Preface xvii About the Authors xixGlossary xxiNotation xxv Unit I: First and Second Laws 1 Chapter 1: Basic Concepts 3 1.1 Introduction 51.2 The Molecular Nature of Energy, Temperature, and Pressure 61.3 The Molecular Nature of Entropy 151.4 Basic Concepts 151.5 Real Fluids and Tabulated Properties 221.6 Summary 33 1.7 Practice Problems 341.8 Homework Problems 35 Chapter 2: The Energy Balance 392.1 Expansion/Contraction Work 402.2 Shaft Work 412.3 Work Associated with Flow 412.4 Lost Work versus Reversibility 422.5 Heat Flow 462.6 Path Properties and State Properties 462.7 The Closed-System Energy Balance 482.8 The Open-System, Steady-State Balance 512.9 The Complete Energy Balance 562.10 Internal Energy, Enthalpy, and Heat Capacities 572.11 Reference States 632.12 Kinetic and Potential Energy 662.13 Energy Balances for Process Equipment 682.14 Strategies for Solving Process Thermodynamics Problems 742.15 Closed and Steady-State Open Systems 752.16 Unsteady-State Open Systems 802.17 Details of Terms in the Energy Balance 852.18 Summary 862.19 Practice Problems 882.20 Homework Problems 90 Chapter 3: Energy Balances for Composite Systems 953.1 Heat Engines and Heat Pumps - The Carnot Cycle 963.2 Distillation Columns 1013.3 Introduction to Mixture Properties 1053.4 Ideal Gas Mixture Properties 1063.5 Mixture Properties for Ideal Solutions 1063.6 Energy Balance for Reacting Systems 1093.7 Reactions in Biological Systems 1193.8 Summary 1213.9 Practice Problems 1223.10 Homework Problems 122 Chapter 4: Entropy 1294.1 The Concept of Entropy 1304.2 The Microscopic View of Entropy 1324.3 The Macroscopic View of Entropy 1424.4 The Entropy Balance 1534.5 Internal Reversibility 1584.6 Entropy Balances for Process Equipment 1594.7 Turbine, Compressor, and Pump Efficiency 1644.8 Visualizing Energy and Entropy Changes 1654.9 Turbine Calculations 1664.10 Pumps and Compressors 1734.11 Strategies for Applying the Entropy Balance 1754.12 Optimum Work and Heat Transfer 1774.13 The Irreversibility of Biological Life 181 4.14 Unsteady-State Open Systems 1824.15 The Entropy Balance in Brief 185 4.16 Summary 1854.17 Practice Problems 1874.18 Homework Problems 189 Chapter 5: Thermodynamics Of Processes 1995.1 The Carnot Steam Cycle 1995.2 The Rankine Cycle 2005.3 Rankine Modifications 2035.4 Refrigeration 2085.5 Liquefaction 2125.6 Engines 2145.7 Fluid Flow 2145.8 Problem-Solving Strategies 2145.9 Summary 2155.10 Practice Problems 2155.11 Homework Problems 216 Unit II: Generalized Analysis of Fluid Properties 223 Chapter 6: Classical Thermodynamics - Generalizations For Any Fluid 2256.1 The Fundamental Property Relation 2266.2 Derivative Relations 2296.3 Advanced Topics 2446.4 Summary 2476.5 Practice Problems 2486.6 Homework Problems 248 Chapter 7: Engineering Equations of State for PVT Properties 2517.1 Experimental Measurements 2527.2 Three-Parameter Corresponding States 2537.3 Generalized Compressibility Factor Charts 2567.4 The Virial Equation of State 2587.5 Cubic Equations of State 2607.6 Solving the Cubic Equation of State for Z 2637.7 Implications of Real Fluid Behavior 2697.8 Matching the Critical Point 2707.9 The Molecular Basis of Equations of State: Concepts and Notation 2717.10 The Molecular Basis of Equations of State: Molecular Simulation 2767.11 The Molecular Basis of Equations of State: Analytical Theories 2827.12 Summary 2897.13 Practice Problems 2907.14 Homework Problems 291 Chapter 8: Departure Functions 3018.1 The Departure Function Pathway 3028.2 Internal Energy Departure Function 3048.3 Entropy Departure Function 3078.4 Other Departure Functions 3088.5 Summary of Density-Dependent Formulas 3088.6 Pressure-Dependent Formulas 3098.7 Implementation of Departure Formulas3108.8 Reference States 3188.9 Generalized Charts for the Enthalpy Departure 3238.10 Summary 3238.11 Practice Problems 3258.12 Homework Problems326 Chapter 9: Phase Equilibrium in a Pure Fluid 3359.1 Criteria for Phase Equilibrium 3369.2 The Clausius-Clapeyron Equation 3379.3 Shortcut Estimation of Saturation Properties 3399.4 Changes in Gibbs Energy with Pressure 342 9.5 Fugacity and Fugacity Coefficient 344 9.6 Fugacity Criteria for Phase Equilibria 346 9.7 Calculation of Fugacity (Gases) 347 9.8 Calculation of Fugacity (Liquids) 3489.9 Calculation of Fugacity (Solids) 3539.10 Saturation Conditions from an Equation of State 3539.11 Stable Roots and Saturation Conditions 359 9.12 Temperature Effects on G and f 3619.13 Summary 3619.14 Practice Problems 3629.15 Homework Problems 363 Unit III: Fluid Phase Equilibria in Mixtures 367 Chapter 10: Introduction to Multicomponent Systems 36910.1 Introduction to Phase Diagrams 37010.2 Vapor-Liquid Equilibrium (VLE) Calculations 37210.3 Binary VLE Using Raoult's Law 37410.4 Multicomponent VLE Raoult's Law Calculations 38110.5 Emissions and Safety 38610.6 Relating VLE to Distillation 39010.7 Nonideal Systems 39310.8 Concepts for Generalized Phase Equilibria 39710.9 Mixture Properties for Ideal Gases 40110.10 Mixture Properties for Ideal Solutions 40310.11 The Ideal Solution Approximation and Raoult's Law 40410.12 Activity Coefficient and Fugacity Coefficient Approaches 40510.13 Summary 40510.14 Practice Problems 40710.15 Homework Problems 407 Chapter 11: An Introduction To Activity Models 41111.1 Modified Raoult's Law and Excess Gibbs Energy 41211.2 Calculations Using Activity Coefficients 41611.3 Deriving Modified Raoult's Law 42311.4 Excess Properties 42611.5 Modified Raoult's Law and Excess Gibbs Energy 42711.6 Redlich-Kister and the Two-Parameter Margules Models 42911.7 Activity Coefficients at Special Compositions 43211.8 Preliminary Indications of VLLE 43411.9 Fitting Activity Models to Multiple Data 43511.10 Relations for Partial Molar Properties 43911.11 Distillation and Relative Volatility of Nonideal Solutions 44211.12 Lewis-Randall Rule and Henry's Law 44311.13 Osmotic Pressure 44911.14 Summary 45411.15 Practice Problems 45511.16 Homework Problems 455 Chapter 12: van der Waals Activity Models 46512.1 The van der Waals Perspective for Mixtures 46612.2 The van Laar Model 46912.3 Scatchard-Hildebrand Theory 47112.4 The Flory-Huggins Model 47412.5 MOSCED and SSCED Theories 47912.6 Molecular Perspective and VLE Predictions 48312.7 Multicomponent Extensions of van der Waals' Models 48612.8 Flory-Huggins and van der Waals Theories 49112.9 Summary 49212.10 Practice Problems 49412.11 Homework Problems 495 Chapter 13: Local Composition Activity Models 49913.1 Local Composition Theory 50113.2 Wilson's Equation 50513.3 NRTL 50813.4 UNIQUAC 50913.5 UNIFAC 51413.6 COSMO-RS Methods 52013.7 The Molecular Basis of Solution Models 52613.8 Summary 53213.9 Important Equations 53313.10 Practice Problems 53313.11 Homework Problems 534 Chapter 14: Liquid-Liquid and Solid-Liquid Phase Equilibria 53914.1 The Onset of Liquid-Liquid Instability 53914.2 Stability and Excess Gibbs Energy 54214.3 Binary LLE by Graphing the Gibbs Energy of Mixing 54314.4 LLE Using Activities 54514.5 VLLE with Immiscible Components 54814.6 Binary Phase Diagrams 54914.7 Plotting Ternary LLE Data 55114.8 Critical Points in Binary Liquid Mixtures 55214.9 Numerical Procedures for Binary, Ternary LLE 55614.10 Solid-Liquid Equilibria 55614.11 Summary 56914.12 Practice Problems 57014.13 Homework Problems 570 Chapter 15: Phase Equilibria in Mixtures by an Equation of State 579 15.1 Mixing Rules for Equations of State 58015.2 Fugacity and Chemical Potential from an EOS 58215.3 Differentiation of Mixing Rules 58815.4 VLE Calculations by an Equation of State 59415.5 Strategies for Applying VLE Routines 60315.6 Summary 60315.7 Practice Problems 60415.8 Homework Problems 606 Chapter 16: Advanced Phase Diagrams 61316.1 Phase Behavior Sections of 3D Objects 61316.2 Classification of Binary Phase Behavior 61716.3 Residue Curves 63016.4 Practice Problems 63616.5 Homework Problems 636 Unit IV: Reaction Equilibria 639 Chapter 17: Reaction Equilibria 64117.1 Introduction 64217.2 Reaction Equilibrium Constraint 64417.3 The Equilibrium Constant 64617.4 The Standard State Gibbs Energy of Reaction 64717.5 Effects of Pressure, Inerts, and Feed Ratios 64917.6 Determining the Spontaneity of Reactions 65217.7 Temperature Dependence of Ka 65217.8 Shortcut Estimation of Temperature Effects 65517.9 Visualizing Multiple Equilibrium Constants 65617.10 Solving Equilibria for Multiple Reactions 65817.11 Driving Reactions by Chemical Coupling 66217.12 Energy Balances for Reactions 66417.13 Liquid Components in Reactions 66717.14 Solid Components in Reactions 66917.15 Rate Perspectives in Reaction Equilibria 671 17.16 Entropy Generation via Reactions 672 17.17 Gibbs Minimization 67317.18 Reaction Modeling with Limited Data 677 17.19 Simultaneous Reaction and VLE 67717.20 Summary 68317.21 Practice Problems 68417.22 Homework Problems 686 Chapter 18: Electrolyte Solutions 69318.1 Introduction to Electrolyte Solutions 69318.2 Colligative Properties 69518.3 Speciation and the Dissociation Constant 69718.4 Concentration Scales and Standard States 69918.5 The Definition of pH 70118.6 Thermodynamic Network for Electrolyte Equilibria 70218.7 Perspectives on Speciation 70318.8 Acids and Bases 70418.9 Sillen Diagram Solution Method71218.10 Applications 72318.11 Redox Reactions 72718.12 Biological Reactions 73118.13 Nonideal Electrolyte Solutions: Background 73918.14 Overview of Model Development 74018.15 The Extended Debye-Huckel Activity Model 74218.16 Gibbs Energies for Electrolytes 74318.17 Transformed Biological Gibbs Energies and Apparent Equilibrium Constants 74518.18 Coupled Multireaction and Phase Equilibria 74918.19 Mean Ionic Activity Coefficients 75318.20 Extending Activity Calculations to High Concentrations 75518.21 Summary 75518.22 Supplement 1: Interconversion of Concentration Scales 75718.23 Supplement 2: Relation of Apparent Chemical Potential to Species Potentials 75818.24 Supplement 3: Standard States 75918.25 Supplement 4: Conversion of Equilibrium Constants 76018.26 Practice Problems 76118.27 Homework Problems 761 Chapter 19: Molecular Association and Solvation 76719.1 Introducing the Chemical Contribution 76819.2 Equilibrium Criteria 77219.3 Balance Equations for Binary Systems 77519.4 Ideal Chemical Theory for Binary Systems 77619.5 Chemical-Physical Theory 77919.6 Wertheim's Theory for Complex Mixtures 78219.7 Mass Balances for Chain Association 79219.8 The Chemical Contribution to the Fugacity Coefficient and Compressibility Factor 79319.9 Wertheim's Theory of Polymerization 79519.10 Statistical Associating Fluid Theory (The SAFT Model) 79919.11 Fitting the Constants for an Associating Equation of State 80219.12 Summary 80419.13 Practice Problems 80619.14 Homework Problems 806 Appendix A: Summary of Computer Programs 811A.1 Programs for Pure Component Properties 811A.2 Programs for Mixture Phase Equilibria 812A.3 Reaction Equilibria 813A.4 Notes on Excel Spreadsheets 813A.5 Notes on MATLAB 814A.6 Disclaimer 815 Appendix B: Mathematics 817B.1 Important Relations 817B.2 Solutions to Cubic Equations 822B.3 The Dirac Delta Function 825 Appendix C: Strategies for Solving VLE Problems 831C.1 Modified Raoult's Law Methods 832C.2 EOS Methods 835C.3 Activity Coefficient (Gamma-Phi) Methods 838 Appendix D: Models for Process Simulators 839D.1 Overview 839D.2 Equations of State 839D.3 Solution Models 840D.4 Hybrid Models 840D.5 Recommended Decision Tree 841 Appendix E: Themodynamic Properties 843E.1 Thermochemical Data 843E.2 Latent Heats 846E.3 Antoine Constants 847E.4 Henry's Constant with Water as Solvent 847E.5 Dielectric Constant for Water 848E.6 Dissociation Constants of Polyprotic Acids 849E.7 Standard Reduction Potentials 849E.8 Biochemical Data 852E.9 Properties of Water 854E.10 Pressure-Enthalpy Diagram for Methane 865E.11 Pressure-Enthalpy Diagram for Propane 866E.12 Pressure-Enthalpy Diagram for R134a (1,1,1,2-Tetraflouroethane) 867 Index 869