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### Fundamentals of Thermodynamics

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Engineering Heat Transfer

Thermodynamics Engineering

Fundamentals of Thermodynamics

Richard E. Sonntag

Claus Borgnakke

University of Michigan

GORDON J. VAN WYLEN

Hope College (emeritus)

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Open: Fundamentals of Thermodynamics

PREFACE

In this edition we have incorporated a number of developments and approaches included in our recent textbook, Introduction to Engineering Thermodynamics, Richard E. Sonntag and Claus Borgnakke, John Wiley & Sons, Inc. (2001). In Chapter 3, we first introduce thermodynamic tables, and then note the behavior of superheated vapor at progressively lower densities, which leads to the definition of the ideal gas model, then the compres- sibility factor and equations of state. In Chapter 5, the result of ideal gas energy depend- ing only on temperature follows the examination of steam table values at different temperatures and pressures. Second law presentation in Chapter 7 is streamlined, with better integration of the concepts of thermodynamic temperature and ideal gas tempera- ture. Coverage of ideal gas and ideal gas mixtures focuses on unit mass basis, instead of mole basis, and is simpler. Development of availability and reversible work in Chapter 10 focuses on the steady-state process, and leads to the general expression for exergy. We have therefore included a new section on the general exergy balance to amplify the con- cept of transport and destruction of exergy. The chapter with property relations is slightly reorganized and streamlined to also focus on properties on a mass basis. Due to current technology developments we have expanded our discussion of the fuel cells and also up- dated the chapter with combustion.

TOC

Some Introductory Comments 1

1.1 The Simple Steam Power Plant, 1

1.2 Fuel Cells, 2

1 .3 The Vapor-Compression-Refrigeration Cycle, 5

1.4 The Thermoelectric Refrigerator, 7

1.5 The Air Separation Plant, 8

1.6 The Gas Turbine, 9

1.7 The Chemical Rocket Engine, 11

1.8 Other Applications and Environmental Issues, 72

SOME CONCEPTS AND DEFINITIONS 14

2. 1 A Thermodynamic System and the Control Volume, 14

2.2 Macroscopic Versus Microscopic Point of View, 15

2.3 Properties and State of a Substance, 16

2.4 Processes and Cycles, 17

2.5 Units for Mass, Length, Time, and Force, 18

2.6 Energy, 21

2.7 Specific Volume and Density, 23

2.8 Pressure, 25

2.9 Equality of Temperature, 31

2.10 The Zeroth Law of Thermodynamics, 31

2. 11 Temperature Scales, 32

Problems, 34

PROPERTIES OF A PURE SUBSTANCE 43

3 . 1 The Pure Substance, 44

3.2 Vapor-Liquid-Solid-Phase Equilibrium in a Pure Substance, 44

3.3 Independent Properties of a Pure Substance, 51

3.4 Tables of Thermodynamic Properties, 51

3.5 Thermodynamic Surfaces, 59

3.6 The P- V-TBehavior ofLow- and Moderate-Density Gases, 61

3.7 Computerized Tables, 69

Problems, 72

WORK AND HEAT 84

4.1 Definition ofWork, 84

4.2 Units for Work, 86

4.3 Work Done at the Moving Boundary of a Simple Compressible System, 87

4.4 Other Systems that Involve Work, 96

4.5 Concluding Remarks Regarding Work, 98

4.6 Definition of Heat, 100

4.7 Heat Transfer Modes, 101

4.8 Comparison of Heat and Work, JOS

Problems, 105

The First Law of thermodynamics 116

5.1 The First Law of Thermodynamics for a Control Mass Undergoing a Cycle, 116

5.2 The First Law ofThermodynamics for a Change in State of a Control Mass, 117

5.3 Internal Energy—A Thermodynamic Property, 124

5.4 Problem Analysis and Solution Technique, 126

5.5 The Thermodynamic Property Enthalpy, 130

5.6 The Constant-Volume and Constant-Pressure Specific Heats, 133

5.7 The Internal Energy, Enthalpy, and Specific Heat of Ideal Gases, 135

5.8 The First Law as a Rate Equation, 141

5.9 Conservation of Mass, 143

Problems, 145

First Law analysis for a Control volume 162

6.1 Conservation of Mass and the Control Volume, 162

6.2 The First Law ofThermodynamics for a Control Volume, 165

6.3 The Steady-State Process, 1 67

6.4 Examples of Steady-State Processes, 169

6.5 The Transient Process, 183

Problems, 195

The Second Law of thermodynamics 214

7.1 Heat Engines and Refrigerators, 214

7.2 The Second Law of Thermodynamics, 220

7.3 The Reversible Process, 223

7.4 Factors that Render Processes Irreversible, 224

7.5 The Camot Cycle, 227

7.6 Two Propositions Regarding the Efficiency of a Carnot Cycle, 229

7.7 The Thermodynamic Temperature Scale, 230

7.8 The Ideal-Gas Temperature Scale, 233

7.9 Ideal versus Real Machines, 236

Problems, 240

8.1 The Inequality of Clausius, 251

8.2 Entropy—A Property of a System, 255

8.3 The Entropy of a Pure Substance, 257

8.4 Entropy Change in Reversible Processes, 259

8.5 The Thermodynamic Property Relation, 263

8.6 Entropy Change of a Control Mass During an Irreversible Process, 264

8.7 Entropy Generation, 266

8.8 Principle of the Increase of Entropy, 268

8.9 Entropy Change of a Solid or Liquid, 272

8.10 Entropy Change of an Ideal Gas, 273

8.11 The Reversible Polytropic Process for an Ideal Gas, 2 78

8.12 Entropy as a Rate Equation, 282

Problems, 285

SECOND LAW ANALYSIS FOR A CONTROL VOLUME 302

9. 1 The Second Law ofThermodynamics for a Control Volume, 302

9.2 The Steady-State Process and the Transient Process, 304

9.3 The Reversible Steady-State Process, 313

9.4 Principle of the Increase of Entropy, 316

9.5 Efficiency, 317

9.6 Some General Comments Regarding Entropy, 323

Problems, 325

IRREVERSIBILITY AND AVAILABILITY 343

1 0. 1 Available Energy, Reversible Work, and Irreversibility, 343

10.2 Availability and Second-Law Efficiency, 355

10.3 Exergy Balance Equation, 363

Problems, 370

POWER AND REFRIGERATION SYSTEMS 382

11.1 Introduction to Power Systems, 382

11 .2 The Rankine Cycle, 384

1 1 .3 Effect of Pressure and Temperature on the Rankine Cycle, 388

11.4 The Reheat Cycle, 393

11.5 The Regernative Cycle, 396

1 1 .6 Deviation of Actual Cycles from Ideal Cycles, 403

1 1 .7 Cogeneration, 409

11.8 Air-Standard Power Cycles, 41

11.9 The Brayton Cycle, 411

11.10 The Simple Gas-Turbine Cycle with a Regenerator, 418

11.11 Gas-Turbine Power Cycle Configurations, 421

1 1.12 The Air-Standard Cycle for Jet Propulsion, 424

11.13 Reciprocating Engine Power Cycles, 426

11.14 The Otto Cycle, 427

1 1.15 The Diesel Cycle, 431

11.16 The Stirling Cycle, 433

11.17 Introduction to Refrigeration Systems, 434

1 1.18 The Vapor-Compression Refrigeration Cycle, 435

11.19 Working Fluids for Vapor-Compression Refrigeration Systems, 438

1 1.20 Deviation of the Actual Vapor-Compression Refrigeration Cycle from the Ideal Cycle, 439

1 1 .2 1 The Ammonia Absorption Refrigeration Cycle, 441

1 1.22 The Air-Standard Refrigeration Cycle, 442

1 1.23 Combined-Cycle Power and Refrigeration Systems, 446

Problems, 450

GAS MIXTURES 473

12.1 General Considerations and Mixtures of Ideal Gases, 473

12.2 A Simplified Model of a Mixture Involving Gases and a Vapor, 480

12.3 The First Law Applied to Gas-Vapor Mixtures, 485

12.4 The Adiabatic Saturation Process, 488

12.5 Wet-Bulb and Dry-Bulb Temperatures, 490

12.6 The Psychrometric Chart, 491

Problems, 494

THERMODYNAMIC RELATIONS 511

13.1 The Clapeyron Equation, 51

1

13.2 Mathematical Relations for a Homogeneous Phase, 515

13.3 The Maxwell Relations, 516

13.4 Thermodynamic Relations Involving Enthalpy, Internal Energy, and Entropy, 519

13.5 Volume Expansivity and Isothermal and Adiabatic Compressibility, 524

13.6 Real Gas Behavior and Equations of State, 527

13.7 The Generalized Chart for Changes of Enthalpy at Constant Temperature, 532

13.8 The Generalized Chart for Changes of Entropy at Constant Temperature, 535

13.9 Developing Tables ofThermodynamic Properties from Experimental Data, 538

13.10 The Property Relation for Mixtures, 540

13.11 Pseudopure Substance Models for Real-Gas Mixtures, 543

Problems, 550

CHEMICAL REACTIONS 561

14.1 Fuels, 561

14.2 The Combustion Process, 564

14.3 Enthalpy of Formation, 572

14.4 First-Law Analysis of Reacting Systems, 574

14.5 Enthalpy and Internal Energy of Combustion; Heat of Reaction, 581

14.6 Adiabatic Flame Temperature, 585

14.7 The Third Law of Thermodynamics and Absolute Entropy, 557

14.8 Second-Law Analysis of Reacting Systems, 589

14.9 Fuel Cells, 596

14.10 Evaluation of Actual Combustion Processes, 599

Problems, 604

introduction to Phase and Chemical equilibrium 61

15.1 Requirements for Equilibrium, 617

15.2 Equilibrium Between Two Phases of a Pure Substance, 619

15.3 Metastable Equilibrium, 623

15.4 Chemical Equilibrium, 625

15.5 Simultaneous Reactions, 634

15.6 Ionization, 638

Problems, 643

COMPRESSIBLE FLOW W16-1

{available on the website: www.wiley.com/college/sonntag)

16.1 Stagnation Properties, W16-1

16.2 The Momentum Equation for a Control Volume, W16-3

16.3 Forces Acting on a Control Surface, W16-6

16.4 Adiabatic, One-Dimensional, Steady-State Flow of an Incompressible Fluid Through a Nozzle, W16-8

16.5 Velocity of Sound in an Ideal Gas, W16-10

1 6.6 Reversible, Adiabatic, One-Dimensional Flow of an Ideal Gas through a Nozzle, W16-12

16.7 Mass Rate ofFlow of an Ideal Gas through an Isentropic Nozzle, W16-16

16.8 Normal Shock in an Ideal Gas Flowing through a Nozzle, W16-20

16.9 Nozzle and Diffuser Coefficients, W16-26

16.10 Nozzle and Orifices as Flow-Measuring Devices, W16-28

Problems, W16-37

CONTENTS OF APPENDIX

Appendix A SI units: Single State properties 653

Appendix B SI Units: Thermodynamic Tables 673

Appendix C Ideal-Gas Specific Heat 723

Appendix D equations of State 725

appendix E Figures 731

Appendix F English Unit Tables 737

ANSWERS TO SELECTED PROBLEMS 779

INDEX 789