Engineering and Chemical Thermodynamics Book

CHAPTER 1 Measured Thermodynamic Properties and Other Basic Concepts 1

Learning Objectives 1

1.1 Thermodynamics 2

1.2 Preliminary Concepts—The Language of Thermo 3

1.3 Measured Thermodynamic Properties 7

1.4 Equilibrium 15

1.6 The PvT Surface and Its Projections for Pure Substances 20

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

2.2 Construction of Hypothetical Paths 46

2.3 Reversible and Irreversible Processes 48

2.4 The First Law of Thermodynamics for Closed Systems 55

2.5 The First Law of Thermodynamics for Open Systems 60

2.6 Thermochemical Data For U and H 67

2.7 Reversible Processes in Closed Systems 92

2.8 Open-System Energy Balances on Process Equipment 95

2.9 Thermodynamic Cycles and the Carnot Cycle 102

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

3.7 Calculation of Ds 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

3.10 Exergy (Availability) Analysis 172

3.11 Molecular View of Entropy 182

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

4.2 Intermolecular Forces 211

4.3 Equations of State 232

4.4 Generalized Compressibility Charts 246

4.5 Determination of Parameters for Mixtures 249

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

5.2 Thermodynamic Property Relationships 267

5.3 Calculation of Fundamental and Derived Properties Using Equations of State and Other Measured Quantities 276

5.4 Departure Functions 290

5.5 Joule-Thomson Expansion and Liquefaction 298

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

6.2 Pure Species Phase Equilibrium 318

6.3 Thermodynamics of Mixtures 334

6.4 Multicomponent Phase Equilibria 367

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

7.3 Fugacity in the Vapor Phase 396

7.4 Fugacity in the Liquid Phase 414

7.5 Fugacity in the Solid Phase 449

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 Vapor–Liquid Equilibrium (VLE) 467

8.2 Liquid 1a2—Liquid 1b2 Equilibrium: LLE 511

8.3 Vapor–Liquid 1a2— Liquid 1b2 Equilibrium: VLLE 519

8.4 Solid–Liquid and Solid–Solid Equilibrium: SLE and SSE 523

8.5 Colligative Properties 531

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

9.5 Relationship Between the Equilibrium Constant and the Concentrations of Reacting Species 579

9.6 Equilibrium in Electrochemical Systems 589

9.7 Multiple Reactions 599

9.8 Reaction Equilibria of Point Defects in Crystalline Solids 612

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 Lee–Kesler Generalized Correlation Tables 660

APPENDIX D Unit Systems 676

APPENDIX E ThermoSolver Software 680

APPENDIX F References 685

Index 687