CHAPTER ONEBASICCONCEPTSOFTHERMODYNAMICS

1-1

1-2

1-31-41-51-6

1-7

1-8

1-9

Thermodynamics and Energy 2

ApplicationAreasof Thermodynamics 3

A Note on Dimensions and Units 3

SomeSI and EnglishUnits 5DimensionalHomogeneity 7

Closed and Open SystemsProperties of a System 10

State and Equilibrium 12Processes and Cycles 13The Steady-Flow Process 14

Forms of Energy 14SomePhysical Insightto Internal Energy 16Moreon Nuclear Energy 18

8

Energy and Environment 19Ozoneand Smog 21Acid Rain 21

The GreenhouseEffect:GlobalWarmingand ClimateChange 22

Temperature and the Zeroth Law ofThermodynamics 25TemperatureScales 25

1-10 Pressure 28

Variationof Pressurewith Depth 30

1-11 The Manometer 33OtherPressureMeasurementDevices 35

1-12 Barometer and the Atmospheric Pressure

1-13 Problem-Solving Technique 38ARemarkofSignificantDigits 40EngineeringSoftwarePackages41EngineeringEquationSolver(EES) 42

Topics of Special Interest: ThermodynamicAspects of Biological Systems 43Foodand Exercise 45Dieting 48

36

Summary 51Referencesand SuggestedReading 51Problems 52

CHAPTER TWOPROPERTIESOFPURESUBSTANCES63

2-12-22-3

Pure Substance 64Phases of a Pure Substance

Phase-Change Processes ofPure Substances 65

64

2-4

CompressedLiquid and SaturatedLiquid 65SaturatedVaporand SuperheatedVapor 66SaturationTemperatureandSaturationPressure 67SomeConsequencesof Tsatand PsatDependence 68

Property Diagrams forPhase-Change Processes 701 The T-vDiagram 702 The P-vDiagram 71Extendingthe Diagramsto Include the Solid Phase 733 The P-T Diagram 74The P-v-TSurface 76

2-5 Property Tables 77Enthalpy-A CombinationProperty 77la SaturatedLiquid and SaturatedVaporStates 78Ib SaturatedLiquid-Vapor Mixture 792 SuperheatedVapor 833 Compressed Liquid 84ReferenceStateand ReferenceValues 85

The Ideal-Gas Equation of State 87

Is WaterVaporan IdealGas? 89

Compressibility Factor-A Measure ofDeviation from Ideal-Gas Behavior 89

Other Equations of State 94Van der WaalsEquationof State 94Beattie-BridgemanEquationof State 95Benedict-Webb-RubinEquationof State 95Virial Equationof State 96

2-6

2-7

2-8

2-9 Specific Heats 98

vii

2-10 Internal Energy, Enthalpy, and Specific Heats ofIdeal Gases 100

Specific-Heat Relations of Ideal Gases 103

2-11 Internal Energy, Enthalpy, and Specific Heats ofSolids and Liquids 105Internal Energy Changes 106Enthalpy Changes 106

Topics of Special Interest:Vapor Pressure and Phase EquilibriumSummary 111References and Suggested Reading 112Problems 112

107

CHAPTER THREEENERGYTRANSFERBYHEAT,WORK,ANDMASS 123

3-1 Heat Transfer 124

Historical Background on Heat 125

3-2 Energy Transfer by WorkElectrical Work 129

126

3-3 Mechanical Forms of Work 129

3-43-5

1 Moving Boundary Work 1302 Shaft Work 136

3 Spring Work 1374 Other Mechanical Forms of Work 138

Nonmechanical Forms of Work 140

Conservation of Mass Principle 141Mass and Volume Flow Rates 141

Conservation of Mass Principle 143Mass Balance for Steady-Flow Processes 144

3-6 Flow Work and the Energyof a Flowing Fluid 147

Total Energy of a Flowing Fluid 148Energy Transport by Mass 148

Topics of Special Interest:Mechanisms of Heat Transfer 150

Summary 155Referencesand SuggestedReading 156Problems 156

CHAPTER FOURTHEFIRSTLAWOFTHERMODYNAMICS

4-1

165

The First Law of ThermodynamicsEnergyBalance 167

166

4-24-3

Energy Change of a System, 6.Esystem 168Mechanisms of Energy Transfer, E;nand Eout 168

Energy Balance for Closed Systems 170

Energy Balance for Steady-Flow Systems 181

4-4Energy Balance for Steady-Flow Systems 182

Some Steady-Flow Engineering Devices

1 Nozzlesand Diffusers 1842 Turbinesand Compressors 1883 ThrottlingValves 1904a MixtureChambers 1924b Heat Exchangers 1935 Pipeand DuctFlow 196

Energy Balance forUnsteady-Flow Processes 197Mass Balance 198EnergyBalance 198

Topics of Special Interest:

Refrigeration and Freezing 9f FoodsThermalPropertiesof Foods 205Refrigeration of Fruits and Vegetables 207Refrigeration of Meats 208Poultry Products 209

Summary 214Referenced and Suggested Reading 215Problems 216

184

4-5

203

CHAPTER FIVETHESECONDLAWOFTHERMODYNAMICS245

5-15-25-3

Introduction to the Second Law 246

Thermal Energy Reservoirs 247

Heat Engines 247

CanWeSave Ouot? 250The Second Law of Thermodynamics: Kelvin-Planck

Statement 253

5-45-5

Energy Conversion Efficiencies 253

Refrigerators and Heat Pumps 257CoefficientPerformance 258Heat Pumps 259The Second Lawof Thermodynamics:

ClausiusStatement 262Equivalence of the Two Statements 262

5-65-7

Perpetual-Motion Machines 263Reversible and Irreversible Processes 265

Irreversibilities 267

Internally and Externally Reversible Processes 268

5-8 The Carnot Cycle 269

The Reversed Carnot Cycle 271

5-9 The Carnot Principles 2715-1 0 The Thermodynamic Temperature Scale5-11 The Carnot Heat Engine 275

The Qualityof Energy 276QuantityversusQuality in DailyLife 277

5-12 The Carnot Refrigerator and Heat PumpTopics of Special Interest:Household Refrigerators 281

Summary 285Referencesand SuggestedReading 286Problems 286

272

278

CHAPTERENTROPY301

SIX

6-1 Entropy 302ASpecialCase:Internally Reversible

IsothermalHeatTransferProcesses 304

The Increase of Entropy Principle 305Some Remarksabout Entropy 307

Entropy Change of Pure Substances 309Isentropic Processes 313Property Diagrams Involving Entropy 314

What Is Entropy? 316Entropyand EntropyGenerationin DailyLife 318

6-2

6-36-46-56-6

6-76-86-9

The T ds Relations 319

Entropy Change of Liquids and Solids 321

The Entropy Change of Ideal Gases 324ConstantSpecific Heats(ApproximateAnalysis) 325VariableSpecific Heats(ExactAnalysis) 326IsentropicProcessesof IdealGases 327ConstantSpecific Heats(ApproximateAnalysis) 328VariableSpecific Heats(ExactAnalysis) 328RelativePressureand RelativeSpecificVolume 329

6-10 Reversible Steady-Flow Work 332

Proofthat Steady-FlowDevicesDeliverthe MostandConsumethe LeastWorkwhen the ProcessIsReversible 335

6-11 Minimizing the Compressor Work 336

MultistageCompressionwith Intercooling 337

6-12 Isentropic Efficiencies ofSteady-Flow Devices 340IsentropicEfficiencyof Turbines 341IsentropicEfficienciesof Compressorsand Pumps 343IsentropicEfficiencyof Nozzles 345

6-13 Entropy Balance 347

~"r"i".c.'i:_~i'.r:~;)[tf'::~ft::l~ix ~0:;,:;;~,:7lt:t1;~jf!a~~Iiif:'f";.,"'. .':.CONTENTS

EntropyChangeof a System,Ssystem 348Mechanismsof EntropyTransfer,Sinand Soul 348Entropy Generation, Sgen 350Closed Systems 351Control Volumes 351

Entropy Generation Associated with aHeat Transfer Process 358

Topics of Special Interest:Reducing the Cost of Compressed Air 360

Summary 370ReferencesandSuggestedReading 372Problems 372

CHAPTER SEVENEXERGY:A MEASUREOFWORKPOTENTIAL391

7-1 Exergy: Work Potential of Energy 392Exergy(Work Potential)Associatedwith

Kinetic Energy,ke 395ExergyAssociatedwith PotentialEnergy,pe 395

Reversible Work and Irreversibility 395Second-Law Efficiency, 'YJn 399

Exergy Change of a System 402Energyof a FixedMass:Nonflow(or ClosedSystem)

Exergy 405Exergyof a FlowStream: Flow(or Stream)Exergy 407

Exergy Transfer by Heat, Work, and MassExergyTransferby HeatTransfer,Q 410ExergyTransferby Work, W 411ExergyTransferby Mass,m 412

The Decrease of Exergy Principleand Exergy Destruction 410Exergy Destruction 413

Exergy Balance: Closed Systems 412

Exergy Balance: Control Volumes 424

ExergyBalancefor Steady-FlowSystems 425

Topics of Special Interest:Second-Law Aspects of Daily Life 432

7-27-37-4

7-5 408

7-6

7-77-8

Summary 435Referencesand SuggestedReading 437Problems 437

CHAPTER EIGHTGASPOWERCYCLES451

8-1 Basic Considerations in the Analysis ofPower Cycles 452

'~,',"~~'.~~[' ,.y:",:..' .;;;:tj". . ,';:1}!ftf"8T?:',: x~CONTENTS

8-2

8-38-48-5

8-6

8-7

8-8

The Carnot Cycle and Its Valuein Engineering 454

Air-Standard Assumptions 456

An Overview of Reciprocating Engines 456

Otto Cycle: The Ideal Cycle forSpark-Ignition Engines 457

Diesel Cycle: The Ideal Cycle forCompression- Ignition Engines 463

Stirling and Ericsson Cycles 466

Brayton Cycle: The Ideal Cycle forGas-Turbine Engines 470Development of Gas Turbines 473Deviation of Actual Gas-Turbine Cycles

from Idealized Ones 476

8-9 The Brayton Cycle with Regeneration 477

8-10 The Brayton Cycle with Intercooling,Reheating, and Regeneration 479

8-11 Ideal Jet-Propulsion Cycles 483Modifications to Turbojet Engines 487

8-12 Second-Law Analysis ofGas Power Cycles 490Topics of Special Interest: Saving Fueland Money by Driving Sensibly 493BeforeDriving 494While Driving 496After Driving 498

Summary 499Referencesand SuggestedReading 501Problems 501

CHAPTER NINEVAPORANDCOMBINEDPOWERCYCLES 513

9-19-2

The Carnot Vapor Cycle 514

Rankine Cycle: The Ideal Cycle forVapor Power Cycles 515Energy Analysis of the Ideal Rankine Cycle 516

Deviation of Actual Vapor Power Cycles fromIdealized Ones 519

How Can We Increase the Efficiency ofthe Rankine Cycle? 5211 Loweringthe CondenserPressure (Lowers Tiaw,av) 5222 Superheating the Steam to High Temperatures

(Increases Thigh,av) 5223 Increasing the Boiler Pressure (Increases Thigh,av) 523

9-3

9-4

9-5

9-6The Ideal Reheat Rankine Cycle 525

The Ideal Regenerative Rankine Cycle 529Open FeedwaterHeaters 529ClosedFeedwaterHeaters 531

9-7 Second-Law Analysis ofVapor Power Cycles 537

Cogeneration 539

Combined Gas-Vapor Power Cycles 543Topics of Special Interest:Binary Vapor Cycles 547Summary549ReferencesandSuggestedReading 550Problems 550

9-89-9

CHAPTER TENREFRIGERATIONCYCLES563

10-1 Refrigerators and Heat Pumps 564

10-2 TheReversedCarnotCycle 565

10-3 The Ideal Vapor-CompressionRefrigeration Cycle 567

10-4 Actual Vapor-CompressionRefrigerationCycle 570

10-5 Selecting the Right Refrigerant 573

10-6 Heat Pump Systems 575

10-7 Innovative Vapor-CompressionRefrigeration Systems 576Cascade RefrigerationSystems 577MultistageCompressionRefrigerationSystems 579MultipurposeRefrigerationSystemswith a

SingleCompressor 582Liquefactionof Gases 583

10-8 Gas Refrigeration Cycles 584

10-9 Absorption Refrigeration Systems 588Topics of Special Interest: Thermoelectric PowerGeneration and Refrigeration Systems 590Summary 592Referencesand SuggestedReading 593Problems 594

CHAPTER ELEVENTHERMODYNAMICPROPERTYRELATIONS603

11-1 A Little Math-Partial Derivatives andAssociated Relations 604

PartialDifferentia,s 605PartialDifferentialRelations 607

11-2 The Maxwell Relations 609

11-3 The Clapeyron Equation 610

11-4 General Relations for

du, dh, ds, Cv, and Cp 613InternalEnergyChanges 613EnthalpyChanges 614EntropyChanges 615Specific Heats Cyand Cp 616

11-5 The Joule-Thomson Coefficient 620

11-6 The jj.h, jj.u, and jj.s of Real Gases 622EnthalpyChangesof RealGases 622Internal EnergyChangesof RealGases 623EntropyChangesof RealGases 623

Summary 626Referencesand SuggestedReading 627Problems 627

CHAPTER TWELVEGASMIXTURES633

12-1 Composition of a Gas Mixture:Mass and Mole Fractions 634

12-2 P-v-TBehavior of Gas Mixtures:Ideal and Real Gases 636Ideal-GasMixtures 637Real-GasMixtures 637

12-3 Properties of Gas Mixtures:Ideal and Real Gases 641Ideal-GasMixtures 642Real-GasMixtures 645

Topics of Special Interest: Chemical Potentialand the Separation Work of Mixtures 648IdealGasMixturesand IdealSolutions 651Minimum Workof Separationof Mixtures 653ReversibleMixing Processes 654Second-LawEfficiency 654Special-Case:Separationof a Two-ComponentMixture 655An Application: DesalinationProcesses 656

Summary 659Referencesand SuggestedReading 660Problems 660

CHAPTER THIRTEENGAS-VAPORMIXTURESANDAIR-CONDITIONING667

13-1 Dry and AtmosphericAir 668

"~ '..13-2 Specific and Relative Humidity of Air 66913-3 Dew-Point Temperature 67213-4 Adiabatic Saturation and

Wet-Bulb Temperatures 673

13-5 The Psychrometric Chart 676

13-6 Human Comfort and Air-Conditioning 678

13- 7 Air-Conditioning Processes 6801 SimpleHeatingandCooling(w= constant) 6802 Heatingwith Humidification 6813 Coolingwith Dehumidification 6834 EvaporativeCooling 6855 Adiabatic Mixingof Airstreams 6876 Wet CoolingTowers 689

Summary 691Referencesand SuggestedReading 692Problems 693

CHAPTER FOURTEENCHEMICALREACTIONS701

14-1 Fuels and Combustion 702

14-2 Theoretical and ActualCombustion Processes 706

14-3 Enthalpy of Formation andEnthalpy of Combustion 711

14-4 First-Law Analysis of Reacting Systems 715Steady-FlowSystems 715Closed Systems 716

14-5 Adiabatic Flame Temperature 72014-6 Entropy Change of Reacting Systems 723

14- 7 Second-Law Analysis ofReacting Systems 724Topics of Special Interest: Fuel Cells 730Summary 732Referencesand SuggestedReading 733Problems 734

CHAPTER FIFTEENCHEMICALANDPHASEEQUILIBRIUM743

15-1 Criterion for Chemical Equilibrium 744

15-2 The Equilibrium Constant forIdeal-Gas Mixtures 746

15-3 Some Remarks about the Kp ofIdeal-Gas Mixtures 749

15-4 Chemical Equilibrium forSimultaneous Reactions 754

- -- __xiiCONTENTS

15-5 Variation of Kp with Temperature 75615-6 Phase Equilibrium 757

Phase Equilibriumfor a Single-ComponentSystem 758The PhaseRule 759PhaseEquilibriumfor a MulticomponentSystem 760

Summary 765Referencesand SuggestedReading 766Problems 766

CHAPTER SIXTEENTHERMODYNAMICSOFHIGH-SPEEDGASFLOW773

16-1 Stagnation Properties 774

16-2 Velocity of Sound and Mach Number 778

16-3 One-Dimensional Isentropic Flow 782

Variationof FluidVelocitywith FlowArea 784PropertyRelationsfor IsentropicFlowof IdealGases 786

16-4 Isentropic Flow through Nozzles 788

ConvergingNozzles 789Converging-Diverging Nozzles 793

16-5 Normal Shocks in Nozzle Flow 797

16-6 Flow through Actual Nozzlesand Diffusers 803

16-7 Steam Nozzles 810

Summary 813Referencesand SuggestedReading 815Problems 815

APPENDIX 1PROPERTYTABLESANDCHARTS(SI UNITS) 823

Table A-I Molar Mass, Gas Constant, andCritical-Point Properties 824

Ideal-Gas Specific Heats of VariousCommon Gases 825

Properties of Common Liquids, Solids,and Foods 828

Saturated Water-Temperature Table 830Saturated Water-Pressure Table 832

Superheated Water 834

Compressed Liquid Water 838

Saturated Ice Water-Vapor 839

Table A-2

Table A-3

Table A-4

Table A-5

Table A-6

Table A-7

Table A-8

Figure A-9

Figure A-lO

Table A-ll

T-s Diagram for Water 840

Monier Diagram for Water 841

Saturated Refrigerant -134a-Temperature Table 842

Saturated Refrigerant -134a-Pressure Table 843

Superheated Refrigerant-134a 844

P-h Diagram for Refrigerant-134a 846

One-Dimensional IsentropicCompressible-Flow Functions for anIdeal Gas with Constant Specific Heatsand Molar Mass, and k = 1.4 847

One-Dimensional Normal-ShockFunctions for an Ideal Gas withConstant Specific Heats and Molar Mass,and k = 1.4 848

Ideal-Gas Properties of Air 849

Ideal-Gas Propertiesof Nitrogen, Nz 851

Table A-19 Ideal-Gas Properties of Oxygen, Oz 853

Table A-20 Ideal-Gas Propertiesof Carbon Dioxide, COz 855

Table A-21 Ideal-Gas Propertiesof Carbon Monoxide, CO 857

Table A-22 Ideal-Gas Propertiesof Hydrogen, Hz 859

Table A-23 Ideal-Gas Propertiesof Water Vapor, HzO 860

Table A-24 Ideal-Gas Propertiesof Monatomic Oxygen, a 862

Table A-25 Ideal-Gas Propertiesof Hydroxyl, OH 862

Table A-26 Enthalpy of Formation, Gibbs Functionof Formation, and Absolute Entropy at25°C, 1 atm 863

Table A-27 Properties of Some Common Fuelsand Hydrocarbons 864

Table A-28 Logarithms to Base e of theEquilibrium Constant Kp 865

Table A-29 Properties of the Atmosphere atHigh Altitude 866

Figure A-30a Nelson-Obert GeneralizedCompressibility Chart-Low Pressures 867

Table A-12

Table A-13

FigureA-14

TableA-15

TableA-16

Table A-17

Table A-18

Figure A-30b Nelson-Obert GeneralizedCompressibility Chart-Intermediate Pressures 868

Figure A-30c Nelson-Obert GeneralizedCompressibility Chart-High Pressures 869

Figure A-31 Generalized EnthalpyDeparture Chart 870

Figure A-32 Generalized EntropyDeparture Chart 871

Figure A-33 Psychrometric Chart at 1 atmTotal Pressure 872

APPENDIX 2PROPERTYTABLESANDCHARTS(ENGLISHUNITS) 873

TableA-IE Molar Mass, Gas Constant, andCritical-Point Properties 874

TableA-2E Ideal-Gas Specific Heats ofVarious Common Gases 875

TableA-3E Properties of Common Liquids,Solids and Foods 878

TableA-4E Saturated Water-Temperature Table 880

TableA-5E Saturated Water-Pressure Table 881

TableA-6E Superheated Water 883

TableA-7E Compressed Liquid Water 887

TableA-8E Saturated Ice-Water Vapor 888

Figure A-9E T-s Diagram for Water 889

Figure A-WE Monier Diagram for Water 890

TableA-lIE Saturated Refrigerant -134a-Temperature Table 891

Table A-12E Saturated Refrigerant-134a-Pressure Table 892

Table A-13E Superheated Refrigerant -134a 893

Figure A-14E P-h Diagram for Refrigerant-134a 895

Table A-17E Ideal-Gas Properties of Air 896

Table A-18E Ideal-Gas Properties ofNitrogen, N2 898

Table A-19E Ideal-Gas Properties ofOxygen, O2 900

Table A-20E Ideal-Gas Properties ofCarbon Dioxide, CO2 902

Table A-2lE Ideal-Gas Properties ofCarbon Monoxide, CO 904

Table A-22E Ideal-Gas Properties ofHydrogen, H2 906

Table A-23E Ideal-Gas Properties ofWater Vapor, H2O 907

Table A-26E Enthalpy of Formation,Gibbs Function of Formation,and Absolute Entropy 909

Table A-27E Properties of Some Common Fuelsand Hydrocarbons 910

Table A-29E Properties of the Atmosphereat High Altitude 911

Figure A-33E Psychrometric Chart at 1 atmTotal Pressure 912

APPENDIX 3INTRODUCTIONTOEES 913

Index 926