Preface Acknowledgments Nomenclature

CONTENTS Preface Acknowledgments Nomenclature page xv xvii xix 1 BASIC CONCEPTS 1 1.1 Overview 1 1.2 Thermodynamic Systems 3 1.3 States and Properties 4 1.3.1 State of a System 4 1.3.2 Measurable and Derived Properties 4 1.3.3 Intensive and Extensive Properties 5 1.3.4 Internal and External Properties 5 1.4 Balances 6 1.5 Introduction to EES (Engineering Equation Solver) 8 1.6 Dimensions and Units 11 1.6.1 The SI and English Unit Systems 11 EXAMPLE 1.6-1: WEIGHT ON MARS 14 1.6.2 Working with Units in EES 14 EXAMPLE 1.6-2: POWER REQUIRED BY A VEHICLE 15 1.7 Specific Volume, Pressure, and Temperature 24 1.7.1 Specific Volume 24 1.7.2 Pressure 24 1.7.3 Temperature 26 References 28 Problems 28 2 THERMODYNAMIC PROPERTIES 34 2.1 Equilibrium and State Properties 34 2.2 General Behavior of Fluids 36 2.3 Property Tables 41 2.3.1 Saturated Liquid and Vapor 41 EXAMPLE 2.3-1: PRODUCTION OF A VACUUM BY CONDENSATION 45 2.3.2 Superheated Vapor 47 Interpolation 49 2.3.3 Compressed Liquid 50 2.4 EES Fluid Property Data 51 2.4.1 Thermodynamic Property Functions 51 v

vi EXAMPLE 2.4-1: THERMOSTATIC EXPANSION VALVE 55 2.4.2 Arrays and Property Plots 59 EXAMPLE 2.4-2: LIQUID OXYGEN TANK 63 2.5 The Ideal Gas Model 69 EXAMPLE 2.5-1: THERMALLY-DRIVEN COMPRESSOR 72 2.6 The Incompressible Substance Model 78 EXAMPLE 2.6-1: FIRE EXTINGUISHING SYSTEM 80 References 85 Problems 85 3 ENERGY AND ENERGY TRANSPORT 92 3.1 Conservation of Energy Applied to a Closed System 92 3.2 Forms of Energy 93 3.2.1 Kinetic Energy 93 3.2.2 Potential Energy 94 3.2.3 Internal Energy 94 3.3 Specific Internal Energy 94 3.3.1 Property Tables 95 3.3.2 EES Fluid Property Data 96 EXAMPLE 3.3-1: HOT STEAM EQUILIBRATING WITH COLD LIQUID WATER 96 3.3.3 Ideal Gas 101 3.3.4 Incompressible Substances 106 EXAMPLE 3.3-2: AIR IN A TANK 107 3.4 Heat 110 3.4.1 Heat Transfer Mechanisms 111 EXAMPLE 3.4-1: RUPTURE OF A HELIUM DEWAR 112 3.4.2 The Caloric Theory 115 3.5 Work 116 EXAMPLE 3.5-1: COMPRESSION OF AMMONIA 121 EXAMPLE 3.5-2: HELIUM BALLOON 129 3.6 What is Energy and How Can you Prove that it is Conserved? 133 References 137 Problems 137 4 GENERAL APPLICATION OF THE FIRST LAW 151 4.1 General Statement of the First Law 151 4.2 Specific Enthalpy 155 4.2.1 Property Tables 155 4.2.2 EES Fluid Property Data 156 4.2.3 Ideal Gas 156 4.2.4 Incompressible Substance 159 4.3 Methodology for Solving Thermodynamics Problems 159 EXAMPLE 4.3-1: PORTABLE COOLING SYSTEM 161 4.4 Thermodynamic Analyses of Steady-State Applications 163 4.4.1 Turbines 163 4.4.2 Compressors 165 4.4.3 Pumps 166 4.4.4 Nozzles 167 4.4.5 Diffusers 167

vii 4.4.6 Throttles 168 4.4.7 Heat Exchangers 168 EXAMPLE 4.4-1: DE-SUPERHEATER IN AN AMMONIA REFRIGERATION SYSTEM 170 4.5 Analysis of Open Unsteady Systems 175 EXAMPLE 4.5-1: HYDROGEN STORAGE TANK FOR A VEHICLE 176 EXAMPLE 4.5-2: EMPTYING AN ADIABATIC TANK FILLED WITH IDEAL GAS 180 EXAMPLE 4.5-3: EMPTYING A BUTANE TANK 184 Reference 187 Problems 187 5 THE SECOND LAW OF THERMODYNAMICS 204 5.1 The Second Law of Thermodynamics 204 5.1.1 Second Law Statements 207 5.1.2 Continuous Operation 207 5.1.3 Thermal Reservoir 208 5.1.4 Equivalence of the Second Law Statements 209 5.2 Reversible and Irreversible Processes 210 EXAMPLE 5.2-1: REVERSIBLE AND IRREVERSIBLE WORK 214 5.3 Maximum Thermal Efficiency of Heat Engines and Heat Pumps 217 5.4 Thermodynamic Temperature Scale 220 EXAMPLE 5.4-1: THERMODYNAMIC TEMPERATURE SCALES 222 5.5 The Carnot Cycle 225 Problems 232 6 ENTROPY 237 6.1 Entropy, a Property of Matter 237 6.2 Fundamental Property Relations 241 6.3 Specific Entropy 243 6.3.1 Property Tables 243 6.3.2 EES Fluid Property Data 243 EXAMPLE 6.3-1: ENTROPY CHANGE DURING A PHASE CHANGE 244 6.3.3 Entropy Relations for Ideal Gases 245 EXAMPLE 6.3-2: SPECIFIC ENTROPY CHANGE FOR NITROGEN 247 6.3.4 Entropy Relations for Incompressible Substances 249 6.4 A General Statement of the Second Law of Thermodynamics 249 EXAMPLE 6.4-1: ENTROPY GENERATED BY HEATING WATER 254 6.5 The Entropy Balance 257 6.5.1 Entropy Generation 257 6.5.2 Solution Methodology 260 6.5.3 Choice of System Boundary 260 System Encloses all Irreversible Processes 261 EXAMPLE 6.5-1: AIR HEATING SYSTEM 262 System Excludes all Irreversible Processes 264 EXAMPLE 6.5-2: EMPTYING AN ADIABATIC TANK WITH IDEAL GAS (REVISITED) 265 6.6 Efficiencies of Thermodynamic Devices 266 6.6.1 Turbine Efficiency 266 EXAMPLE 6.6-1: TURBINE ISENTROPIC EFFICIENCY 267 EXAMPLE 6.6-2: TURBINE POLYTROPIC EFFICIENCY 270 6.6.2 Compressor Efficiency 277

viii EXAMPLE 6.6-3: INTERCOOLED COMPRESSION 278 6.6.3 Pump Efficiency 287 EXAMPLE 6.6-4: SOLAR POWERED LIVESTOCK PUMP 289 6.6.4 Nozzle Efficiency 292 EXAMPLE 6.6-5: JET-POWERED WAGON 294 6.6.5 Diffuser Efficiency 300 EXAMPLE 6.6-6: DIFFUSER IN A GAS TURBINE ENGINE 302 6.6.6 Heat Exchanger Effectiveness 305 EXAMPLE 6.6-7: ARGON REFRIGERATION CYCLE 308 Heat Exchangers with Constant Specific Heat Capacity 312 EXAMPLE 6.6-8: ENERGY RECOVERY HEAT EXCHANGER 316 References 322 Problems 322 7 EXERGY 350 7.1 Definition of Exergy and Second Law Efficiency 350 7.2 Exergy of Heat 351 EXAMPLE 7.2-1: SECOND LAW EFFICIENCY 353 7.3 Exergy of a Flow Stream 355 EXAMPLE 7.3-1: HEATING SYSTEM 358 7.4 Exergy of a System 361 EXAMPLE 7.4-1: COMPRESSED AIR POWER SYSTEM 364 7.5 Exergy Balance 367 EXAMPLE 7.5-1: EXERGY ANALYSIS OF A COMMERCIAL LAUNDRY FACILITY 369 7.6 Relation Between Exergy Destruction and Entropy Generation (E1) 378 Problems 379 8 POWER CYCLES 385 8.1 The Carnot Cycle 385 8.2 The Rankine Cycle 388 8.2.1 The Ideal Rankine Cycle 388 Effect of Boiler Pressure 395 Effect of Heat Source Temperature 397 Effect of Heat Sink Temperature 397 8.2.2 The Non-Ideal Rankine Cycle 399 8.2.3 Modifications to the Rankine Cycle 405 Reheat 405 Regeneration 410 EXAMPLE 8.2-1: SOLAR TROUGH POWER PLANT 413 8.3 The Gas Turbine Cycle 426 8.3.1 The Basic Gas Turbine Cycle 427 Effect of Air-Fuel Ratio 433 Effect of Pressure Ratio and Turbine Inlet Temperature 434 Effect of Compressor and Turbine Efficiencies 437 8.3.2 Modifications to the Gas Turbine Cycle 437 Reheat and Intercooling 437 EXAMPLE 8.3-1: OPTIMAL INTERCOOLING PRESSURE 439 Recuperation 442 Section can be found on the Web site that accompanies this book (/kleinandnellis).

ix EXAMPLE 8.3-2: GAS TURBINE ENGINE FOR SHIP PROPULSION 443 8.3.3 The Gas Turbine Engines for Propulsion 452 Turbojet Engine 452 EXAMPLE 8.3-3: TURBOJET ENGINE 454 Turbofan Engine 458 EXAMPLE 8.3-4: TURBOFAN ENGINE 460 Turboprop Engine 467 8.3.4 The Combined Cycle and Cogeneration 467 8.4 Reciprocating Internal Combustion Engines 468 8.4.1 The Spark-Ignition Reciprocating Internal Combustion Engine 468 Spark-Ignition, Four-Stroke Engine Cycle 469 Simple Model of Spark-Ignition, Four-Stroke Engine 472 Octane Number of Gasoline 477 EXAMPLE 8.4-1: POLYTROPIC MODEL WITH RESIDUAL COMBUSTION GAS 479 Spark-Ignition, Two-Stroke Internal Combustion Engine 488 8.4.2 The Compression-Ignition Reciprocating Internal Combustion Engine 491 EXAMPLE 8.4-2: TURBOCHARGED DIESEL ENGINE 493 8.5 The Stirling Engine 501 8.5.1 The Stirling Engine Cycle 502 8.5.2 Simple Model of the Ideal Stirling Engine Cycle (E2) 504 8.6 Tradeoffs Between Power and Efficiency 505 8.6.1 The Heat Transfer Limited Carnot Cycle 505 8.6.2 Carnot Cycle using Fluid Streams as the Heat Source and Heat Sink (E3) 511 8.6.3 Internal Irreversibilities (E4) 511 8.6.4 Application to other Cycles 511 References 512 Problems 512 9 REFRIGERATION AND HEAT PUMP CYCLES 529 9.1 The Carnot Cycle 529 9.2 The Vapor Compression Cycle 532 9.2.1 The Ideal Vapor Compression Cycle 532 Effect of Refrigeration Temperature 538 9.2.2 The Non-Ideal Vapor Compression Cycle 540 EXAMPLE 9.2-1: INDUSTRIAL FREEZER 542 EXAMPLE 9.2-2: INDUSTRIAL FREEZER DESIGN 545 9.2.3 Refrigerants 550 Desirable Refrigerant Properties 550 Positive Evaporator Gage Pressure 551 Moderate Condensing Pressure 551 Appropriate Triple Point and Critical Point Temperatures 551 High Density/Low Specific Volume at the Compressor Inlet 553 High Latent Heat (Specific Enthalpy Change) of Vaporization 553 High Dielectric Strength 553 Compatibility with Lubricants 553 Non-Toxic 554 Non-Flammable 554 Section can be found on the Web site that accompanies this book (/kleinandnellis).

x Inertness and Stability 554 Refrigerant Naming Convention 554 Ozone Depletion and Global Warming Potential 556 9.2.4 Vapor Compression Cycle Modifications 557 Liquid-Suction Heat Exchanger 559 EXAMPLE 9.2-3: REFRIGERATION CYCLE WITH A LIQUID-SUCTION HEAT EXCHANGER 560 Liquid Overfed Evaporator 564 Intercooled Cycle 567 Economized Cycle 568 Flash-Intercooled Cycle 571 EXAMPLE 9.2-4: FLASH INTERCOOLED CYCLE FOR A BLAST FREEZER 571 EXAMPLE 9.2-5: CASCADE CYCLE FOR A BLAST FREEZER 578 9.3 Heat Pumps 584 EXAMPLE 9.3-1: HEATING SEASON PERFORMANCE FACTOR 588 9.4 The Absorption Cycle 598 9.4.1 The Basic Absorption Cycle 598 9.4.2 Absorption Cycle Working Fluids (E6) 601 9.5 Recuperative Cryogenic Cooling Cycles 601 9.5.1 The Reverse Brayton Cycle 603 9.5.2 The Joule-Thomson Cycle 611 9.5.3 Liquefaction Cycles (E7) 614 9.6 Regenerative Cryogenic Cooling Cycles (E8) 614 References 614 Problems 615 10 PROPERTY RELATIONS FOR PURE FLUIDS 629 10.1 Equations of State for Pressure, Volume, and Temperature 629 10.1.1 Compressibility Factor and Reduced Properties 630 10.1.2 Characteristics of the Equation of State 633 Limiting Ideal Gas Behavior 633 The Boyle Isotherm 633 Critical Point Behavior 634 10.1.3 Two-Parameter Equations of State 637 The van der Waals Equation of State 637 EXAMPLE 10.1-1: APPLICATION OF THE VAN DER WAALS EQUATION OF STATE 641 The Dieterici Equation of State 646 EXAMPLE 10.1-2: DIETERICI EQUATION OF STATE 646 The Redlich-Kwong Equation of State 649 The Redlich-Kwong-Soave (RKS) Equation of State 650 The Peng-Robinson (PR) Equation of State 651 EXAMPLE 10.1-3: PENG-ROBINSON EQUATION OF STATE 653 10.1.4 Multiple Parameter Equations of State 656 10.2 Application of Fundamental Property Relations 657 10.2.1 The Fundamental Property Relations 658 10.2.2 Complete Equations of State 659 EXAMPLE 10.2-1: USING A COMPLETE EQUATION OF STATE 660 EXAMPLE 10.2-2: THE REDUCED HELMHOLTZ EQUATION OF STATE 661 Section can be found on the Web site that accompanies this book (/kleinandnellis).

xi 10.3 Derived Thermodynamic Properties 670 10.3.1 Maxwell s Relations 670 10.3.2 Calculus Relations for Partial Derivatives 672 10.3.3 Derived Relations for u, h,ands 673 EXAMPLE 10.3-1: ISOTHERMAL COMPRESSION PROCESS 676 10.3.4 Derived Relations for other Thermodynamic Quantities 681 EXAMPLE 10.3-2: SPEED OF SOUND OF CARBON DIOXIDE 682 10.3.5 Relations Involving Specific Heat Capacity 685 10.4 Methodology for Calculating u, h,ands 688 EXAMPLE 10.4-1: CALCULATING THE PROPERTIES OF ISOBUTANE 692 10.5 Phase Equilibria for Pure Fluids 697 10.5.1 Criterion for Phase Equilibrium 697 10.5.2 Relations between Properties during a Phase Change 699 EXAMPLE 10.5-1: EVALUATING A NEW REFRIGERANT 701 10.5.3 Estimating Saturation Properties using an Equation of State (E9) 703 10.6 Fugacity 704 10.6.1 The Fugacity of Gases 706 Calculating Fugacity using the RKS and PR Equations of State (E10) 708 10.6.2 The Fugacity of Liquids 708 References 710 Problems 710 11 MIXTURES AND MULTI-COMPONENT PHASE EQUILIBRIUM 721 11.1 P-v-T Relations for Ideal Gas Mixtures 721 11.1.1 Composition Relations 721 11.1.2 Mixture Rules for Ideal Gas Mixtures 723 11.2 Energy, Enthalpy, and Entropy for Ideal Gas Mixtures 726 11.2.1 Changes in Properties for Ideal Gas Mixtures with Fixed Composition 728 11.2.2 Enthalpy and Entropy Change of Mixing 729 EXAMPLE 11.2-1: POWER AND EFFICIENCY OF A GAS TURBINE 731 EXAMPLE 11.2-2: SEPARATING CO 2 FROM THE ATMOSPHERE 734 11.3 P-v-T Relations for Non-Ideal Gas Mixtures 738 11.3.1 Dalton s Rule 738 11.3.2 Amagat s Rule 739 11.3.3 Empirical Mixing Rules 740 Kay s Rule 740 Mixing Rules 741 EXAMPLE 11.3-1: SPECIFIC VOLUME OF A GAS MIXTURE 742 11.4 Energy and Entropy for Non-Ideal Gas Mixtures 746 11.4.1 Enthalpy and Entropy Changes of Mixing 746 11.4.2 Enthalpy and Entropy Departures 749 Molar Specific Enthalpy and Entropy Departures from a Two-Parameter Equation of State (E11) 751 11.4.3 Enthalpy and Entropy for Ideal Solutions 752 11.4.4 Enthalpy and Entropy using a Two-Parameter Equation of State 753 The RKS Equation of State (E12) 753 The Peng-Robinson Equation of State 754 EXAMPLE 11.4-1: ANALYSIS OF A COMPRESSOR WITH A GAS MIXTURE 754 Section can be found on the Web site that accompanies this book (/kleinandnellis).

xii 11.4.5 Peng-Robinson Library Functions 764 EXAMPLE 11.4-2: ANALYSIS OF A COMPRESSOR WITH A GAS MIXTURE (REVISITED) 765 11.5 Multi-Component Phase Equilibrium 769 11.5.1 Criterion of Multi-Component Phase Equilibrium (E13) 769 11.5.2 Chemical Potentials 769 11.5.3 Evaluation of Chemical Potentials for Ideal Gas Mixtures 771 11.5.4 Evaluation of Chemical Potentials for Ideal Solutions (E14) 772 11.5.5 Evaluation of Chemical Potentials for Liquid Mixtures (E15) 772 11.5.6 Applications of Multi-Component Phase Equilibrium 773 EXAMPLE 11.5-1: USE OF A MIXTURE IN A REFRIGERATION CYCLE 776 11.6 The Phase Rule 783 References 784 Problems 784 12 PSYCHROMETRICS 791 12.1 Psychrometric Definitions 791 EXAMPLE 12.1-1: BUILDING AIR CONDITIONING SYSTEM 795 12.2 Wet Bulb and Adiabatic Saturation Temperatures 799 12.3 The Psychrometric Chart and EES Psychrometric Functions 802 12.3.1 Psychrometric Properties 802 12.3.2 The Psychrometric Chart 804 EXAMPLE 12.3-1: BUILDING AIR CONDITIONING SYSTEM (REVISITED) 808 12.3.3 Psychrometric Properties in EES 810 EXAMPLE 12.3-2: BUILDING AIR CONDITIONING SYSTEM (REVISITED AGAIN) 812 12.4 Psychrometric Processes for Comfort Conditioning 814 12.4.1 Humidification Processes 815 EXAMPLE 12.4-1: HEATING/HUMIDIFICATION SYSTEM 816 12.4.2 Dehumidification Processes 822 EXAMPLE 12.4-2: AIR CONDITIONING SYSTEM 823 12.4.3 Evaporative Cooling 827 12.4.4 Desiccants (E16) 829 12.5 Cooling Towers 830 12.5.1 Cooling Tower Nomenclature 831 12.5.2 Cooling Tower Analysis 832 EXAMPLE 12.5-1: ANALYSIS OF A COOLING TOWER 834 12.6 Entropy for Psychrometric Mixtures (E17) 838 References 838 Problems 838 13 COMBUSTION 852 13.1 Introduction to Combustion 852 13.2 Balancing Chemical Reactions 854 13.2.1 Air as an Oxidizer 855 13.2.2 Methods for Quantifying Excess Air 856 13.2.3 Psychrometric Issues 857 EXAMPLE 13.2-1: COMBUSTION OF A PRODUCER GAS 858 13.3 Energy Considerations 864 Section can be found on the Web site that accompanies this book (/kleinandnellis).

xiii 13.3.1 Enthalpy of Formation 864 13.3.2 Heating Values 866 EXAMPLE 13.3-1: HEATING VALUE OF A PRODUCER GAS 871 13.3.3 Enthalpy and Internal Energy as a Function of Temperature 873 EXAMPLE 13.3-2: PROPANE HEATER 875 13.3.4 Use of EES for Determining Properties 879 EXAMPLE 13.3-3: FURNACE EFFICIENCY 882 13.3.5 Adiabatic Reactions 889 EXAMPLE 13.3-4: DETERMINATION OF THE EXPLOSION PRESSURE OF METHANE 894 13.4 Entropy Considerations 898 EXAMPLE 13.4-1: PERFORMANCE OF A GAS TURBINE ENGINE 901 13.5 Exergy of Fuels (E18) 907 References 907 Problems 908 14 CHEMICAL EQUILIBRIUM 922 14.1 Criterion for Chemical Equilibrium 922 14.2 Reaction Coordinates 924 EXAMPLE 14.2-1: SIMULTANEOUS CHEMICAL REACTIONS 927 14.3 The Law of Mass Action 931 14.3.1 The Criterion of Equilibrium in terms of Chemical Potentials 931 14.3.2 Chemical Potentials for an Ideal Gas Mixture 933 14.3.3 Equilibrium Constant and the Law of Mass Action for Ideal Gas Mixtures 933 EXAMPLE 14.3-1: REFORMATION OF METHANE 935 14.3.4 Equilibrium Constant and the Law of Mass Action for an Ideal Solution 938 EXAMPLE 14.3-2: AMMONIA SYNTHESIS 939 14.4 Alternative Methods for Chemical Equilibrium Problems 943 14.4.1 Direct Minimization of Gibbs Free Energy 944 EXAMPLE 14.4-1: REFORMATION OF METHANE (REVISITED) 945 14.4.2 Lagrange Method of Undetermined Multipliers 949 EXAMPLE 14.4-2: REFORMATION OF METHANE (REVISITED AGAIN) 951 14.5 Heterogeneous Reactions (E19) 953 14.6 Adiabatic Reactions 954 EXAMPLE 14.6-1: ADIABATIC COMBUSTION OF HYDROGEN 954 EXAMPLE 14.6-2: ADIABATIC COMBUSTION OF ACETYLENE 960 Reference 967 Problems 967 15 STATISTICAL THERMODYNAMICS 972 15.1 A Brief Review of Quantum Theory History 973 15.1.1 Electromagnetic Radiation 973 15.1.2 Extension to Particles 975 15.2 The Wave Equation and Degeneracy for a Monatomic Ideal Gas 976 15.2.1 Probability of Finding a Particle 976 15.2.2 Application of a Wave Equation 976 15.2.3 Degeneracy 979 15.3 The Equilibrium Distribution 979 15.3.1 Macrostates and Thermodynamic Probability 980 Section can be found on the Web site that accompanies this book (/kleinandnellis).

xiv 15.3.2 Identification of the Most Probable Macrostate 982 15.3.3 The Significance of β 985 15.3.4 Boltzmann s Law 987 15.4 Properties and the Partition Function 989 15.4.1 Definition of the Partition Function 989 15.4.2 Internal Energy from the Partition Function 990 15.4.3 Entropy from the Partition Function 991 15.4.4 Pressure from the Partition Function 992 15.5 Partition Function for an Monatomic Ideal Gas 993 15.5.1 Pressure for a Monatomic Ideal Gas 994 15.5.2 Internal Energy for a Monatomic Ideal Gas 995 15.5.3 Entropy for a Monatomic Ideal Gas 995 EXAMPLE 15.5-1: CALCULATION OF ABSOLUTE ENTROPY VALUES 997 15.6 Extension to More Complex Particles 998 15.7 Heat and Work from a Statistical Thermodynamics Perspective 1001 References 1004 Problems 1005 16 COMPRESSIBLE FLOW (E20) 1009 Appendices Problems 1009 A: Unit Conversions and Useful Information 1015 B: Property Tables for Water 1019 C: Property Tables for R134a 1031 D: Ideal Gas & Incompressible Substances 1037 E: Ideal Gas Properties of Air 1039 F: Ideal Gas Properties of Common Combustion Gases 1045 G: Numerical Solution to ODEs 1056 H: Introduction to Maple (E26) 1057 Index 1059 Section can be found on the Web site that accompanies this book (/kleinandnellis).