1 INTRODUCTION 1
1.1 The Scope of Thermodynamics 1
1.2 Dimensions and Units 2
1.3 Measures of Amount or Size 2
1.4 Force 3
1.5 Temperature 5
1.6 Pressure 6
1.7 Work 9
1.8 Energy 10
1.9 Heat 15
2 THE FIRST LAW AND OTHER BASIC CONCEPTS 20
2.1 Joule's Experiments 20
2.2 Internal Energy 20
2.3 The First Law of Thermodynamics 21
2.4 Energy Balance for Closed Systems 22
2.5 Thermodynamic State and State Functions 25
2.6 Equilibrium 28
2.7 The Phase Rule 29
2.8 The Reversible Process 31
2.9 Constant-V and Constant-P Processes 37
2.10 Enthalpy 38
2.11 Heat Capacity 40
2.12 Mass and Energy Balances for Open Systems 44
3 VOLUMETRIC PROPERTIES OF PURE FLUIDS 62
3.1 PVT Behavior ofPure Substances 62
3.2 Virial Equations of State 68
3.3 The Ideal Gas 71
3.4 Application ofthe Virial Equations 87
3.5 Cubic Equations of State 91
3.6 Generalized Correlations for Gases 100
3.7 Generalized Correlations for Liquids 108
4 HEAT EFFECTS 122
4.1 Sensible Heat Effects 122
4.2 Latent Heats of Pure Substances 129
4.3 Standard Heat of Reaction 132
4.4 Standard Heat of Formation 133
4.5 Standard Heat of Combustion 136
4.6 Temperature Dependence of △H° 137
4.7 Heat Effects of Industrial Reactions 140
5 THE SECOND LAW OF THERMODYNAMICS 155
5.1 Statements of the Second Law 156
5.2 Heat Engines 157
5.3 Thermodynamic Temperature Scales 159
5.4 Entropy 163
5.5 Entropy Changes of an Ideal Gas 166
5.6 Mathematical Statement of the Second Law 169
5.7 Entropy Balance for Open Systems 172
5.8 Calculation of Ideal Work 177
5.9 Lost Work 181
5.10 The Third Law of Thermodynamics 185
5.11 Entropy from the Microscopic Viewpoint 185
6.1 Property Relations for Homogeneous Phases 195
6 THERMODYNAMIC PROPERTIES OF FLUIDS 195
6.2 Residual Properties 205
6.3 Residual Properties by Equations of State 211
6.4 Two-Phase Systems 217
6.5 Thermodynamic Diagrams 220
6.6 Tables of Thermodynamic Properties 221
6.7 Generalized Property Correlations for Gases 225
7 APPLICATIONS OF THERMODYNAMICS TO FLOW PROCESSES 247
7.1 Duct Flow of Compressible Fluids 248
7.2 Turbines(Expanders) 262
7.3 Compression Processes 267
8 PRODUCTION OF POWER FROM HEAT 283
8.1 The Steam Power Plant 284
8.2 Internal-Combustion Engines 295
8.3 Jet Engines;Rocket Engines 303
9 REFRIGERATION AND LIQUEFACTION 309
9.1 The Carnot Refrigerator 309
9.2 The Vapor-Compression Cycle 310
9.3 The Choice of Refrigerant 313
9.4 Absorption Refrigeration 316
9.5 The Heat Pump 318
9.6 Liquefaction Processes 319
10 VAPOR/LIQUID EQUILIBRIUM:INTRODUCTION 329
10.1 The Nature of Equilibrium 329
10.2 The Phase Rule.Duhem's Theorem 330
10.3 VLE:Qualitative Behavior 332
10.4 Simple Models for Vapor/Liquid Equilibrium 338
10.5 VLE by Modified Raoult's Law 349
10.6 VLE from K-Value Correlations 354
11 SOLUTION THERMODYNAMICS:THEORY 368
11.1 Fundamental Property Relation 369
11.2 The Chemical Potential and Phase Equilibria 370
11.3 Partial Properties 371
11.4 Ideal-Gas Mixtures 381
11.5 Fugacity and Fugacity Coefficient:Pure Species 384
11.6 Fugacity and Fugacity Coefficient:Species in Solution 390
11.7 Generalized Correlations for the Fugacity Coefficient 396
11.8 The Ideal Solution 400
11.9 Excess Properties 402
12 SOLUTION THERMODYNAMICS:APPLICATIONS 416
12.1 Liquid-Phase Properties from VLE Data 416
12.2 Models for the Excess Gibbs Energy 432
12.3 Property Changes of Mixing 435
12.4 Heat Effects of Mixing Processes 442
13 CHEMICAL-REACTION EQUILIBRIA 467
13.1 The Reaction Coordinate 468
13.2 Application of Equilibrium Criteria to Chemical Reactions 472
13.3 The Standard Gibbs-Energy Change and the Equilibrium Constant 473
13.4 Effect of Temperature on the Equilibrium Constant 476
13.5 Evaluation of Equilibrium Constants 480
13.6 Relation of Equilibrium Constants to Composition 482
13.7 Equilibrium Conversions for Single Reactions 486
13.8 Phase Rule and Duhem's Theorem for Reacting Systems 498
13.9 Multireaction Equilibria 502
13.10 Fuel Cells 513
14 TOPICS IN PHASE EQUILIBRIA 526
14.1 The Gamma/Phi Formulation of VLE 526
14.2 VLE from Cubic Equations of State 538
14.3 Equilibrium and Stability 554
14.4 Liquid/Liquid Equilibrium(LLE) 560
14.5 Vapor/Liquid/Liquid Equilibrium(VLLE) 569
14.6 Solid/Liquid Equilibrium (SLE) 576
14.7 Solid/Vapor Equilibrium(SVE) 581
14.8 Equilibrium Adsorption of Gases on Solids 585
14.9 Osmotic Equilibrium and Osmotic Pressure 600
15 THERMODYNAMIC ANALYSIS OF PROCESSES 611
15.1 Thermodynamic Analysis of Steady-State Flow Processes 611
16 INTRODUCTION TO MOLECULAR THERMODYNAMICS 622
16.1 Molecular Theory of Fluids 622
16.2 Second Virial Coefficients from Potential Functions 629
16.3 Internal Energy of Ideal Gases:Microscopic View 632
16.4 Thermodynamic Properties and Statistical Mechanics 635
16.5 Hydrogen Bonding and Charge-Transfer Complexing 637
16.6 Behavior of Excess Properties 640
16.7 Molecular Basis for Mixture Behavior 644
16.8 VLE by Molecular Simulation 647
A Conversion Factors and Values of the Gas Constant 651
B Properties of Pure Species 653
C Heat Capacities and Property Changes of Formation 656
D Representative Computer Programs 661
D.1 Defined Functions 661
D.2 Solution of Example Problems by Mathcad？ 664
E The Lee/Kesler Generalized-correlation Tables 667
F Steam Tables 684
F.1 Interpolation 684
G Thermodynamic Diagrams 760
H UNIFAC Method 763
I Newton's Method 770
Author Index 775
Subject Index 779