any Number of Temperature Reservoirs 51
2.2 Open Systems 54
2.3 Local Equilibrium 56
2.4 Entropy Maximum and Energy Minimum 57
2.5 Caratheodory’s Two Axioms 62
2.6 A Heat Transfer Man’s Two Axioms 71
2.7 History 77
References 78
Problems 80
3 Entropy Generation, Or Exergy Destruction 95
3.1 Lost Available Work 96
3.2 Cycles 102
3.2.1 Heat Engine Cycles 103
3.2.2 Refrigeration Cycles 104
3.2.3 Heat Pump Cycles 107
3.3 Nonflow Processes 109
3.4 Steady-Flow Processes 113
3.5 Mechanisms of Entropy Generation 119
3.5.1 Heat Transfer across a Temperature Difference 119
3.5.2 Flow with Friction 122
3.5.3 Mixing 124
3.6 Entropy Generation Minimization 126
3.6.1 The Method 126
3.6.2 Tree-Shaped Fluid Flow 127
3.6.3 Entropy Generation Number 130
References 132
Problems 133
4 Single-Phase Systems 140
4.1 Simple System 140
4.2 Equilibrium Conditions 141
4.3 The Fundamental Relation 146
4.3.1 Energy Representation 147
4.3.2 Entropy Representation 148
4.3.3 Extensive Properties versus Intensive Properties 149
4.3.4 The Euler Equation 150
4.3.5 The Gibbs–Duhem Relation 151
4.4 Legendre Transforms 154
4.5 Relations between Thermodynamic Properties 163
4.5.1 Maxwell’s Relations 163
4.5.2 Relations Measured during Special Processes 166
4.5.3 Bridgman’s Table 173
4.5.4 Jacobians in Thermodynamics 176
4.6 Partial Molal Properties 179
4.7 Ideal Gas Mixtures 183
4.8 Real Gas Mixtures 186
References 189
Problems 190
5 Exergy Analysis 195
5.1 Nonflow Systems 195
5.2 Flow Systems 198
5.3 Generalized Exergy Analysis 201
5.4 Air Conditioning 203
5.4.1 Mixtures of Air and Water Vapor 203
5.4.2 Total Flow Exergy of Humid Air 205
5.4.3 Total Flow Exergy of Liquid Water 207
5.4.4 Evaporative Cooling 208
References 210
Problems 210
6 Multiphase Systems 213
6.1 The Energy Minimum Principle 213
6.1.1 The Energy Minimum 214
6.1.2 The Enthalpy Minimum 215
6.1.3 The Helmholtz Free-Energy Minimum 216
6.1.4 The Gibbs Free-Energy Minimum 217
6.1.5 The Star Diagram 217
6.2 The Stability of a Simple System 219
6.2.1 Thermal Stability 219
6.2.2 Mechanical Stability 221
6.2.3 Chemical Stability 222
6.3 The Continuity of the Vapor and Liquid States 224
6.3.1 The Andrews Diagram and J. Thomson’s Theory 224
6.3.2 The van der Waals Equation of State 226
6.3.3 Maxwell’s Equal-Area Rule 233
6.3.4 The Clapeyron Relation 235
6.4 Phase Diagrams 236
6.4.1 The Gibbs Phase Rule 236
6.4.2 Single-Component Substances 237
6.4.3 Two-Component Mixtures 239
6.5 Corresponding States 247
6.5.1 Compressibility Factor 247
6.5.2 Analytical P(v, T) Equations of State 253
6.5.3 Calculation of Properties Based on P(v, T) and Specific Heat 257
6.5.4 Saturated Liquid and Saturated Vapor States 259
6.5.5 Metastable States 261
References 264
Problems 266
7 Chemically Reactive Systems 271
7.1 Equilibrium 271
7.1.1 Chemical Reactions 271
7.1.2 Affinity 274
7.1.3 Le Chatelier–Braun Principle 277
7.1.4 Ideal Gas Mixtures 280
7.2 Irreversible Reactions 287
7.3 Steady-Flow Combustion 295
7.3.1 Combustion Stoichiometry 295
7.3.2 The First Law 297
7.3.3 The Second Law 303
7.3.4 Maximum Power Output 306
7.4 The Chemical Exergy of Fuels 316
7.5 Combustion at Constant Volume 320
7.5.1 The First Law 320
7.5.2 The Second Law 322
7.5.3 Maximum Work Output 323
References 324
Problems 325
8 Power Generation 328
8.1 Maximum Power Subject to Size Constraint 328
8.2 Maximum Power from a Hot Stream 332
8.3 External Irreversibilities 338
8.4 Internal Irreversibilities 344
8.4.1 Heater 344
8.4.2 Expander 346
8.4.3 Cooler 346
8.4.4 Pump 348
8.4.5 Relative Importance of Internal Irreversibilities 348
8.5 Advanced Steam Turbine Power Plants 352
8.5.1 Superheater, Reheater, and Partial Condenser Vacuum 352
8.5.2 Regenerative Feed Heating 355
8.5.3 Combined Feed Heating and Reheating 362
8.6 Advanced Gas Turbine Power Plants 366
8.6.1 External and Internal Irreversibilities 366
8.6.2 Regenerative Heat Exchanger, Reheaters, and Intercoolers 371
8.6.3 Cooled Turbines 374
8.7 Combined Steam Turbine and Gas Turbine Power Plants 376
References 379
Problems 381
9 Solar Power 394
9.1 Thermodynamic Properties of Thermal Radiation 394
9.1.1 Photons 395
9.1.2 Temperature 396
9.1.3 Energy 397
9.1.4 Pressure 399
9.1.5 Entropy 400
9.2 Reversible Processes 403
9.2.1 Reversible and Adiabatic Expansion or Compression 403
9.2.2 Reversible and Isothermal Expansion or Compression 403
9.2.3 Carnot Cycle 404
9.3 Irreversible Processes 404
9.3.1 Adiabatic Free Expansion 404
9.3.2 Transformation of Monochromatic Radiation into Blackbody Radiation 405
9.3.3 Scattering 407
9.3.4 Net Radiative Heat Transfer 408
9.3.5 Kirchhoff’s Law 412
9.4 The Ideal Conversion of Enclosed Blackbody Radiation 413
9.4.1 Petela’s Theory 413
9.4.2 Unifying Theory 416
9.5 Maximization of Power Output Per Unit Collector Area 424
9.5.1 Ideal Concentrators 424
9.5.2 Omnicolor Series of Ideal Concentrators 427
9.5.3 Unconcentrated Solar Radiation 428
9.6 Convectively Cooled Collectors 431
9.6.1 Linear Convective Heat Loss Model 432
9.6.2 Effect of Collector–Engine Heat Exchanger Irreversibility 433
9.6.3 Combined Convective and Radiative Heat Loss 434
9.7 Extraterrestrial Solar Power Plant 436
9.8 Climate 438
9.9 Self-Pumping and Atmospheric Circulation 449
References 453
Problems 455
10 Refrigeration 461
10.1 Joule–Thomson Expansion 461
10.2 Work-Producing Expansion 468
10.3 Brayton Cycle 471
10.4 Intermediate Cooling 477
10.4.1 Counterflow Heat Exchanger 477
10.4.2 Bioheat Transfer 479
10.4.3 Distribution of Expanders 480
10.4.4 Insulation 484
10.5 Liquefaction 492
10.5.1 Liquefiers versus Refrigerators 492
10.5.2 Heylandt Nitrogen Liquefier 494
10.5.3 Efficiency of Liquefiers and Refrigerators 498
10.6 Refrigerator Models with Internal Heat Leak 502
10.6.1 Heat Leak in Parallel with Reversible Compartment 502
10.6.2 Time-Dependent Operation 505
10.7 Magnetic Refrigeration 509
10.7.1 Fundamental Relations 509
10.7.2 Adiabatic Demagnetization 513
10.7.3 Paramagnetic Thermometry 514
10.7.4 The Third Law of Thermodynamics 517
References 518
Problems 521
11 Entropy Generation Minimization 531
11.1 Competing Irreversibilities 531
11.1.1 Internal Flow and Heat Transfer 531
11.1.2 Heat Transfer Augmentation 536
11.1.3 External Flow and Heat Transfer 538
11.1.4 Convective Heat Transfer in General 541
11.2 Balanced Counterflow Heat Exchangers 543
11.2.1 The Ideal Limit 545
11.2.2 Area Constraint 548
11.2.3 Volume Constraint 550
11.2.4 Combined Area and Volume Constraint 551
11.2.5 Negligible Pressure Drop Irreversibility 551
11.2.6 The Structure of Heat Exchanger Irreversibility 553
11.3 Storage Systems 555
11.3.1 Sensible-Heat Storage 555
11.3.2 Storage Time Interval 556
11.3.3 Heat Exchanger Size 558
11.3.4 Storage Followed by Removal of Exergy 561
11.3.5 Heating and Cooling Subject to Time Constraint 564
11.3.6 Latent-Heat Storage 567
11.4 Power Maximization or Entropy Generation Minimization 570
11.4.1 Heat Transfer Irreversible Power Plant Models 571
11.4.2 Minimum Entropy Generation Rate 573
11.4.3 Fluid Flow Systems 577
11.4.4 Electrical Machines 581
11.5 From Entropy Generation Minimization to Constructal Law 583
11.5.1 The Generation-of-Configuration Phenomenon 583
11.5.2 Organ Size 586
References 592
Problems 595
12 Irreversible Thermodynamics 601
12.1 Conjugate Fluxes and Forces 602
12.2 Linearized Relations 606
12.3 Reciprocity Relations 607
12.4 Thermoelectric Phenomena 610
12.4.1 Formulations 610
12.4.2 The Peltier Effect 613
12.4.3 The Seebeck Effect 615
12.4.4 The Thomson Effect 616
12.4.5 Power Generation 618
12.4.6 Refrigeration 623
12.5 Heat Conduction in Anisotropic Media 625
12.5.1 Formulation in Two Dimensions 626
12.5.2 Principal Directions and Conductivities 628
12.5.3 The Concentrated Heat Source Experiment 631
12.5.4 Three-Dimensional Conduction 633
12.6 Mass Diffusion 635
12.6.1 Nonisothermal Diffusion of a Single Component 635
12.6.2 Nonisothermal Binary Mixtures 637
12.6.3 Isothermal Diffusion 639
References 640
Problems 642
13 The Constructal Law 646
13.1 Evolution 646
13.2 Mathematical Formulation of the Constructal Law 649
13.2.1 Properties of Flow Systems with Configuration 649
13.2.2 Evolution by Increasing Global Performance 651
13.2.3 Evolution by Increasing Compactness 652
13.2.4 Evolution by Increasing Flow Territory 652
13.2.5 Freedom Is Good for Evolution and Survival (Persistence) 654
13.3 Inanimate Flow Systems 655
13.3.1 Duct Cross Sections 655
13.3.2 Open-Channel Cross Sections 657
13.3.3 Tree-Shaped Fluid Flow and River Basins 658
13.3.4 Turbulent Flow Structure 664
13.3.5 Coalescence of Flowing Solid Packets 668
13.3.6 Cracks, Splashes, and Splats 669
13.3.7 Dendritic Solidification 669
13.3.8 Global Circulation and Climate 671
13.4 Animate Flow Systems 673
13.4.1 Body Heat Loss 673
13.4.2 Branches, Diameters, and Lengths 678
13.4.3 Breathing and Heartbeating 680
13.4.4 Flying, Running, and Swimming 681
13.4.5 Life Span and Life Travel 687
13.4.6 Athletics Evolution 688
13.5 Size and Efficiency: Economies of Scale 689
13.6 Growth, Spreading, and Collecting 691
13.7 Asymmetry and Vascularization 693
13.8 Human Preferences for Shapes 697
13.9 The Arrow of Time 699
References 702
Problems 706
Appendix 725
Constants 725
Mathematical Formulas 726
Variational Calculus 727
Properties of Moderately Compressed Liquid States 728
Properties of Slightly Superheated Vapor States 729
Properties of Cold Water Near the Density Maximum 729
References 730
Symbols 731
Index 741
