Engineering and Chemical Thermodynamics

Milo D. Koretsky received his Ph.D. in Chemical Engineering from the University of California at Berkeley in 1991. He is currently of professor of Chemical Engineering at Oregon State University. His research interests in thin film materials processing, including plasma chemistry and physics, electrochemical processes and semiconductor yield prediction. His teaching interests include integration of microelectronic unit operations into the ChE curriculum and thermodynamics.

• CHAPTER 1 Measured Thermodynamic Properties and Other Basic Concepts 1Learning Objectives 11.1 Thermodynamics 21.2 Preliminary Concepts—The Language of Thermo 3Thermodynamic Systems 3Properties 4Processes 5Hypothetical Paths 6Phases of Matter 6Length Scales 6Units 71.3 Measured Thermodynamic Properties 7Volume (Extensive or Intensive) 7Temperature (Intensive) 8Pressure (Intensive) 11The Ideal Gas 131.4 Equilibrium 15Types of Equilibrium 15Molecular View of Equilibrium 161.5 Independent and Dependent Thermodynamic Properties 17The State Postulate 17Gibbs Phase Rule 181.6 The PʋT Surface and Its Projections for Pure Substances 20Changes of State During a Process 22Saturation Pressure vs. Vapor Pressure 23The Critical Point 241.7 Thermodynamic Property Tables 261.8 Summary 301.9 Problems 31Conceptual Problems 31Numerical Problems 34CHAPTER 2 The First Law of Thermodynamics 36Learning Objectives 362.1 The First Law of Thermodynamics 37Forms of Energy 37Ways We Observe Changes in U 39Internal Energy of an Ideal Gas 40Work and Heat: Transfer of Energy Between the System and the Surroundings 422.2 Construction of Hypothetical Paths 462.3 Reversible and Irreversible Processes 48Reversible Processes 48Irreversible Processes 48Efficiency 552.4 The First Law of Thermodynamics for Closed Systems 55Integral Balances 55Differential Balances 572.5 The First Law of Thermodynamics for Open Systems 60Material Balance 60Flow Work 60Enthalpy 62Steady-State Energy Balances 62Transient Energy Balance 632.6ThermochemicalData For U and H 67Heat Capacity: cʋ and cP 67Latent Heats 76Enthalpy of Reactions 802.7 Reversible Processes in Closed Systems 92Reversible, Isothermal Expansion (Compression) 92Adiabatic Expansion (Compression) with Constant Heat Capacity 93Summary 952.8 Open-System Energy Balances on Process Equipment 95Nozzles and Diffusers 96Turbines and Pumps (or Compressors) 97Heat Exchangers 98Throttling Devices 1012.9 Thermodynamic Cycles and the Carnot Cycle 102Efficiency 1042.10 Summary 1082.11 Problems 110Conceptual Problems 110Numerical Problems 113CHAPTER 3 Entropy and the Second Law Of Thermodynamics 127Learning Objectives 1273.1 Directionality of Processes/Spontaneity 1283.2 Reversible and Irreversible Processes (Revisited) and their Relationship to Directionality 1293.3 Entropy, the Thermodynamic Property 1313.4 The Second Law of Thermodynamics 1403.5 Other Common Statements of the Second Law of Thermodynamics 1423.6 The Second Law of Thermodynamics for Closed and Open Systems 143Calculation of Δs for Closed Systems 143Calculation of Δs for Open Systems 1473.7 Calculation of Δs for an Ideal Gas 1513.8 The Mechanical Energy Balance and the Bernoulli Equation 1603.9 Vapor-Compression Power and Refrigeration Cycles 164The Rankine Cycle 164The Vapor-Compression Refrigeration Cycle 1693.10 Exergy (Availability) Analysis 172Exergy 173Exthalpy—Flow Exergy in Open Systems 1783.11 Molecular View of Entropy 182Maximizing Molecular Confi gurations over Space 185Maximizing Molecular Confi gurations over Energy 1863.12 Summary 1903.13 Problems 191Conceptual Problems 191Numerical Problems 195CHAPTER 4 Equations of State and Intermolecular Forces 209Learning Objectives 2094.1 Introduction 210Motivation 210The Ideal Gas 2114.2 Intermolecular Forces 211Internal (Molecular) Energy 211The Electric Nature of Atoms and Molecules 212Attractive Forces 213Intermolecular Potential Functions and Repulsive Forces 223Principle of Corresponding States 226Chemical Forces 2284.3 Equations of State 232The van der Waals Equation of State 232Cubic Equations of State (General) 238The Virial Equation of State 240Equations of State for Liquids and Solids 2454.4 Generalized Compressibility Charts 2464.5 Determination of Parameters for Mixtures 249Cubic Equations of State 250Virial Equation of State 251Corresponding States 2524.6 Summary 2544.7 Problems 255Conceptual Problems 255Numerical Problems 257CHAPTER 5 The Thermodynamic Web 265Learning Objectives 2655.1 Types of Thermodynamic Properties 265Measured Properties 265Fundamental Properties 266Derived Thermodynamic Properties 2665.2 Thermodynamic Property Relationships 267Dependent and Independent Properties 267Hypothetical Paths (revisited) 268Fundamental Property Relations 269Maxwell Relations 271Other Useful Mathematical Relations 272Using the Thermodynamic Web to Access Reported Data 2735.3 Calculation of Fundamental and Derived Properties Using Equations of State and Other Measured Quantities 276Relation of ds in Terms of Independent Properties T and ʋ and Independent Properties T and P 276Relation of du in Terms of Independent Properties T and ʋ 277Relation of dh in Terms of Independent Properties T and P 281Alternative Formulation of the Web using T and P as Independent Properties 2875.4 Departure Functions 290Enthalpy Departure Function 290Entropy Departure Function 2935.5 Joule-Thomson Expansion and Liquefaction 298Joule-Thomson Expansion 298Liquefaction 3015.6 Summary 3045.7 Problems 305Conceptual Problems 305Numerical Problems 307CHAPTER 6 Phase Equilibria I: Problem Formulation 315Learning Objectives 3156.1 Introduction 315The Phase Equilibria Problem 3166.2 Pure Species Phase Equilibrium 318Gibbs Energy as a Criterion for ChemicalEquilibrium 318Roles of Energy and Entropy in Phase Equilibria 321The Relationship Between Saturation Pressure and Temperature: The Clapeyron Equation 327Pure Component Vapor–Liquid Equilibrium: The Clausius–Clapeyron Equation 3286.3 Thermodynamics of Mixtures 334Introduction 334Partial Molar Properties 335The Gibbs–Duhem Equation 340Summary of the Different Types of Thermodynamic Properties 342Property Changes of Mixing 343Determination of Partial Molar Properties 357Relations Among Partial Molar Quantities 3666.4 Multicomponent Phase Equilibria 367The Chemical Potential—The Criteria for Chemical Equilibrium 367Temperature and Pressure Dependence of μi 3706.5 Summary 3726.6 Problems 373Conceptual Problems 373Numerical Problems 377CHAPTER 7 Phase Equilibria II: Fugacity 391Learning Objectives 3917.1 Introduction 3917.2 The Fugacity 392Definition of Fugacity 392Criteria for Chemical Equilibria in Terms of Fugacity 3957.3 Fugacity in the Vapor Phase 396Fugacity and Fugacity Coefficient of Pure Gases 396Fugacity and Fugacity Coefficient of Species i in a Gas Mixture 403The Lewis Fugacity Rule 411Property Changes of Mixing for Ideal Gases 4127.4 Fugacity in the Liquid Phase 414Reference States for the Liquid Phase 414Thermodynamic Relations Between γi 422Models for γi Using gE 428Equation of State Approach to the Liquid Phase 4497.5 Fugacity in the Solid Phase 449Pure Solids 449Solid Solutions 449Interstitials and Vacancies in Crystals 4507.6 Summary 4507.7 Problems 452Conceptual Problems 452Numerical Problems 454CHAPTER 8 Phase Equilibria III: Applications 466Learning Objectives 4668.1 Vapor–Liquid Equilibrium (VLE) 467Raoult’s Law (Ideal Gas and Ideal Solution) 467Nonideal Liquids 475Azeotropes 484Fitting Activity Coeffi cient Models with VLE Data 490Solubility of Gases in Liquids 495Vapor–Liquid Equilibrium Using the Equations of State Method 5018.2 Liquid 1a2—Liquid 1b2 Equilibrium: LLE 5118.3 Vapor–Liquid 1a2— Liquid 1b2 Equilibrium: VLLE 5198.4 Solid–Liquid and Solid–Solid Equilibrium:SLE and SSE 523Pure Solids 523Solid Solutions 5298.5 Colligative Properties 531Boiling Point Elevation and Freezing Point Depression 531Osmotic Pressure 5358.6 Summary 5388.7 Problems 540Conceptual Problems 540Numerical Problems 544CHAPTER 9 Chemical Reaction Equilibria 562Learning Objectives 5629.1 Thermodynamics and Kinetics 5639.2 Chemical Reaction and Gibbs Energy 5659.3 Equilibrium for a Single Reaction 5689.4 Calculation of K from Thermochemical Data 572Calculation of K from Gibbs Energy of Formation 572The Temperature Dependence of K 5749.5 Relationship Between the Equilibrium Constant and the Concentrations of Reacting Species 579The Equilibrium Constant for a Gas-Phase Reaction 579The Equilibrium Constant for a Liquid-Phase (or Solid-Phase) Reaction 586The Equilibrium Constant for a Heterogeneous Reaction 5879.6 Equilibrium in Electrochemical Systems 589Electrochemical Cells 590Shorthand Notation 591Electrochemical Reaction Equilibrium 592Thermochemical Data: Half-Cell Potentials 594Activity Coeffi cients in Electrochemical Systems 5979.7 Multiple Reactions 599Extent of Reaction and Equilibrium Constant for R Reactions 599Gibbs Phase Rule for Chemically Reacting Systems and Independent Reactions 601Solution of Multiple Reaction Equilibria by Minimization of Gibbs Energy 6109.8 Reaction Equilibria of Point Defects in Crystalline Solids 612Atomic Defects 613Electronic Defects 616Effect of Gas Partial Pressure on Defect Concentrations 6199.9 Summary 6249.10 Problems 626Conceptual Problems 626Numerical Problems 628APPENDIX A Physical Property Data 639APPENDIX B Steam Tables 647APPENDIX C Lee–Kesler Generalized Correlation Tables 660APPENDIX D Unit Systems 676APPENDIX E ThermoSolver Software 680APPENDIX F References 685Index 687