Preface Acknowledgments Nomenclature

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1 CONTENTS Preface Acknowledgments Nomenclature page xv xvii xix 1 BASIC CONCEPTS Overview Thermodynamic Systems States and Properties State of a System Measurable and Derived Properties Intensive and Extensive Properties Internal and External Properties Balances Introduction to EES (Engineering Equation Solver) Dimensions and Units The SI and English Unit Systems 11 EXAMPLE 1.6-1: WEIGHT ON MARS Working with Units in EES 14 EXAMPLE 1.6-2: POWER REQUIRED BY A VEHICLE Specific Volume, Pressure, and Temperature Specific Volume Pressure Temperature 26 References 28 Problems 28 2 THERMODYNAMIC PROPERTIES Equilibrium and State Properties General Behavior of Fluids Property Tables Saturated Liquid and Vapor 41 EXAMPLE 2.3-1: PRODUCTION OF A VACUUM BY CONDENSATION Superheated Vapor 47 Interpolation Compressed Liquid EES Fluid Property Data Thermodynamic Property Functions 51 v

2 vi EXAMPLE 2.4-1: THERMOSTATIC EXPANSION VALVE Arrays and Property Plots 59 EXAMPLE 2.4-2: LIQUID OXYGEN TANK The Ideal Gas Model 69 EXAMPLE 2.5-1: THERMALLY-DRIVEN COMPRESSOR The Incompressible Substance Model 78 EXAMPLE 2.6-1: FIRE EXTINGUISHING SYSTEM 80 References 85 Problems 85 3 ENERGY AND ENERGY TRANSPORT Conservation of Energy Applied to a Closed System Forms of Energy Kinetic Energy Potential Energy Internal Energy Specific Internal Energy Property Tables EES Fluid Property Data 96 EXAMPLE 3.3-1: HOT STEAM EQUILIBRATING WITH COLD LIQUID WATER Ideal Gas Incompressible Substances 106 EXAMPLE 3.3-2: AIR IN A TANK Heat Heat Transfer Mechanisms 111 EXAMPLE 3.4-1: RUPTURE OF A HELIUM DEWAR The Caloric Theory Work 116 EXAMPLE 3.5-1: COMPRESSION OF AMMONIA 121 EXAMPLE 3.5-2: HELIUM BALLOON What is Energy and How Can you Prove that it is Conserved? 133 References 137 Problems GENERAL APPLICATION OF THE FIRST LAW General Statement of the First Law Specific Enthalpy Property Tables EES Fluid Property Data Ideal Gas Incompressible Substance Methodology for Solving Thermodynamics Problems 159 EXAMPLE 4.3-1: PORTABLE COOLING SYSTEM Thermodynamic Analyses of Steady-State Applications Turbines Compressors Pumps Nozzles Diffusers 167

3 vii Throttles Heat Exchangers 168 EXAMPLE 4.4-1: DE-SUPERHEATER IN AN AMMONIA REFRIGERATION SYSTEM 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 THE SECOND LAW OF THERMODYNAMICS The Second Law of Thermodynamics Second Law Statements Continuous Operation Thermal Reservoir Equivalence of the Second Law Statements Reversible and Irreversible Processes 210 EXAMPLE 5.2-1: REVERSIBLE AND IRREVERSIBLE WORK Maximum Thermal Efficiency of Heat Engines and Heat Pumps Thermodynamic Temperature Scale 220 EXAMPLE 5.4-1: THERMODYNAMIC TEMPERATURE SCALES The Carnot Cycle 225 Problems ENTROPY Entropy, a Property of Matter Fundamental Property Relations Specific Entropy Property Tables EES Fluid Property Data 243 EXAMPLE 6.3-1: ENTROPY CHANGE DURING A PHASE CHANGE Entropy Relations for Ideal Gases 245 EXAMPLE 6.3-2: SPECIFIC ENTROPY CHANGE FOR NITROGEN Entropy Relations for Incompressible Substances A General Statement of the Second Law of Thermodynamics 249 EXAMPLE 6.4-1: ENTROPY GENERATED BY HEATING WATER The Entropy Balance Entropy Generation Solution Methodology 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) Efficiencies of Thermodynamic Devices Turbine Efficiency 266 EXAMPLE 6.6-1: TURBINE ISENTROPIC EFFICIENCY 267 EXAMPLE 6.6-2: TURBINE POLYTROPIC EFFICIENCY Compressor Efficiency 277

4 viii EXAMPLE 6.6-3: INTERCOOLED COMPRESSION Pump Efficiency 287 EXAMPLE 6.6-4: SOLAR POWERED LIVESTOCK PUMP Nozzle Efficiency 292 EXAMPLE 6.6-5: JET-POWERED WAGON Diffuser Efficiency 300 EXAMPLE 6.6-6: DIFFUSER IN A GAS TURBINE ENGINE 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 EXERGY Definition of Exergy and Second Law Efficiency Exergy of Heat 351 EXAMPLE 7.2-1: SECOND LAW EFFICIENCY Exergy of a Flow Stream 355 EXAMPLE 7.3-1: HEATING SYSTEM Exergy of a System 361 EXAMPLE 7.4-1: COMPRESSED AIR POWER SYSTEM Exergy Balance 367 EXAMPLE 7.5-1: EXERGY ANALYSIS OF A COMMERCIAL LAUNDRY FACILITY Relation Between Exergy Destruction and Entropy Generation (E1) 378 Problems POWER CYCLES The Carnot Cycle The Rankine Cycle The Ideal Rankine Cycle 388 Effect of Boiler Pressure 395 Effect of Heat Source Temperature 397 Effect of Heat Sink Temperature The Non-Ideal Rankine Cycle Modifications to the Rankine Cycle 405 Reheat 405 Regeneration 410 EXAMPLE 8.2-1: SOLAR TROUGH POWER PLANT The Gas Turbine Cycle 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 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).

5 ix EXAMPLE 8.3-2: GAS TURBINE ENGINE FOR SHIP PROPULSION 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 The Combined Cycle and Cogeneration Reciprocating Internal Combustion Engines 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 The Compression-Ignition Reciprocating Internal Combustion Engine 491 EXAMPLE 8.4-2: TURBOCHARGED DIESEL ENGINE The Stirling Engine The Stirling Engine Cycle Simple Model of the Ideal Stirling Engine Cycle (E2) Tradeoffs Between Power and Efficiency The Heat Transfer Limited Carnot Cycle Carnot Cycle using Fluid Streams as the Heat Source and Heat Sink (E3) Internal Irreversibilities (E4) Application to other Cycles 511 References 512 Problems REFRIGERATION AND HEAT PUMP CYCLES The Carnot Cycle The Vapor Compression Cycle The Ideal Vapor Compression Cycle 532 Effect of Refrigeration Temperature The Non-Ideal Vapor Compression Cycle 540 EXAMPLE 9.2-1: INDUSTRIAL FREEZER 542 EXAMPLE 9.2-2: INDUSTRIAL FREEZER DESIGN 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).

6 x Inertness and Stability 554 Refrigerant Naming Convention 554 Ozone Depletion and Global Warming Potential 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 Heat Pumps 584 EXAMPLE 9.3-1: HEATING SEASON PERFORMANCE FACTOR The Absorption Cycle The Basic Absorption Cycle Absorption Cycle Working Fluids (E6) Recuperative Cryogenic Cooling Cycles The Reverse Brayton Cycle The Joule-Thomson Cycle Liquefaction Cycles (E7) Regenerative Cryogenic Cooling Cycles (E8) 614 References 614 Problems PROPERTY RELATIONS FOR PURE FLUIDS Equations of State for Pressure, Volume, and Temperature Compressibility Factor and Reduced Properties Characteristics of the Equation of State 633 Limiting Ideal Gas Behavior 633 The Boyle Isotherm 633 Critical Point Behavior Two-Parameter Equations of State 637 The van der Waals Equation of State 637 EXAMPLE : APPLICATION OF THE VAN DER WAALS EQUATION OF STATE 641 The Dieterici Equation of State 646 EXAMPLE : 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 : PENG-ROBINSON EQUATION OF STATE Multiple Parameter Equations of State Application of Fundamental Property Relations The Fundamental Property Relations Complete Equations of State 659 EXAMPLE : USING A COMPLETE EQUATION OF STATE 660 EXAMPLE : THE REDUCED HELMHOLTZ EQUATION OF STATE 661 Section can be found on the Web site that accompanies this book (/kleinandnellis).

7 xi 10.3 Derived Thermodynamic Properties Maxwell s Relations Calculus Relations for Partial Derivatives Derived Relations for u, h,ands 673 EXAMPLE : ISOTHERMAL COMPRESSION PROCESS Derived Relations for other Thermodynamic Quantities 681 EXAMPLE : SPEED OF SOUND OF CARBON DIOXIDE Relations Involving Specific Heat Capacity Methodology for Calculating u, h,ands 688 EXAMPLE : CALCULATING THE PROPERTIES OF ISOBUTANE Phase Equilibria for Pure Fluids Criterion for Phase Equilibrium Relations between Properties during a Phase Change 699 EXAMPLE : EVALUATING A NEW REFRIGERANT Estimating Saturation Properties using an Equation of State (E9) Fugacity The Fugacity of Gases 706 Calculating Fugacity using the RKS and PR Equations of State (E10) The Fugacity of Liquids 708 References 710 Problems MIXTURES AND MULTI-COMPONENT PHASE EQUILIBRIUM P-v-T Relations for Ideal Gas Mixtures Composition Relations Mixture Rules for Ideal Gas Mixtures Energy, Enthalpy, and Entropy for Ideal Gas Mixtures Changes in Properties for Ideal Gas Mixtures with Fixed Composition Enthalpy and Entropy Change of Mixing 729 EXAMPLE : POWER AND EFFICIENCY OF A GAS TURBINE 731 EXAMPLE : SEPARATING CO 2 FROM THE ATMOSPHERE P-v-T Relations for Non-Ideal Gas Mixtures Dalton s Rule Amagat s Rule Empirical Mixing Rules 740 Kay s Rule 740 Mixing Rules 741 EXAMPLE : SPECIFIC VOLUME OF A GAS MIXTURE Energy and Entropy for Non-Ideal Gas Mixtures Enthalpy and Entropy Changes of Mixing Enthalpy and Entropy Departures 749 Molar Specific Enthalpy and Entropy Departures from a Two-Parameter Equation of State (E11) Enthalpy and Entropy for Ideal Solutions 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 : ANALYSIS OF A COMPRESSOR WITH A GAS MIXTURE 754 Section can be found on the Web site that accompanies this book (/kleinandnellis).

8 xii Peng-Robinson Library Functions 764 EXAMPLE : ANALYSIS OF A COMPRESSOR WITH A GAS MIXTURE (REVISITED) Multi-Component Phase Equilibrium Criterion of Multi-Component Phase Equilibrium (E13) Chemical Potentials Evaluation of Chemical Potentials for Ideal Gas Mixtures Evaluation of Chemical Potentials for Ideal Solutions (E14) Evaluation of Chemical Potentials for Liquid Mixtures (E15) Applications of Multi-Component Phase Equilibrium 773 EXAMPLE : USE OF A MIXTURE IN A REFRIGERATION CYCLE The Phase Rule 783 References 784 Problems PSYCHROMETRICS Psychrometric Definitions 791 EXAMPLE : BUILDING AIR CONDITIONING SYSTEM Wet Bulb and Adiabatic Saturation Temperatures The Psychrometric Chart and EES Psychrometric Functions Psychrometric Properties The Psychrometric Chart 804 EXAMPLE : BUILDING AIR CONDITIONING SYSTEM (REVISITED) Psychrometric Properties in EES 810 EXAMPLE : BUILDING AIR CONDITIONING SYSTEM (REVISITED AGAIN) Psychrometric Processes for Comfort Conditioning Humidification Processes 815 EXAMPLE : HEATING/HUMIDIFICATION SYSTEM Dehumidification Processes 822 EXAMPLE : AIR CONDITIONING SYSTEM Evaporative Cooling Desiccants (E16) Cooling Towers Cooling Tower Nomenclature Cooling Tower Analysis 832 EXAMPLE : ANALYSIS OF A COOLING TOWER Entropy for Psychrometric Mixtures (E17) 838 References 838 Problems COMBUSTION Introduction to Combustion Balancing Chemical Reactions Air as an Oxidizer Methods for Quantifying Excess Air Psychrometric Issues 857 EXAMPLE : COMBUSTION OF A PRODUCER GAS Energy Considerations 864 Section can be found on the Web site that accompanies this book (/kleinandnellis).

9 xiii Enthalpy of Formation Heating Values 866 EXAMPLE : HEATING VALUE OF A PRODUCER GAS Enthalpy and Internal Energy as a Function of Temperature 873 EXAMPLE : PROPANE HEATER Use of EES for Determining Properties 879 EXAMPLE : FURNACE EFFICIENCY Adiabatic Reactions 889 EXAMPLE : DETERMINATION OF THE EXPLOSION PRESSURE OF METHANE Entropy Considerations 898 EXAMPLE : PERFORMANCE OF A GAS TURBINE ENGINE Exergy of Fuels (E18) 907 References 907 Problems CHEMICAL EQUILIBRIUM Criterion for Chemical Equilibrium Reaction Coordinates 924 EXAMPLE : SIMULTANEOUS CHEMICAL REACTIONS The Law of Mass Action The Criterion of Equilibrium in terms of Chemical Potentials Chemical Potentials for an Ideal Gas Mixture Equilibrium Constant and the Law of Mass Action for Ideal Gas Mixtures 933 EXAMPLE : REFORMATION OF METHANE Equilibrium Constant and the Law of Mass Action for an Ideal Solution 938 EXAMPLE : AMMONIA SYNTHESIS Alternative Methods for Chemical Equilibrium Problems Direct Minimization of Gibbs Free Energy 944 EXAMPLE : REFORMATION OF METHANE (REVISITED) Lagrange Method of Undetermined Multipliers 949 EXAMPLE : REFORMATION OF METHANE (REVISITED AGAIN) Heterogeneous Reactions (E19) Adiabatic Reactions 954 EXAMPLE : ADIABATIC COMBUSTION OF HYDROGEN 954 EXAMPLE : ADIABATIC COMBUSTION OF ACETYLENE 960 Reference 967 Problems STATISTICAL THERMODYNAMICS A Brief Review of Quantum Theory History Electromagnetic Radiation Extension to Particles The Wave Equation and Degeneracy for a Monatomic Ideal Gas Probability of Finding a Particle Application of a Wave Equation Degeneracy The Equilibrium Distribution Macrostates and Thermodynamic Probability 980 Section can be found on the Web site that accompanies this book (/kleinandnellis).

10 xiv Identification of the Most Probable Macrostate The Significance of β Boltzmann s Law Properties and the Partition Function Definition of the Partition Function Internal Energy from the Partition Function Entropy from the Partition Function Pressure from the Partition Function Partition Function for an Monatomic Ideal Gas Pressure for a Monatomic Ideal Gas Internal Energy for a Monatomic Ideal Gas Entropy for a Monatomic Ideal Gas 995 EXAMPLE : CALCULATION OF ABSOLUTE ENTROPY VALUES Extension to More Complex Particles Heat and Work from a Statistical Thermodynamics Perspective 1001 References 1004 Problems 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).

Chapter 1 Introduction and Basic Concepts

Chapter 1 Introduction and Basic Concepts 1-1 Thermodynamics and Energy Application Areas of Thermodynamics 1-2 Importance of Dimensions and Units Some SI and English Units Dimensional Homogeneity Unity