* Section can be found on the website that accompanies this book (www.cambridge.org/kleinandnellis)

THERMODYNAMICS S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

CONTENTS

Preface Acknowledgments Nomenclature Chapter 1: Basic Concepts 1.1 Overview 1.2 Thermodynamic Systems 1.3 States and Properties 1.3.1 State of a System 1.3.2 Measurable and Derived Properties 1.3.3 Intensive and Extensive Properties 1.3.4 Internal and External Properties 1.4 Balances 1.5 Introduction to EES (Engineering Equation Solver) 1.6 Dimensions and Units 1.6.1 The SI and English Unit Systems EXAMPLE 1.6-1: Weight on Mars 1.6.2 Working with Units in EES EXAMPLE 1.6-2: Power Required by a Vehicle 1.7 Specific Volume, Pressure, and Temperature 1.7.1 Specific Volume 1.7.2 Pressure 1.7.3 Temperature References Problems Chapter 2: Thermodynamic Properties 2.1 Equilibrium and State Properties 2.2 General Behavior of Fluids 2.3 Property Tables 2.3.1 Saturated Liquid and Vapor EXAMPLE 2.3-1: Production of a Vacuum by Condensation 2.3.2 Superheated Vapor Interpolation

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2.3.3 Compressed Liquid 2.4 EES Fluid Property Data 2.4.1 Thermodynamic Property Functions EXAMPLE 2.4-1: Thermostatic Expansion Valve 2.4.2 Arrays and Property Plots EXAMPLE 2.4-2: Liquid Oxygen Tank 2.5 The Ideal Gas Model EXAMPLE 2.5-1: Thermally-Driven Compressor 2.6 The Incompressible Substance Model EXAMPLE 2.6-1: Fire Extinguishing System References Problems Chapter 3: Energy and Energy Transport 3.1 Conservation of Energy Applied to a Closed System 3.2 Forms of Energy 3.2.1 Kinetic Energy 3.2.2 Potential Energy 3.2.3 Internal Energy 3.3 Specific Internal Energy 3.3.1 Property Tables 3.3.2 EES Fluid Property Data EXAMPLE 3.3-1: Hot Steam Equilibrating with Cold Liquid Water 3.3.3 Ideal Gas 3.3.4 Incompressible Substances EXAMPLE 3.3-2: Air in a Tank 3.4 Heat 3.4.1 Heat Transfer Mechanisms EXAMPLE 3.4-1: Rupture of a Helium Dewar 3.4.2 The Caloric Theory 3.5 Work EXAMPLE 3.5-1: Compression of Ammonia EXAMPLE 3.5-2: Helium Balloon 3.6 What is Energy and How Can you Prove that it is Conserved? References Problems Chapter 4: General Application of the First Law 4.1 General Statement of the First Law 4.2 Specific Enthalpy 4.2.1 Property Tables 4.2.2 EES Fluid Property Data 4.2.3 Ideal Gas

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4.2.4 Incompressible Substance 4.3 Methodology for Solving Thermodynamics Problems EXAMPLE 4.3-1: Portable Cooling System 4.4 Thermodynamic Analyses of Steady-State Applications 4.4.1 Turbines 4.4.2 Compressors 4.4.3 Pumps 4.4.4 Nozzles 4.4.5 Diffusers 4.4.6 Throttles 4.4.7 Heat Exchangers EXAMPLE 4.4-1: De-Superheater in an Ammonia Refrigeration System 4.5 Analysis of Open Unsteady Systems EXAMPLE 4.5-1: Hydrogen Storage Tank for a Vehicle EXAMPLE 4.5-2: Emptying an Adiabatic Tank filled with Ideal Gas EXAMPLE 4.5-3: Emptying a Butane Tank References Problems Chapter 5: The Second Law of Thermodynamics 5.1 The Second Law of Thermodynamics 5.1.1 Second Law Statements 5.1.2 Continuous Operation 5.1.3 Thermal Reservoir 5.1.4 Equivalence of the Second Law Statements 5.2 Reversible and Irreversible Processes EXAMPLE 5.2-1: Reversible and Irreversible Work 5.3 Maximum Thermal Efficiency of Heat Engines 5.4 Thermodynamic Temperature Scale 5.5 The Carnot Cycle Problems Chapter 6: Entropy 6.1 Entropy, a Property of Matter 6.2 Fundamental Property Relations 6.3 Specific Entropy 6.3.1 Property Tables 6.3.2 EES Fluid Property Data EXAMPLE 6.3-1: Entropy Change during a Phase Change 6.3.3 Entropy Relations for Ideal Gases EXAMPLE 6.3-2: Specific Entropy Change for Nitrogen 6.3.4 Entropy Relations for Incompressible Substances 6.4 A General Statement of the Second Law of Thermodynamics

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EXAMPLE 6.4-1: Entropy Generated by Heating Water 6.5 The Entropy Balance 6.5.1 Entropy Generation 6.5.2 Solution Methodology 6.5.3 Choice of System Boundary System Encloses allIrreversible Processes EXAMPLE 6.5-1: Air Heating System System Excludes all Irreversible Processes EXAMPLE 6.5-2: Emptying an Adiabatic Tank with Ideal Gas (revisited) 6.6 Efficiencies of Thermodynamic Devices 6.6.1 Turbine Efficiency EXAMPLE 6.6-1: Turbine Isentropic Efficiency EXAMPLE 6.6-2: Turbine Polytropic Efficiency 6.6.2 Compressor Efficiency EXAMPLE 6.6-3: Intercooled Compression 6.6.3 Pump Efficiency EXAMPLE 6.6-4: Solar Powered Livestock Pump 6.6.4 Nozzle Efficiency EXAMPLE 6.6-5: Jet-Powered Wagon 6.6.5 Diffuser Efficiency EXAMPLE 6.6-6: Diffuser in a Gas Turbine Engine 6.6.6 Heat Exchanger Effectiveness EXAMPLE 6.6-7: Argon Refrigeration Cycle Heat Exchangers with Constant Specific Heat Capacity EXAMPLE 6.6-8: Energy Recovery Heat Exchanger References Problems

Chapter 7: Exergy 7.1 Definition of Exergy and Second Law Efficiency 7.2 Exergy of Heat EXAMPLE 7.2-1: Second Law Efficiency 7.3 Exergy of a Flow Stream EXAMPLE 7.3-1: Heating System 7.4 Exergy of a System EXAMPLE 7.4-1: Compressed Air Power System 7.5 Exergy Balance EXAMPLE 7.5-1: Exergy Analysis of a Commercial Laundry Facility 7.6 Relation of Exergy Destruction to Entropy Generation* (E1) Problems Chapter 8: Power Cycles 8.1 The Carnot Cycle

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8.2 The Rankine Cycle 8.2.1 The Ideal Rankine Cycle Effect of Boiler Pressure Effect of Heat Source Temperature Effect of Heat Sink Temperature 8.2.2 The Non-Ideal Rankine Cycle 8.2.3 Modifications to the Rankine Cycle Reheat Regeneration EXAMPLE 8.2-1: Solar Trough Power Plant 8.3 The Gas Turbine Cycle 8.3.1 The Basic Gas Turbine Cycle Effect of Air Fuel Ratio Effect of Pressure Ratio and Turbine Inlet Temperature Effect of Compressor and Turbine Efficiencies 8.3.2 Modifications to the Gas Turbine Cycle Reheat and Intercooling EXAMPLE 8.3-1: Optimal Intercooling Pressure Recuperation EXAMPLE 8.3-2: Gas Turbine Engine for Ship Propulsion 8.3.3 Gas Turbine Engines for Propulsion Turbojet Engine EXAMPLE 8.3-3: Turbojet Engine Turbofan Engine EXAMPLE 8.3-4: Turbofan Engine Turboprop Engine EXAMPLE 8.3-1: Performance of a Cross-Flow Heat Exchanger (revisited) 8.3.4 The Combined Cycle and Cogeneration 8.4 Reciprocating Internal Combustion Engines 8.4.1 The Spark-Ignition Reciprocating Internal Combustion Engine Spark-Ignition, Four-Stroke Engine Cycle Simple Model of Spark-Ignition, Four-Stroke Engine Octane Number of Gasoline EXAMPLE 8.4-1: Polytropic Model with Residual Combustion Gas Spark-Ignition, Two-Stroke Internal Combustion Engine 8.4.2 The Compression-Ignition Reciprocating Internal Combustion Engine EXAMPLE 8.4-2: Turbocharged Diesel Engine 8.5 The Stirling Engine 8.5.1 The Stirling Engine Cycle 8.5.2 Simple Model of the Ideal Stirling Engine Cycle* (E2) 8.6 Tradeoffs Between Power and Efficiency 8.6.1 The Heat Transfer Limited Carnot Cycle 8.6.2 Carnot Cycle using Fluid Streams as the Heat Source and Heat Sink* (E3) 8.6.3 Internal Irreversibilities* (E4) 8.6.4 Application to other Cycles EXAMPLE 8.6-1: Optimizing the Operation of a Rankine Power Plant* (E5)

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References Problems Chapter 9: Refrigeration and Heat Pump Cycles 9.1 The Carnot Cycle 9.2 The Vapor Compression Cycle 9.2.1 The Ideal Vapor Compression Cycle Effect of Refrigeration Temperature 9.2.2 The Non-Ideal Vapor Compression Cycle EXAMPLE 9.2-1: Industrial Freezer EXAMPLE 9.2-2: Industrial Freezer Design 9.2.3 Refrigerants Desirable Refrigerant Properties Refrigerant Naming Convention Ozone Depletion and Global Warming Potential 9.2.4 Vapor Compression Cycle Modifications Liquid-Suction Heat Exchanger EXAMPLE 9.2-3: Refrigeration Cycle with a Liquid-Suction Heat Exchanger Liquid Overfed Evaporator Intercooled Cycle Economized Cycle Flash-Intercooled Cycle EXAMPLE 9.2-4: Flash Intercooled Cycle for a Blast Freezer EXAMPLE 9.2-5: Cascade Cycle for a Blast Freezer 9.3 Heat Pumps EXAMPLE 9.3-1: Heating Season Performance Factor 9.4 The Absorption Cycle 9.4.1 The Basic Absorption Cycle 9.4.2 Absorption Cycle Working Fluids* (E6) EXAMPLE 9.4-1: Waste Heat Driven Absorption Cooling System* (E6) 9.5 Recuperative Cryogenic Cooling Cycles 9.5.1 The Reverse Brayton Cycle 9.5.2 The Joule-Thomson Cycle 9.5.3 Liquefaction Cycles* (E7) EXAMPLE 9.5-1: Precooled Linde-Hampson Cycle* (E7) 9.6 Regenerative Cryogenic Cooling Cycles* (E8) References Problems

Chapter 10: Property Relations for Pure Fluids 10.1 Equations of State for Pressure, Volume, and Temperature 10.1.1 Compressibility Factor and Reduced Properties 10.1.2 Characteristics of the Equation of State Limiting Ideal Gas Behavior

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The Boyle Isotherm Critical Point Behavior 10.1.3 Two-Parameter Equations of State The van der Waals Equation of State EXAMPLE 10.1-1: Application of the van der Waals Equation of State The Dieterici Equation of State EXAMPLE 10.1-2: Dieterici Equation of State The Redlich-Kwong Equation of State The Redlich-Kwong-Soave (RKS) Equation of State The Peng-Robinson (PR) Equation of State EXAMPLE 10.1-3: Peng-Robinson Equation of State 10.1.4 Multiple Parameter Equations of State 10.2 Application of Fundamental Property Relations 10.2.1 The Fundamental Property Relations 10.2.2 Complete Equations of State EXAMPLE 10.2-1: Using a Complete Equation of State EXAMPLE 10.2-2: The Reduced Helmholtz Equation of State 10.3 Derived Thermodynamic Properties 10.3.1 Maxwell's Relations 10.3.2 Calculus Relations for Partial Derivatives 10.3.3 Derived Relations for u, h, and s EXAMPLE 10.3-1: Isothermal Compression Process 10.3.4 Derived Relations for other Thermodynamic Quantities EXAMPLE 10.3-2: Speed of Sound of Carbon Dioxide 10.3.5 Relations Involving Specific Heat Capacity 10.4 Methodology for Calculating u, h, and s EXAMPLE 10.4-1: Calculating the Properties of Isobutane 10.5 Phase Equilibria for Pure Fluids 10.5.1 Criterion for Phase Equilibrium 10.5.2 Relations between Properties during a Phase Change EXAMPLE 10.5-1: Evaluating a New Refrigerant 10.5.3 Estimating Saturation Properties using an Equation of State* (E9) 10.6 Fugacity 10.6.1 The Fugacity of Gases Calculating Fugacity using the RKS and PR Equations of State* (E10) 10.6.2 The Fugacity of Liquids References Problems Chapter 11: Mixtures and Multi-Component Phase Equilibrium 11.1 P-v-T Relations for Ideal Gas Mixtures 11.1.1 Composition Relations 11.1.2 Mixture Rules for Ideal Gas Mixtures 11.2 Energy, Enthalpy, and Entropy for Ideal Gas Mixtures

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11.2.1 Changes in Properties for Ideal Gas Mixtures with Fixed Composition 11.2.2 Enthalpy and Entropy Change of Mixing EXAMPLE 11.2-1: Power and Efficiency of a Gas Turbine EXAMPLE 11.2-2: Separating CO2 from the Atmosphere 11.3 P-v-T Relations for Non-Ideal Gas Mixtures 11.3.1 Dalton's Rule 11.3.2 Amagat's Rule 11.3.3 Empirical Mixing Rules Kay's Rule Mixing Rules EXAMPLE 11.3-1: Specific Volume of a Gas Mixture 11.4 Energy and Entropy for Non-Ideal Gas Mixtures 11.4.1 Enthalpy and Entropy Change of Mixing 11.4.2 Enthalpy and Entropy Departures Molar Specific Enthalpy and Entropy Departures from a Two-Parameter

Equation of State* (E11) 11.4.3 Enthalpy and Entropy for Ideal Solutions 11.4.4 Enthalpy and Entropy using a Two-Parameter Equation of State The RKS Equation of State* (E12) The Peng Robinson Equation of State EXAMPLE 11.4-1: Analysis of a Compressor with a Gas Mixture 11.4.5 Peng-Robinson Library Functions EXAMPLE 11.4-2: Analysis of a Compressor with a Gas Mixture (revisited) 11.5 Multi-Component Phase Equilibrium 11.5.1 Criterion of Multi-Component Phase Equilibrium* (E13) 11.5.2 Chemical Potentials 11.5.3 Evaluation of Chemical Potentials for Ideal Gas Mixtures 11.5.4 Evaluation of Chemical Potentials for Ideal Solutions* (E14) 11.5.5 Evaluation of Chemical Potentials for Liquid Mixtures* (E15) 11.5.6 Applications of Multi-Component Phase Equilibrium EXAMPLE 11.5-1: Use of a Mixture in a Refrigeration Cycle 11.6 The Phase Rule References Problems

Chapter 12: Psychrometrics 12.1 Psychrometric Definitions EXAMPLE 12.1-1: Building Air Conditioning System 12.2 Wet Bulb and Adiabatic Saturation Temperatures 12.3 The Psychrometric Chart and EES' Psychrometric Functions 12.3.1 Psychrometric Properties 12.3.2 The Psychrometric Chart EXAMPLE 12.3-1: Building Air Conditioning System (revisited) 12.3.3 Psychrometric Properties in EES EXAMPLE 12.3-2: Building Air Conditioning System (revisted again)

* Section can be found on the website that accompanies this book (www.cambridge.org/kleinandnellis)

12.4 Psychrometric Processes for Comfort Conditioning 12.4.1 Humidification Processes EXAMPLE 12.4-1: Heating/Humidification System 12.4.2 Dehumidification Processes EXAMPLE 12.4-2: Air Conditioning System 12.4.3 Evaporative Cooling 12.4.4 Desiccants* (E16) EXAMPLE 12.4-3: Desiccant Air-Conditioning System* (E16) 12.5 Cooling Towers 12.5.1 Cooling Tower Nomenclature 12.5.2 Cooling Tower Analysis EXAMPLE 12.5-1: Analysis of a Cooling Tower 12.6 Entropy for Psychrometric Mixtures* (E17) EXAMPLE 12.5-2: Analysis of a Cooling Tower (continued)* (E17) References Problems

Chapter 13: Combustion 13.1 Introduction to Combustion 13.2 Balancing Chemical Reactions 13.2.1 Air as an Oxidizer 13.2.2 Methods for Quantifying Excess Air 13.2.3 Psychrometric Issues EXAMPLE 13.2-1: Combustion of a Producer Gas 13.3 Energy Considerations 13.3.1 Enthalpy of Formation 13.3.2 Heating Values EXAMPLE 13.3-1: Heating Value of a Producer Gas 13.3.3 Enthalpy and InternalEnergy as a Function of Temperature EXAMPLE 13.3-2: Propane Heater 13.3.4 Use of EES for Determining Properties EXAMPLE 13.3-3: Furnace Efficiency 13.3.5 Adiabatic Reactions EXAMPLE 13.3-4: Determination of the Explosion Pressure of Methane 13.4 Entropy Considerations EXAMPLE 13.4-1: Performance of a Gas Turbine Engine 13.5 Exergy of Fuel* (E18) 13.5.1 Energy and Entropy Balances on a Reversible Combustion Reaction* (E18) 13.5.2 Evaluation of the Exergy of a Fuel* (E18) EXAMPLE 13.5-1: Second Law Efficiency of a Furnace* (E18) References Problems

Chapter 14: Chemical Equilibrium

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14.1 Criterion for Chemical Equilibrium 14.2 Reaction Coordinates EXAMPLE 14.2-1: Simultaneous Chemical Reactions 14.3 The Law of Mass Action 14.3.1 The Criterion of Equilibrium in terms of Chemical Potentials 14.3.2 Chemical Potentials for an Ideal Gas Mixture 14.3.3 Equilibrium Constant and the Law of Mass Action for Ideal Gas Mixtures EXAMPLE 14.3-1: Reformation of Methane 14.3.4 Equilibrium Constant and the Law of Mass Action for an Ideal Solution EXAMPLE 14.3-2: Ammonia Synthesis 14.4 Alternative Methods for Chemical Equilibrium Problems 14.4.1 Direct Minimization of Gibbs Free Energy EXAMPLE 14.4-1: Reformation of Methane (revisited) 14.4.2 Lagrange Method of Undetermined Multipliers EXAMPLE 14.4-2: Reformation of Methane (revisited again) 14.5 Heterogeneous Reactions* (E19) 14.6 Adiabatic Reactions EXAMPLE 14.6-1: Adiabatic Combustion of Hydrogen EXAMPLE 14.6-2: Adiabatic Combustion of Acetylene References Problems

Chapter 15: Statistical Thermodynamics 15.1 A Brief Review of Quantum Theory History 15.1.1 Electromagnetic Radiation 15.1.2 Extension to Particles 15.2 The Wave Equation and Degeneracy for a Monatomic Ideal Gas 15.2.1 Probability of Finding a Particle 15.2.2 Application of a Wave Equation 15.2.3 Degeneracy 15.3 The Equilibrium Distribution 15.3.1 Macrostates and Thermodynamic Probability 15.3.2 Identification of the Most Probable Macrostate 15.3.3 The Significance of 15.3.4 Bolzmann's Law 15.4 Properties and the Partition Function 15.4.1 Definition of the Partition Function 15.4.2 Internal Energy from the Partition Function 15.4.3 Entropy from the Partition Function 15.4.3 Pressure from the Partition Function 15.5 Partition Function for an Monatomic Ideal Gas 15.5.1 Pressure for a Monatomic Ideal Gas 15.5.2 Internal Energy for a Monatomic Ideal Gas 15.5.3 Entropy for a Monatomic Ideal Gas

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EXAMPLE 15.5-1: Calculation of Absolute Entropy Values 15.6 Extension to More Complex Particles 15.7 Heat and Work from a Statistical Thermodynamics Perspective References Problems

Chapter 16: Compressible Flow* (E20) Problems

Appendix A: Unit Conversions and Useful Information Appendix B: Property Tables for Water Appendix C: Property Tables for R134a Appendix D: Ideal Gas & Incompressible Substances Appendix E: Ideal Gas Properties of Air Appendix F: Ideal Gas Properties of Common Combustion Gases Appendix G: Numerical Solution to ODEs (E21) G.1 Euler's Method G.2 Heun's Method* G.3 Fully Implicit Method* G.4 Crank-Nicolson Method* G.5 EES' Integral Command Appendix H: Introduction to Maple* (E22)