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Fundamentals of Thermodynamics

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Fundamentals of Thermodynamics

Richard E. Sonntag
Claus Borgnakke
University of Michigan
GORDON J. VAN WYLEN
Hope College (emeritus)

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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

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