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