CHAPTER 1 Measured Thermodynamic Properties and Other Basic Concepts 1
Learning Objectives 1
1.1 Thermodynamics 2
1.2 Preliminary Conceptsâ"The Language of Thermo 3
Thermodynamic Systems 3
Properties 4
Processes 5
Hypothetical Paths 6
Phases of Matter 6
Length Scales 6
Units 7
1.3 Measured Thermodynamic Properties 7
Volume (Extensive or Intensive) 7
Temperature (Intensive) 8
Pressure (Intensive) 11
The Ideal Gas 13
1.4 Equilibrium 15
Types of Equilibrium 15
Molecular View of Equilibrium 16
1.5 Independent and Dependent Thermodynamic Properties 17
The State Postulate 17
Gibbs Phase Rule 18
1.6 The PÊT Surface and Its Projections for Pure Substances 20
Changes of State During a Process 22
Saturation Pressure vs. Vapor Pressure 23
The Critical Point 24
1.7 Thermodynamic Property Tables 26
1.8 Summary 30
1.9 Problems 31
Conceptual Problems 31
Numerical Problems 34
CHAPTER 2 The First Law of Thermodynamics 36
Learning Objectives 36
2.1 The First Law of Thermodynamics 37
Forms of Energy 37
Ways We Observe Changes in U 39
Internal Energy of an Ideal Gas 40
Work and Heat: Transfer of Energy Between the System and the Surroundings 42
2.2 Construction of Hypothetical Paths 46
2.3 Reversible and Irreversible Processes 48
Reversible Processes 48
Irreversible Processes 48
Efficiency 55
2.4 The First Law of Thermodynamics for Closed Systems 55
Integral Balances 55
Differential Balances 57
2.5 The First Law of Thermodynamics for Open Systems 60
Material Balance 60
Flow Work 60
Enthalpy 62
Steady-State Energy Balances 62
Transient Energy Balance 63
2.6ThermochemicalData For U and H 67
Heat Capacity: cÊ and cP 67
Latent Heats 76
Enthalpy of Reactions 80
2.7 Reversible Processes in Closed Systems 92
Reversible, Isothermal Expansion (Compression) 92
Adiabatic Expansion (Compression) with Constant Heat Capacity 93
Summary 95
2.8 Open-System Energy Balances on Process Equipment 95
Nozzles and Diffusers 96
Turbines and Pumps (or Compressors) 97
Heat Exchangers 98
Throttling Devices 101
2.9 Thermodynamic Cycles and the Carnot Cycle 102
Efficiency 104
2.10 Summary 108
2.11 Problems 110
Conceptual Problems 110
Numerical Problems 113
CHAPTER 3 Entropy and the Second Law Of Thermodynamics 127
Learning Objectives 127
3.1 Directionality of Processes/Spontaneity 128
3.2 Reversible and Irreversible Processes (Revisited) and their Relationship to Directionality 129
3.3 Entropy, the Thermodynamic Property 131
3.4 The Second Law of Thermodynamics 140
3.5 Other Common Statements of the Second Law of Thermodynamics 142
3.6 The Second Law of Thermodynamics for Closed and Open Systems 143
Calculation of Î"s for Closed Systems 143
Calculation of Î"s for Open Systems 147
3.7 Calculation of Î"s for an Ideal Gas 151
3.8 The Mechanical Energy Balance and the Bernoulli Equation 160
3.9 Vapor-Compression Power and Refrigeration Cycles 164
The Rankine Cycle 164
The Vapor-Compression Refrigeration Cycle 169
3.10 Exergy (Availability) Analysis 172
Exergy 173
Exthalpyâ"Flow Exergy in Open Systems 178
3.11 Molecular View of Entropy 182
Maximizing Molecular Confi gurations over Space 185
Maximizing Molecular Confi gurations over Energy 186
3.12 Summary 190
3.13 Problems 191
Conceptual Problems 191
Numerical Problems 195
CHAPTER 4 Equations of State and Intermolecular Forces 209
Learning Objectives 209
4.1 Introduction 210
Motivation 210
The Ideal Gas 211
4.2 Intermolecular Forces 211
Internal (Molecular) Energy 211
The Electric Nature of Atoms and Molecules 212
Attractive Forces 213
Intermolecular Potential Functions and Repulsive Forces 223
Principle of Corresponding States 226
Chemical Forces 228
4.3 Equations of State 232
The van der Waals Equation of State 232
Cubic Equations of State (General) 238
The Virial Equation of State 240
Equations of State for Liquids and Solids 245
4.4 Generalized Compressibility Charts 246
4.5 Determination of Parameters for Mixtures 249
Cubic Equations of State 250
Virial Equation of State 251
Corresponding States 252
4.6 Summary 254
4.7 Problems 255
Conceptual Problems 255
Numerical Problems 257
CHAPTER 5 The Thermodynamic Web 265
Learning Objectives 265
5.1 Types of Thermodynamic Properties 265
Measured Properties 265
Fundamental Properties 266
Derived Thermodynamic Properties 266
5.2 Thermodynamic Property Relationships 267
Dependent and Independent Properties 267
Hypothetical Paths (revisited) 268
Fundamental Property Relations 269
Maxwell Relations 271
Other Useful Mathematical Relations 272
Using the Thermodynamic Web to Access Reported Data 273
5.3 Calculation of Fundamental and Derived Properties Using Equations of State and Other Measured Quantities 276
Relation of ds in Terms of Independent Properties T and Ê and Independent Properties T and P 276
Relation of du in Terms of Independent Properties T and Ê 277
Relation of dh in Terms of Independent Properties T and P 281
Alternative Formulation of the Web using T and P as Independent Properties 287
5.4 Departure Functions 290
Enthalpy Departure Function 290
Entropy Departure Function 293
5.5 Joule-Thomson Expansion and Liquefaction 298
Joule-Thomson Expansion 298
Liquefaction 301
5.6 Summary 304
5.7 Problems 305
Conceptual Problems 305
Numerical Problems 307
CHAPTER 6 Phase Equilibria I: Problem Formulation 315
Learning Objectives 315
6.1 Introduction 315
The Phase Equilibria Problem 316
6.2 Pure Species Phase Equilibrium 318
Gibbs Energy as a Criterion for Chemical
Equilibrium 318
Roles of Energy and Entropy in Phase Equilibria 321
The Relationship Between Saturation Pressure and Temperature: The Clapeyron Equation 327
Pure Component Vaporâ"Liquid Equilibrium: The Clausiusâ"Clapeyron Equation 328
6.3 Thermodynamics of Mixtures 334
Introduction 334
Partial Molar Properties 335
The Gibbsâ"Duhem Equation 340
Summary of the Different Types of Thermodynamic Properties 342
Property Changes of Mixing 343
Determination of Partial Molar Properties 357
Relations Among Partial Molar Quantities 366
6.4 Multicomponent Phase Equilibria 367
The Chemical Potentialâ"The Criteria for Chemical Equilibrium 367
Temperature and Pressure Dependence of μi 370
6.5 Summary 372
6.6 Problems 373
Conceptual Problems 373
Numerical Problems 377
CHAPTER 7 Phase Equilibria II: Fugacity 391
Learning Objectives 391
7.1 Introduction 391
7.2 The Fugacity 392
Definition of Fugacity 392
Criteria for Chemical Equilibria in Terms of Fugacity 395
7.3 Fugacity in the Vapor Phase 396
Fugacity and Fugacity Coefficient of Pure Gases 396
Fugacity and Fugacity Coefficient of Species i in a Gas Mixture 403
The Lewis Fugacity Rule 411
Property Changes of Mixing for Ideal Gases 412
7.4 Fugacity in the Liquid Phase 414
Reference States for the Liquid Phase 414
Thermodynamic Relations Between γi 422
Models for γi Using gE 428
Equation of State Approach to the Liquid Phase 449
7.5 Fugacity in the Solid Phase 449
Pure Solids 449
Solid Solutions 449
Interstitials and Vacancies in Crystals 450
7.6 Summary 450
7.7 Problems 452
Conceptual Problems 452
Numerical Problems 454
CHAPTER 8 Phase Equilibria III: Applications 466
Learning Objectives 466
8.1 Vaporâ"Liquid Equilibrium (VLE) 467
Raoultâs Law (Ideal Gas and Ideal Solution) 467
Nonideal Liquids 475
Azeotropes 484
Fitting Activity Coeffi cient Models with VLE Data 490
Solubility of Gases in Liquids 495
Vaporâ"Liquid Equilibrium Using the Equations of State Method 501
8.2 Liquid 1a2â"Liquid 1b2 Equilibrium: LLE 511
8.3 Vaporâ"Liquid 1a2â" Liquid 1b2 Equilibrium: VLLE 519
8.4 Solidâ"Liquid and Solidâ"Solid Equilibrium:
SLE and SSE 523
Pure Solids 523
Solid Solutions 529
8.5 Colligative Properties 531
Boiling Point Elevation and Freezing Point Depression 531
Osmotic Pressure 535
8.6 Summary 538
8.7 Problems 540
Conceptual Problems 540
Numerical Problems 544
CHAPTER 9 Chemical Reaction Equilibria 562
Learning Objectives 562
9.1 Thermodynamics and Kinetics 563
9.2 Chemical Reaction and Gibbs Energy 565
9.3 Equilibrium for a Single Reaction 568
9.4 Calculation of K from Thermochemical Data 572
Calculation of K from Gibbs Energy of Formation 572
The Temperature Dependence of K 574
9.5 Relationship Between the Equilibrium Constant and the Concentrations of Reacting Species 579
The Equilibrium Constant for a Gas-Phase Reaction 579
The Equilibrium Constant for a Liquid-Phase (or Solid-Phase) Reaction 586
The Equilibrium Constant for a Heterogeneous Reaction 587
9.6 Equilibrium in Electrochemical Systems 589
Electrochemical Cells 590
Shorthand Notation 591
Electrochemical Reaction Equilibrium 592
Thermochemical Data: Half-Cell Potentials 594
Activity Coeffi cients in Electrochemical Systems 597
9.7 Multiple Reactions 599
Extent of Reaction and Equilibrium Constant for R Reactions 599
Gibbs Phase Rule for Chemically Reacting Systems and Independent Reactions 601
Solution of Multiple Reaction Equilibria by Minimization of Gibbs Energy 610
9.8 Reaction Equilibria of Point Defects in Crystalline Solids 612
Atomic Defects 613
Electronic Defects 616
Effect of Gas Partial Pressure on Defect Concentrations 619
9.9 Summary 624
9.10 Problems 626
Conceptual Problems 626
Numerical Problems 628
APPENDIX A Physical Property Data 639
APPENDIX B Steam Tables 647
APPENDIX C Leeâ"Kesler Generalized Correlation Tables 660
APPENDIX D Unit Systems 676
APPENDIX E ThermoSolver Software 680
APPENDIX F References 685
Index 687
