1 Getting Started 1

1.1 Using Thermodynamics 2

1.2 Defining Systems 2

1.2.1 Closed Systems 4

1.2.2 Control Volumes 4

1.2.3 Selecting the System Boundary 5

1.3 Describing Systems and Their Behavior 6

1.3.1 Macroscopic and Microscopic Views of Thermodynamics 6

1.3.2 Property, State, and Process 7

1.3.3 Extensive and Intensive Properties 7

1.3.4 Equilibrium 8

1.4 Measuring Mass, Length, Time, and Force 8

1.4.1 SI Units 9

1.4.2 English Engineering Units 10

1.5 Specific Volume 11

1.6 Pressure 12

1.6.1 Pressure Measurement 12

1.6.2 Buoyancy 14

1.6.3 Pressure Units 14

1.7 Temperature 15

1.7.1 Thermometers 16

1.7.2 Kelvin and Rankine Temperature Scales 17

1.7.3 Celsius and Fahrenheit Scales 17

1.8 Engineering Design and Analysis 19

1.8.1 Design 19

1.8.2 Analysis 19

1.9 Methodology for Solving Thermodynamics Problems 20

Chapter Summary and Study Guide 22

2 Energy and the First Law of Thermodynamics 23

2.1 Reviewing Mechanical Concepts of Energy 24

2.1.1 Work and Kinetic Energy 24

2.1.2 Potential Energy 25

2.1.3 Units for Energy 26

2.1.4 Conservation of Energy in Mechanics 27

2.1.5 Closing Comment 27

2.2 Broadening Our Understanding of Work 27

2.2.1 Sign Convention and Notation 28

2.2.2 Power 29

2.2.3 Modeling Expansion or Compression Work 30

2.2.4 Expansion or Compression Work in Actual Processes 31

2.2.5 Expansion or Compression Work in Quasiequilibrium Processes 31

2.2.6 Further Examples of Work 34

2.2.7 Further Examples of Work in Quasiequilibrium Processes 35

2.2.8 Generalized Forces and Displacements 36

2.3 Broadening Our Understanding of Energy 36

2.4 Energy Transfer by Heat 37

2.4.1 Sign Convention, Notation, and Heat Transfer Rate 38

2.4.2 Heat Transfer Modes 39

2.4.3 Closing Comments 40

2.5 Energy Accounting: Energy Balance for Closed Systems 41

2.5.1 Important Aspects of the Energy Balance 43

2.5.2 Using the Energy Balance: Processes of Closed Systems 44

2.5.3 Using the Energy Rate Balance: Steady-State Operation 47

2.5.4 Using the Energy Rate Balance: Transient Operation 49

2.6 Energy Analysis of Cycles 50

2.6.1 Cycle Energy Balance 51

2.6.2 Power Cycles 52

2.6.3 Refrigeration and Heat Pump Cycles 52

2.7 Energy Storage 53

2.7.1 Overview 54

2.7.2 Storage Technologies 54

Chapter Summary and Study Guide 55

3 Evaluating Properties 57

3.1 Getting Started 58

3.1.1 Phase and Pure Substance 58

3.1.2 Fixing the State 58

3.2 p–υ–T Relation 59

3.2.1 p–υ–T Surface 60

3.2.2 Projections of the p–υ–T Surface 61

3.3 Studying Phase Change 63

3.4 Retrieving Thermodynamic Properties 65

3.5 Evaluating Pressure, Specific Volume, and Temperature 66

3.5.1 Vapor and Liquid Tables 66

3.5.2 Saturation Tables 68

3.6 Evaluating Specific Internal Energy and Enthalpy 72

3.6.1 Introducing Enthalpy 72

3.6.2 Retrieving u and h Data 72

3.6.3 Reference States and Reference Values 74

3.7 Evaluating Properties Using Computer Software 74

3.8 Applying the Energy Balance Using Property Tables and Software 76

3.8.1 Using Property Tables 77

3.8.2 Using Software 79

3.9 Introducing Specific Heats c_υ and c_p 80

3.10 Evaluating Properties of Liquids and Solids 82

3.10.1 Approximations for Liquids Using Saturated Liquid Data 82

3.10.2 Incompressible Substance Model 83

3.11 Generalized Compressibility Chart 85

3.11.1 Universal Gas Constant, R– 85

3.11.2 Compressibility Factor, Z 85

3.11.3 Generalized Compressibility Data, Z Chart 86

3.11.4 Equations of State 89

3.12 Introducing the Ideal Gas Model 90

3.12.1 Ideal Gas Equation of State 90

3.12.2 Ideal Gas Model 90

3.12.3 Microscopic Interpretation 92

3.13 Internal Energy, Enthalpy, and Specific Heats of Ideal Gases 92

3.13.1 Δu, Δh, c_υ , and c_p Relations 92

3.13.2 Using Specific Heat Functions 93

3.14 Applying the Energy Balance Using Ideal Gas Tables, Constant Specific Heats, and Software 95

3.14.1 Using Ideal Gas Tables 95

3.14.2 Using Constant Specific Heats 97

3.14.3 Using Computer Software 98

3.15 Polytropic Process Relations 100

Chapter Summary and Study Guide 102

4 Control Volume Analysis Using Energy 105

4.1 Conservation of Mass for a Control Volume 106

4.1.1 Developing the Mass Rate Balance 106

4.1.2 Evaluating the Mass Flow Rate 107

4.2 Forms of the Mass Rate Balance 107

4.2.1 One-Dimensional Flow Form of the Mass Rate Balance 108

4.2.2 Steady-State Form of the Mass Rate Balance 109

4.2.3 Integral Form of the Mass Rate Balance 109

4.3 Applications of the Mass Rate Balance 109

4.3.1 Steady-State Application 109

4.3.2 Time-Dependent (Transient) Application 110

4.4 Conservation of Energy for a Control Volume 112

4.4.1 Developing the Energy Rate Balance for a Control Volume 112

4.4.2 Evaluating Work for a Control Volume 113

4.4.3 One-Dimensional Flow Form of the Control Volume Energy Rate Balance 114

4.4.4 Integral Form of the Control Volume Energy Rate Balance 114

4.5 Analyzing Control Volumes at Steady State 115

4.5.1 Steady-State Forms of the Mass and Energy Rate Balances 115

4.5.2 Modeling Considerations for Control Volumes at Steady State 116

4.6 Nozzles and Diffusers 117

4.6.1 Nozzle and Diffuser Modeling Considerations 118

4.6.2 Application to a Steam Nozzle 118

4.7 Turbines 119

4.7.1 Steam and Gas Turbine Modeling Considerations 120

4.7.2 Application to a Steam Turbine 121

4.8 Compressors and Pumps 122

4.8.1 Compressor and Pump Modeling Considerations 122

4.8.2 Applications to an Air Compressor and a Pump System 122

4.8.3 Pumped-Hydro and Compressed-Air Energy Storage 125

4.9 Heat Exchangers 126

4.9.1 Heat Exchanger Modeling Considerations 127

4.9.2 Applications to a Power Plant Condenser and Computer Cooling 128

4.10 Throttling Devices 130

4.10.1 Throttling Device Modeling Considerations 130

4.10.2 Using a Throttling Calorimeter to Determine Quality 131

4.11 System Integration 132

4.12 Transient Analysis 135

4.12.1 The Mass Balance in Transient Analysis 135

4.12.2 The Energy Balance in Transient Analysis 135

4.12.3 Transient Analysis Applications 136

Chapter Summary and Study Guide 142

5 The Second Law of Thermodynamics 145

5.1 Introducing the Second Law 146

5.1.1 Motivating the Second Law 146

5.1.2 Opportunities for Developing Work 147

5.1.3 Aspects of the Second Law 148

5.2 Statements of the Second Law 149

5.2.1 Clausius Statement of the Second Law 149

5.2.2 Kelvin–Planck Statement of the Second Law 149

5.2.3 Entropy Statement of the Second Law 151

5.2.4 Second Law Summary 151

5.3 Irreversible and Reversible Processes 151

5.3.1 Irreversible Processes 152

5.3.2 Demonstrating Irreversibility 153

5.3.3 Reversible Processes 155

5.3.4 Internally Reversible Processes 156

5.4 Interpreting the Kelvin–Planck Statement 157

5.5 Applying the Second Law to Thermodynamic Cycles 158

5.6 Second Law Aspects of Power Cycles Interacting with Two Reservoirs 159

5.6.1 Limit on Thermal Efficiency 159

5.6.2 Corollaries of the Second Law for Power Cycles 160

5.7 Second Law Aspects of Refrigeration and Heat Pump Cycles Interacting with Two Reservoirs 161

5.7.1 Limits on Coefficients of Performance 161

5.7.2 Corollaries of the Second Law for Refrigeration and Heat Pump Cycles 162

5.8 The Kelvin and International Temperature Scales 163

5.8.1 The Kelvin Scale 163

5.8.2 The Gas Thermometer 164

5.8.3 International Temperature Scale 165

5.9 Maximum Performance Measures for Cycles Operating Between Two Reservoirs 166

5.9.1 Power Cycles 167

5.9.2 Refrigeration and Heat Pump Cycles 168

5.10 Carnot Cycle 171

5.10.1 Carnot Power Cycle 171

5.10.2 Carnot Refrigeration and Heat Pump Cycles 172

5.10.3 Carnot Cycle Summary 173

5.11 Clausius Inequality 173

Chapter Summary and Study Guide 175

6 Using Entropy 177

6.1 Entropy–A System Property 178

6.1.1 Defining Entropy Change 178

6.1.2 Evaluating Entropy 179

6.1.3 Entropy and Probability 179

6.2 Retrieving Entropy Data 179

6.2.1 Vapor Data 180

6.2.2 Saturation Data 180

6.2.3 Liquid Data 180

6.2.4 Computer Retrieval 181

6.2.5 Using Graphical Entropy Data 181

6.3 Introducing the T dS Equations 182

6.4 Entropy Change of an Incompressible Substance 184

6.5 Entropy Change of an Ideal Gas 184

6.5.1 Using Ideal Gas Tables 185

6.5.2 Assuming Constant Specific Heats 186

6.5.3 Computer Retrieval 187

6.6 Entropy Change in Internally Reversible Processes of Closed Systems 187

6.6.1 Area Representation of Heat Transfer 188

6.6.2 Carnot Cycle Application 188

6.6.3 Work and Heat Transfer in an Internally Reversible Process of Water 189

6.7 Entropy Balance for Closed Systems 190

6.7.1 Interpreting the Closed System Entropy Balance 191

6.7.2 Evaluating Entropy Production and Transfer 192

6.7.3 Applications of the Closed System Entropy Balance 192

6.7.4 Closed System Entropy Rate Balance 195

6.8 Directionality of Processes 196

6.8.1 Increase of Entropy Principle 196

6.8.2 Statistical Interpretation of Entropy 198

6.9 Entropy Rate Balance for Control Volumes 200

6.10 Rate Balances for Control Volumes at Steady State 201

6.10.1 One-Inlet, One-Exit Control Volumes at Steady State 202

6.10.2 Applications of the Rate Balances to Control Volumes at Steady State 202

6.11 Isentropic Processes 207

6.11.1 General Considerations 207

6.11.2 Using the Ideal Gas Model 208

6.11.3 Illustrations: Isentropic Processes of Air 210

6.12 Isentropic Efficiencies of Turbines, Nozzles, Compressors, and Pumps 212

6.12.1 Isentropic Turbine Efficiency 212

6.12.2 Isentropic Nozzle Efficiency 215

6.12.3 Isentropic Compressor and Pump Efficiencies 216

6.13 Heat Transfer and Work in Internally Reversible, Steady-State Flow Processes 218

6.13.1 Heat Transfer 218

6.13.2 Work 219

6.13.3 Work in Polytropic Processes 220

Chapter Summary and Study Guide 222

7 Exergy Analysis 225

7.1 Introducing Exergy 226

7.2 Conceptualizing Exergy 227

7.2.1 Environment and Dead State 227

7.2.2 Defining Exergy 228

7.3 Exergy of a System 228

7.3.1 Exergy Aspects 230

7.3.2 Specific Exergy 230

7.3.3 Exergy Change 232

7.4 Closed System Exergy Balance 233

7.4.1 Introducing the Closed System Exergy Balance 233

7.4.2 Closed System Exergy Rate Balance 236

7.4.3 Exergy Destruction and Loss 237

7.4.4 Exergy Accounting 239

7.5 Exergy Rate Balance for Control Volumes at Steady State 240

7.5.1 Comparing Energy and Exergy for Control Volumes at Steady State 242

7.5.2 Evaluating Exergy Destruction in Control Volumes at Steady State 243

7.5.3 Exergy Accounting in Control Volumes at Steady State 246

7.6 Exergetic (Second Law) Efficiency 249

7.6.1 Matching End Use to Source 249

7.6.2 Exergetic Efficiencies of Common Components 251

7.6.3 Using Exergetic Efficiencies 253

7.7 Thermoeconomics 253

7.7.1 Costing 254

7.7.2 Using Exergy in Design 254

7.7.3 Exergy Costing of a Cogeneration System 256

Chapter Summary and Study Guide 260

8 Vapor Power Systems 261

8.1 Introducing Vapor Power Plants 266

8.2 The Rankine Cycle 268

8.2.1 Modeling the Rankine Cycle 269

8.2.2 Ideal Rankine Cycle 271

8.2.3 Effects of Boiler and Condenser Pressures on the Rankine Cycle 274

8.2.4 Principal Irreversibilities and Losses 276

8.3 Improving Performance—Superheat, Reheat, and Supercritical 279

8.4 Improving Performance—Regenerative Vapor Power Cycle 284

8.4.1 Open Feedwater Heaters 284

8.4.2 Closed Feedwater Heaters 287

8.4.3 Multiple Feedwater Heaters 289

8.5 Other Vapor Power Cycle Aspects 292

8.5.1 Working Fluids 292

8.5.2 Cogeneration 293

8.5.3 Carbon Capture and Storage 295

8.6 Case Study: Exergy Accounting of a Vapor Power Plant 296

Chapter Summary and Study Guide 301

9 Gas Power Systems 303

9.1 Introducing Engine Terminology 304

9.2 Air-Standard Otto Cycle 306

9.3 Air-Standard Diesel Cycle 311

9.4 Air-Standard Dual Cycle 314

9.5 Modeling Gas Turbine Power Plants 317

9.6 Air-Standard Brayton Cycle 318

9.6.1 Evaluating Principal Work and Heat Transfers 318

9.6.2 Ideal Air-Standard Brayton Cycle 319

9.6.3 Considering Gas Turbine Irreversibilities and Losses 324

9.7 Regenerative Gas Turbines 326

9.8 Regenerative Gas Turbines with Reheat and Intercooling 329

9.8.1 Gas Turbines with Reheat 329

9.8.2 Compression with Intercooling 331

9.8.3 Reheat and Intercooling 335

9.8.4 Ericsson and Stirling Cycles 337

9.9 Gas Turbine–Based Combined Cycles 339

9.9.1 Combined Gas Turbine–Vapor Power Cycle 339

9.9.2 Cogeneration 344

9.10 Integrated Gasification Combined-Cycle Power Plants 344

9.11 Gas Turbines for Aircraft Propulsion 346

9.12 Compressible Flow Preliminaries 350

9.12.1 Momentum Equation for Steady One-Dimensional Flow 350

9.12.2 Velocity of Sound and Mach Number 351

9.12.3 Determining Stagnation State Properties 353

9.13 Analyzing One-Dimensional Steady Flow in Nozzles and Diffusers 353

9.13.1 Exploring the Effects of Area Change in Subsonic and Supersonic Flows 353

9.13.2 Effects of Back Pressure on Mass Flow Rate 356

9.13.3 Flow Across a Normal Shock 358

9.14 Flow in Nozzles and Diffusers of Ideal Gases with Constant Specific Heats 359

9.14.1 Isentropic Flow Functions 359

9.14.2 Normal Shock Functions 362

Chapter Summary and Study Guide 366

10 Refrigeration and Heat Pump Systems 369

10.1 Vapor Refrigeration Systems 370

10.1.1 Carnot Refrigeration Cycle 370

10.1.2 Departures from the Carnot Cycle 371

10.2 Analyzing Vapor-Compression Refrigeration Systems 372

10.2.1 Evaluating Principal Work and Heat Transfers 372

10.2.2 Performance of Ideal Vapor-Compression Systems 373

10.2.3 Performance of Actual Vapor-Compression Systems 375

10.2.4 The p–h Diagram 378

10.3 Selecting Refrigerants 379

10.4 Other Vapor-Compression Applications 382

10.4.1 Cold Storage 382

10.4.2 Cascade Cycles 383

10.4.3 Multistage Compression with Intercooling 384

10.5 Absorption Refrigeration 385

10.6 Heat Pump Systems 386

10.6.1 Carnot Heat Pump Cycle 387

10.6.2 Vapor-Compression Heat Pumps 387

10.7 Gas Refrigeration Systems 390

10.7.1 Brayton Refrigeration Cycle 390

10.7.2 Additional Gas Refrigeration Applications 394

10.7.3 Automotive Air Conditioning Using Carbon Dioxide 395

Chapter Summary and Study Guide 396

11 Thermodynamic Relations 399

11.1 Using Equations of State 400

11.1.1 Getting Started 400

11.1.2 Two-Constant Equations of State 401

11.1.3 Multiconstant Equations of State 404

11.2 Important Mathematical Relations 405

11.3 Developing Property Relations 408

11.3.1 Principal Exact Differentials 408

11.3.2 Property Relations from Exact Differentials 409

11.3.3 Fundamental Thermodynamic Functions 413

11.4 Evaluating Changes in Entropy, Internal Energy, and Enthalpy 414

11.4.1 Considering Phase Change 414

11.4.2 Considering Single-Phase Regions 417

11.5 Other Thermodynamic Relations 422

11.5.1 Volume Expansivity, Isothermal and Isentropic Compressibility 422

11.5.2 Relations Involving Specific Heats 423

11.5.3 Joule–Thomson Coefficient 426

11.6 Constructing Tables of Thermodynamic Properties 428

11.6.1 Developing Tables by Integration Using p–υ –T and Specific Heat Data 428

11.6.2 Developing Tables by Differentiating a Fundamental Thermodynamic Function 430

11.7 Generalized Charts for Enthalpy and Entropy 432

11.8 p–υ–T Relations for Gas Mixtures 438

11.9 Analyzing Multicomponent Systems 442

11.9.1 Partial Molal Properties 443

11.9.2 Chemical Potential 445

11.9.3 Fundamental Thermodynamic Functions for Multicomponent Systems 446

11.9.4 Fugacity 448

11.9.5 Ideal Solution 451

11.9.6 Chemical Potential for Ideal Solutions 452

Chapter Summary and Study Guide 453

12 Ideal Gas Mixture and Psychrometric Applications 457

12.1 Describing Mixture Composition 458

12.2 Relating p, V, and T for Ideal Gas Mixtures 461

12.3 Evaluating U, H, S, and Specific Heats 463

12.3.1 Evaluating U and H 463

12.3.2 Evaluating c_υ and c_p 463

12.3.3 Evaluating S 464

12.3.4 Working on a Mass Basis 464

12.4 Analyzing Systems Involving Mixtures 465

12.4.1 Mixture Processes at Constant Composition 465

12.4.2 Mixing of Ideal Gases 470

12.5 Introducing Psychrometric Principles 474

12.5.1 Moist Air 474

12.5.2 Humidity Ratio, Relative Humidity, Mixture Enthalpy, and Mixture Entropy 475

12.5.3 Modeling Moist Air in Equilibrium with Liquid Water 477

12.5.4 Evaluating the Dew Point Temperature 478

12.5.5 Evaluating Humidity Ratio Using the Adiabatic-Saturation Temperature 482

12.6 Psychrometers: Measuring the Wet-Bulb and Dry-Bulb Temperatures 483

12.7 Psychrometric Charts 484

12.8 Analyzing Air-Conditioning Processes 486

12.8.1 Applying Mass and Energy Balances to Air-Conditioning Systems 486

12.8.2 Conditioning Moist Air at Constant Composition 488

12.8.3 Dehumidification 490

12.8.4 Humidification 493

12.8.5 Evaporative Cooling 494

12.8.6 Adiabatic Mixing of Two Moist Air Streams 496

12.9 Cooling Towers 499

Chapter Summary and Study Guide 501

13 Reacting Mixtures and Combustion 503

13.1 Introducing Combustion 504

13.1.1 Fuels 505

13.1.2 Modeling Combustion Air 505

13.1.3 Determining Products of Combustion 508

13.1.4 Energy and Entropy Balances for Reacting Systems 511

13.2 Conservation of Energy—Reacting Systems 511

13.2.1 Evaluating Enthalpy for Reacting Systems 511

13.2.2 Energy Balances for Reacting Systems 514

13.2.3 Enthalpy of Combustion and Heating Values 520

13.3 Determining the Adiabatic Flame Temperature 523

13.3.1 Using Table Data 523

13.3.2 Using Computer Software 523

13.3.3 Closing Comments 525

13.4 Fuel Cells 526

13.4.1 Proton Exchange Membrane Fuel Cell 527

13.4.2 Solid Oxide Fuel Cell 529

13.5 Absolute Entropy and the Third Law of Thermodynamics 530

13.5.1 Evaluating Entropy for Reacting Systems 530

13.5.2 Entropy Balances for Reacting Systems 531

13.5.3 Evaluating Gibbs Function for Reacting Systems 534

13.6 Conceptualizing Chemical Exergy 536

13.6.1 Working Equations for Chemical Exergy 538

13.6.2 Evaluating Chemical Exergy for Several Cases 538

13.6.3 Closing Comments 540

13.7 Standard Chemical Exergy 540

13.7.1 Standard Chemical Exergy of a Hydrocarbon: C_aH_b 541

13.7.2 Standard Chemical Exergy of Other Substances 544

13.8 Applying Total Exergy 545

13.8.1 Calculating Total Exergy 545

13.8.2 Calculating Exergetic Efficiencies of Reacting Systems 549

Chapter Summary and Study Guide 552

14 Chemical and Phase Equilibrium 555

14.1 Introducing Equilibrium Criteria 556

14.1.1 Chemical Potential and Equilibrium 557

14.1.2 Evaluating Chemical Potentials 559

14.2 Equation of Reaction Equilibrium 560

14.2.1 Introductory Case 560

14.2.2 General Case 561

14.3 Calculating Equilibrium Compositions 562

14.3.1 Equilibrium Constant for Ideal Gas Mixtures 562

14.3.2 Illustrations of the Calculation of Equilibrium Compositions for Reacting Ideal Gas Mixtures 565

14.3.3 Equilibrium Constant for Mixtures and Solutions 569

14.4 Further Examples of the Use of the Equilibrium Constant 570

14.4.1 Determining Equilibrium Flame Temperature 570

14.4.2 Van’t Hoff Equation 573

14.4.3 Ionization 574

14.4.4 Simultaneous Reactions 575

14.5 Equilibrium between Two Phases of a Pure Substance 578

14.6 Equilibrium of Multicomponent, Multiphase Systems 579

14.6.1 Chemical Potential and Phase Equilibrium 580

14.6.2 Gibbs Phase Rule 582

Chapter Summary and Study Guide 583

Appendix Tables, Figures, and Charts A-1

Index to Tables in SI Units A-1

Index to Tables in English Units A-49

Index to Figures and Charts A-97

Exercises and Problems P-1

Chapter 1 P-1

Chapter 2 P-8

Chapter 3 P-17

Chapter 4 P-28

Chapter 5 P-42

Chapter 6 P-52

Chapter 7 P-67

Chapter 8 P-82

Chapter 9 P-97

Chapter 10 P-112

Chapter 11 P-122

Chapter 12 P-129

Chapter 13 P-141

Chapter 14 P-150

Index I-1

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