Description In this book, two leading experts and long-time instructors thoroughly explain therodynamics, taking the molecular perspective that working engineers require (and competitive books often avoid). This new Second Edition contains extensive new coverage of today's fast-growing biochemical engineering applications, notably biomass conversion to fuels and chemicals. It also presents many new MATLAB examples and tools to complement its previous usage of Excel and other software. Features ScreenCast supplements available from author website at: http://chethermo.net/screencasts Clear, colloquial, easy to use - and the only book in its market that focuses on the molecular perspective working engineers need Contains new MATLAB examples and tools, extensive new coverage of biochemical engineering and biomass conversions, and many other improvements Teaches molecular modeling and product design techniques that are rapidly being adopted in the marketplace Hierarchical instruction with increasing levels of detail: Content requiring deeper levels of theory is clearly delineated in separate sections and chapters Early introduction to the overall perspective of composite systems like distillation columns, reactive processes, and biological systems Learning objectives, problem-solving strategies for energy balances and phase equilibria, chapter summaries, and “important equations” for every chapter Extensive practical examples, especially coverage of non-ideal mixtures, which include water contamination via hydrocarbons, polymer blending/recycling, oxygenated fuels, hydrogen bonding, osmotic pressure, electrolyte solutions, zwitterions and biological molecules, and other contemporary issues Supporting software in formats for both MATLAB® and spreadsheets Online supplemental sections and resources including instructor slides, ConcepTests, coursecast videos, and other useful resources Please note - the solutions manual for this book is available in print only; it is not available on the IRC. The ISBN for the print solutions manual is 0132788527. New to this Edition This new Second Edition contains extensive new coverage of today's fast-growing biochemical engineering applications, notably biomass conversion to fuels and chemicals. It also presents many new MATLAB examples and tools to complement its previous usage of Excel and other software. New and updated coverage includes: Integrated discussions of biological thermodynamics throughout Clear learning objectives and outcomes for each chapter, provided as a web supplement More examples focusing on the First and Second Laws of thermodynamics and fluid phase equilibria in mixtures A new overview of mixture modeling concepts Reorganized, enhanced coverage of van der Waals and local composition models A brand-new chapter on molecular simulations Expanded coverage of stability theory Updated online supplements and new online teaching tools, including ConceptTesting Table of Contents Preface xvii About the Authors xix Glossary xxi Notation xxv Unit I: First and Second Laws 1 Chapter 1: Basic Concepts 3 1.1 Introduction 5 1.2 The Molecular Nature of Energy, Temperature, and Pressure 6 1.3 The Molecular Nature of Entropy 15 1.4 Basic Concepts 15 1.5 Real Fluids and Tabulated Properties 22 1.6 Summary 33 1.7 Practice Problems 34 1.8 Homework Problems 35 Chapter 2: The Energy Balance 39 2.1 Expansion/Contraction Work 40 2.2 Shaft Work 41 2.3 Work Associated with Flow 41 2.4 Lost Work versus Reversibility 42 2.5 Heat Flow 46 2.6 Path Properties and State Properties 46 2.7 The Closed-System Energy Balance 48 2.8 The Open-System, Steady-State Balance 51 2.9 The Complete Energy Balance 56 2.10 Internal Energy, Enthalpy, and Heat Capacities 57 2.11 Reference States 63 2.12 Kinetic and Potential Energy 66 2.13 Energy Balances for Process Equipment 68 2.14 Strategies for Solving Process Thermodynamics Problems 74 2.15 Closed and Steady-State Open Systems 75 2.16 Unsteady-State Open Systems 80 2.17 Details of Terms in the Energy Balance 85 2.18 Summary 86 2.19 Practice Problems 88 2.20 Homework Problems 90 Chapter 3: Energy Balances for Composite Systems 93 3.1 Heat Engines and Heat Pumps – The Carnot Cycle 94 3.2 Distillation Columns 99 3.3 Introduction to Mixture Properties 103 3.4 Ideal Gas Mixture Properties 104 3.5 Mixture Properties for Ideal Solutions 104 3.6 Energy Balance for Reacting Systems 107 3.7 Reactions in Biological Systems 117 3.8 Summary 119 3.9 Practice Problems 120 3.10 Homework Problems 120 Chapter 4: Entropy 127 4.1 The Concept of Entropy 128 4.2 The Microscopic View of Entropy 130 4.3 The Macroscopic View of Entropy140 4.4 The Entropy Balance 151 4.5 Internal Reversibility 156 4.6 Entropy Balances for Process Equipment 157 4.7 Turbine, Compressor, and Pump Efficiency 162 4.8 Visualizing Energy and Entropy Changes 163 4.9 Turbine Calculations 164 4.10 Pumps and Compressors 171 4.11 Strategies for Applying the Entropy Balance 173 4.12 Optimum Work and Heat Transfer 175 4.13 The Irreversibility of Biological Life 179 4.14 Unsteady-State Open Systems 180 4.15 The Entropy Balance in Brief 183 4.16 Summary 183 4.17 Practice Problems 185 4.18 Homework Problems 187 Chapter 5: Thermodynamics of Processes 197 5.1 The Carnot Steam Cycle 197 5.2 The Rankine Cycle 198 5.3 Rankine Modifications 201 5.4 Refrigeration 206 5.5 Liquefaction 210 5.6 Engines 212 5.7 Fluid Flow 212 5.8 Problem-Solving Strategies 212 5.9 Summary 213 5.10 Practice Problems 213 5.11 Homework Problems 214 Unit II: Generalized Analysis of Fluid Properties 221 Chapter 6: Classical Thermodynamics — Generalizations for Any Fluid 223 6.1 The Fundamental Property Relation 224 6.2 Derivative Relations 227 6.3 Advanced Topics 242 6.4 Summary 245 6.5 Practice Problems 246 6.6 Homework Problems 246 Chapter 7: Engineering Equations of State for PVT Properties 249 7.1 Experimental Measurements 250 7.2 Three-Parameter Corresponding States 251 7.3 Generalized Compressibility Factor Charts 254 7.4 The Virial Equation of State 256 7.5 Cubic Equations of State 258 7.6 Solving the Cubic Equation of State for Z 261 7.7 Implications of Real Fluid Behavior 267 7.8 Matching the Critical Point 268 7.9 The Molecular Basis of Equations of State: Concepts and Notation 269 7.10 The Molecular Basis of Equations of State: Molecular Simulation 274 7.11 The Molecular Basis of Equations of State: Analytical Theories 280 7.12 Summary 287 7.13 Practice Problems 288 7.14 Homework Problems 289 Chapter 8: Departure Functions 299 8.1 The Departure Function Pathway 300 8.2 Internal Energy Departure Function 302 8.3 Entropy Departure Function 305 8.4 Other Departure Functions 306 8.5 Summary of Density-Dependent Formulas 306 8.6 Pressure-Dependent Formulas 307 8.7 Implementation of Departure Formulas 308 8.8 Reference States 316 8.9 Generalized Charts for the Enthalpy Departure 321 8.10 Summary 321 8.11 Practice Problems 323 8.12 Homework Problems 324 Chapter 9: Phase Equilibrium in a Pure Fluid 331 9.1 Criteria for Phase Equilibrium 332 9.2 The Clausius-Clapeyron Equation 333 9.3 Shortcut Estimation of Saturation Properties 335 9.4 Changes in Gibbs Energy with Pressure 338 9.5 Fugacity and Fugacity Coefficient 340 9.6 Fugacity Criteria for Phase Equilibria 342 9.7 Calculation of Fugacity (Gases) 343 9.8 Calculation of Fugacity (Liquids) 344 9.9 Calculation of Fugacity (Solids) 349 9.10 Saturation Conditions from an Equation of State 349 9.11 Stable Roots and Saturation Conditions 355 9.12 Temperature Effects on G and f 357 9.13 Summary 357 9.14 Practice Problems 358 9.15 Homework Problems 359 Unit III: Fluid Phase Equilibria in Mixtures 363 Chapter 10: Introduction to Multicomponent Systems 365 10.1 Introduction to Phase Diagrams 366 10.2 Vapor-Liquid Equilibrium (VLE) Calculations 368 10.3 Binary VLE Using Raoult’s Law 370 10.4 Multicomponent VLE Raoult’s Law Calculations 377 10.5 Emissions and Safety 382 10.6 Relating VLE to Distillation 386 10.7 Nonideal Systems 389 10.8 Concepts for Generalized Phase Equilibria 393 10.9 Mixture Properties for Ideal Gases 397 10.10 Mixture Properties for Ideal Solutions 399 10.11 The Ideal Solution Approximation and Raoult’s Law 400 10.12 Activity Coefficient and Fugacity Coefficient Approaches 401 10.13 Summary 401 10.14 Practice Problems 403 10.15 Homework Problems 403 Chapter 11: An Introduction to Activity Models 407 11.1 Modified Raoult’s Law and Excess Gibbs Energy 408 11.2 Calculations Using Activity Coefficients 412 11.3 Deriving Modified Raoult’s Law 419 11.4 Excess Properties 422 11.5 Modified Raoult’s Law and Excess Gibbs Energy 423 11.6 Redlich-Kister and the Two-Parameter Margules Models 425 11.7 Activity Coefficients at Special Compositions 428 11.8 Preliminary Indications of VLLE 430 11.9 Fitting Activity Models to Multiple Data 431 11.10 Relations for Partial Molar Properties 435 11.11 Distillation and Relative Volatility of Nonideal Solutions 438 11.12 Lewis-Randall Rule and Henry’s Law 439 11.13 Osmotic Pressure 445 11.14 Summary 450 11.15 Practice Problems 451 11.16 Homework Problems 451 Chapter 12: Van der Waals Activity Models 459 12.1 The Van der Waals Perspective for Mixtures 460 12.2 The Van Laar Model 463 12.3 Scatchard-Hildebrand Theory 465 12.4 The Flory-Huggins Model 468 12.5 MOSCED And SSCED Theories 473 12.6 Molecular Perspective and VLE Predictions 477 12.7 Multicomponent Extensions of van der Waals’ Models 480 12.8 Flory-Huggins and van der Waals Theories 485 12.9 Summary 486 12.10 Practice Problems 488 12.11 Homework Problems 489 Chapter 13: Local Composition Activity Models 493 13.1 Local Composition Theory 495 13.2 Wilson’s Equation 499 13.3 NRTL 502 13.4 UNIQUAC 503 13.5 UNIFAC 508 13.6 COSMO-RS Methods 514 13.7 The Molecular Basis of Solution Models 520 13.8 Summary 526 13.9 Important Equations 527 13.10 Practice Problems 527 13.11 Homework Problems 527 Chapter 14: Liquid-Liquid and Solid-Liquid Phase Equilibria 531 14.1 The Onset of Liquid-Liquid Instability 531 14.2 Stability and Excess Gibbs Energy 534 14.3 Binary LLE by Graphing the Gibbs Energy of Mixing 535 14.4 LLE Using Activities 537 14.5 VLLE with Immiscible Components 540 14.6 Binary Phase Diagrams 541 14.7 Plotting Ternary LLE Data 543 14.8 Critical Points in Binary Liquid Mixtures 544 14.9 Numerical Procedures for Binary, Ternary LLE 548 14.10 Solid-Liquid Equilibria 548 14.11 Summary 561 14.12 Practice Problems 562 14.13 Homework Problems 562 Chapter 15: Phase Equilibria in Mixtures by an Equation of State 571 15.1 Mixing Rules for Equations of State 572 15.2 Fugacity and Chemical Potential from an EOS 574 15.3 Differentiation of Mixing Rules 580 15.4 VLE Calculations by an Equation of State 586 15.5 Strategies for Applying VLE Routines 595 15.6 Summary 595 15.7 Practice Problems 596 15.8 Homework Problems 598 Chapter 16: Advanced Phase Diagrams 605 16.1 Phase Behavior Sections of 3D Objects 605 16.2 Classification of Binary Phase Behavior 609 16.3 Residue Curves 622 16.4 Practice Problems 628 16.5 Homework Problems 628 Unit IV: Reaction Equilibria 631 Chapter 17: Reaction Equilibria 633 17.1 Introduction 634 17.2 Reaction Equilibrium Constraint 636 17.3 The Equilibrium Constant 638 17.4 The Standard State Gibbs Energy of Reaction 639 17.5 Effects of Pressure, Inerts, and Feed Ratios 641 17.6 Determining the Spontaneity of Reactions 644 17.7 Temperature Dependence of Ka 644 17.8 Shortcut Estimation of Temperature Effects 647 17.9 Visualizing Multiple Equilibrium Constants 648 17.10 Solving Equilibria for Multiple Reactions 650 17.11 Driving Reactions by Chemical Coupling 654 17.12 Energy Balances for Reactions 656 17.13 Liquid Components in Reactions 659 17.14 Solid Components in Reactions 661 17.15 Rate Perspectives in Reaction Equilibria 663 17.16 Entropy Generation via Reactions 664 17.17 Gibbs Minimization 665 17.18 Reaction Modeling with Limited Data 669 17.19 Simultaneous Reaction and VLE 669 17.20 Summary 675 17.21 Practice Problems 676 17.22 Homework Problems 678 Chapter 18: Electrolyte Solutions 685 18.1 Introduction to Electrolyte Solutions 685 18.2 Colligative Properties 687 18.3 Speciation and the Dissociation Constant 689 18.4 Concentration Scales and Standard States 691 18.5 The Definition of pH 693 18.6 Thermodynamic Network for Electrolyte Equilibria 694 18.7 Perspectives on Speciation 695 18.8 Acids and Bases 696 18.9 Sillèn Diagram Solution Method 704 18.10 Applications 715 18.11 Redox Reactions 719 18.12 Biological Reactions 723 18.13 Nonideal Electrolyte Solutions: Background 731 18.14 Overview of Model Development 732 18.15 The Extended Debye-Hückel Activity Model 734 18.16 Gibbs Energies for Electrolytes 735 18.17 Transformed Biological Gibbs Energies and Apparent Equilibrium Constants 737 18.18 Coupled Multireaction and Phase Equilibria 741 18.19 Mean Ionic Activity Coefficients 745 18.20 Extending Activity Calculations to High Concentrations 747 18.21 Summary 747 18.22 Supplement 1: Interconversion of Concentration Scales 749 18.23 Supplement 2: Relation of Apparent Chemical Potential to Species Potentials 750 18.24 Supplement 3: Standard States 751 18.25 Supplement 4: Conversion of Equilibrium Constants 752 18.26 Practice Problems 753 18.27 Homework Problems 753 Chapter 19: Molecular Association and Solvation 759 19.1 Introducing the Chemical Contribution 760 19.2 Equilibrium Criteria 764 19.3 Balance Equations for Binary Systems 767 19.4 Ideal Chemical Theory for Binary Systems 768 19.5 Chemical-Physical Theory 771 19.6 Wertheim’s Theory for Complex Mixtures 774 19.7 Mass Balances for Chain Association 784 19.8 The Chemical Contribution to the Fugacity Coefficient and Compressibility Factor 785 19.9 Wertheim’s Theory of Polymerization 787 19.10 Statistical Associating Fluid Theory (the SAFT Model) 791 19.11 Fitting the Constants for an Associating Equation of State 794 19.12 Summary 796 19.13 Practice Problems 798 19.14 Homework Problems 798 Appendix A: Summary of Computer Programs 803 A.1 Programs for Pure Component Properties 803 A.2 Programs for Mixture Phase Equilibria 804 A.3 Reaction Equilibria 805 A.4 Notes on Excel Spreadsheets 805 A.5 Notes on MATLAB 806 A.6 Disclaimer 807 Appendix B: Mathematics 809 B.1 Important Relations 809 B.2 Solutions to Cubic Equations 814 B.3 The Dirac Delta Function 817 Appendix C: Strategies for Solving VLE Problems 823 C.1 Modified Raoult’s Law Methods 824 C.2 EOS Methods 827 C.3 Activity Coefficient (Gamma-Phi) Methods 830 Appendix D: Models for Process Simulators 831 D.1 Overview 831 D.2 Equations of State 831 D.3 Solution Models 832 D.4 Hybrid Models 832 D.5 Recommended Decision Tree 833 Appendix E: Themodynamic Properties 835 E.1 Thermochemical Data 835 E.2 Latent Heats 838 E.3 Antoine Constants 839 E.4 Henry’s Constant with Water as Solvent 839 E.5 Dielectric Constant for Water 840 E.6 Dissociation Constants of Polyprotic Acids 841 E.7 Standard Reduction Potentials 841 E.8 Biochemical Data 844 E.9 Properties of Water 846 E.10 Pressure-Enthalpy Diagram for Methane 857 E.11 Pressure-Enthalpy Diagram for Propane 858 E.12 Pressure-Enthalpy Diagram for R134A (1,1,1,2-Tetraflouroethane) 859 Index 861