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Introductory Chemical Engineering Thermodynamics: Prentice Hall International Series in the Physical and Chemi

Autor J. Richard Elliott, Carl T. Lira
en Limba Engleză Hardback – 31 ian 2012
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.
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Specificații

ISBN-13: 9780136068549
ISBN-10: 0136068545
Pagini: 912
Dimensiuni: 208 x 254 x 51 mm
Greutate: 1.88 kg
Ediția:Revised
Editura: Prentice Hall
Seria Prentice Hall International Series in the Physical and Chemi


Notă biografică

J. Richard Elliott is Professor of Chemical Engineering at the University of Akron in Ohio. He has taught courses ranging from freshman tools to senior process design as well as thermodynamics at every level. He has worked with the NIST lab in Boulder and ChemStations in Houston. He holds a Ph.D. from Pennsylvania State University. Carl T. Lira is Associate Professor in the Department of Chemical Engineering and Materials Science at Michigan State University. He teaches thermodynamics at all levels, chemical kinetics, and material and energy balances. He has been recognized with the Amoco Excellence in Teaching Award and multiple presentations of the MSU Withrow Teaching Excellence Award. He holds a Ph.D. from the University of Illinois.

Cuprins

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 95 3.1 Heat Engines and Heat Pumps - The Carnot Cycle 96 3.2 Distillation Columns 101 3.3 Introduction to Mixture Properties 105 3.4 Ideal Gas Mixture Properties 106 3.5 Mixture Properties for Ideal Solutions 106 3.6 Energy Balance for Reacting Systems 109 3.7 Reactions in Biological Systems 119 3.8 Summary 121 3.9 Practice Problems 122 3.10 Homework Problems 122 Chapter 4: Entropy 129 4.1 The Concept of Entropy 130 4.2 The Microscopic View of Entropy 132 4.3 The Macroscopic View of Entropy 142 4.4 The Entropy Balance 153 4.5 Internal Reversibility 158 4.6 Entropy Balances for Process Equipment 159 4.7 Turbine, Compressor, and Pump Efficiency 164 4.8 Visualizing Energy and Entropy Changes 165 4.9 Turbine Calculations 166 4.10 Pumps and Compressors 173 4.11 Strategies for Applying the Entropy Balance 175 4.12 Optimum Work and Heat Transfer 177 4.13 The Irreversibility of Biological Life 181 4.14 Unsteady-State Open Systems 182 4.15 The Entropy Balance in Brief 185 4.16 Summary 185 4.17 Practice Problems 187 4.18 Homework Problems 189 Chapter 5: Thermodynamics Of Processes 199 5.1 The Carnot Steam Cycle 199 5.2 The Rankine Cycle 200 5.3 Rankine Modifications 203 5.4 Refrigeration 208 5.5 Liquefaction 212 5.6 Engines 214 5.7 Fluid Flow 214 5.8 Problem-Solving Strategies 214 5.9 Summary 215 5.10 Practice Problems 215 5.11 Homework Problems 216 Unit II: Generalized Analysis of Fluid Properties 223 Chapter 6: Classical Thermodynamics - Generalizations For Any Fluid 225 6.1 The Fundamental Property Relation 226 6.2 Derivative Relations 229 6.3 Advanced Topics 244 6.4 Summary 247 6.5 Practice Problems 248 6.6 Homework Problems 248 Chapter 7: Engineering Equations of State for PVT Properties 251 7.1 Experimental Measurements 252 7.2 Three-Parameter Corresponding States 253 7.3 Generalized Compressibility Factor Charts 256 7.4 The Virial Equation of State 258 7.5 Cubic Equations of State 260 7.6 Solving the Cubic Equation of State for Z 263 7.7 Implications of Real Fluid Behavior 269 7.8 Matching the Critical Point 270 7.9 The Molecular Basis of Equations of State: Concepts and Notation 271 7.10 The Molecular Basis of Equations of State: Molecular Simulation 276 7.11 The Molecular Basis of Equations of State: Analytical Theories 282 7.12 Summary 289 7.13 Practice Problems 290 7.14 Homework Problems 291 Chapter 8: Departure Functions 301 8.1 The Departure Function Pathway 302 8.2 Internal Energy Departure Function 304 8.3 Entropy Departure Function 307 8.4 Other Departure Functions 308 8.5 Summary of Density-Dependent Formulas 308 8.6 Pressure-Dependent Formulas 309 8.7 Implementation of Departure Formulas310 8.8 Reference States 318 8.9 Generalized Charts for the Enthalpy Departure 323 8.10 Summary 323 8.11 Practice Problems 325 8.12 Homework Problems326 Chapter 9: Phase Equilibrium in a Pure Fluid 335 9.1 Criteria for Phase Equilibrium 336 9.2 The Clausius-Clapeyron Equation 337 9.3 Shortcut Estimation of Saturation Properties 339 9.4 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) 348 9.9 Calculation of Fugacity (Solids) 353 9.10 Saturation Conditions from an Equation of State 353 9.11 Stable Roots and Saturation Conditions 359 9.12 Temperature Effects on G and f 361 9.13 Summary 361 9.14 Practice Problems 362 9.15 Homework Problems 363 Unit III: Fluid Phase Equilibria in Mixtures 367 Chapter 10: Introduction to Multicomponent Systems 369 10.1 Introduction to Phase Diagrams 370 10.2 Vapor-Liquid Equilibrium (VLE) Calculations 372 10.3 Binary VLE Using Raoult,s Law 374 10.4 Multicomponent VLE Raoult,s Law Calculations 381 10.5 Emissions and Safety 386 10.6 Relating VLE to Distillation 390 10.7 Nonideal Systems 393 10.8 Concepts for Generalized Phase Equilibria 397 10.9 Mixture Properties for Ideal Gases 401 10.10 Mixture Properties for Ideal Solutions 403 10.11 The Ideal Solution Approximation and Raoult,s Law 404 10.12 Activity Coefficient and Fugacity Coefficient Approaches 405 10.13 Summary 405 10.14 Practice Problems 407 10.15 Homework Problems 407 Chapter 11: An Introduction To Activity Models 411 11.1 Modified Raoult,s Law and Excess Gibbs Energy 412 11.2 Calculations Using Activity Coefficients 416 11.3 Deriving Modified Raoult,s Law 423 11.4 Excess Properties 426 11.5 Modified Raoult,s Law and Excess Gibbs Energy 427 11.6 Redlich-Kister and the Two-Parameter Margules Models 429 11.7 Activity Coefficients at Special Compositions 432 11.8 Preliminary Indications of VLLE 434 11.9 Fitting Activity Models to Multiple Data 435 11.10 Relations for Partial Molar Properties 439 11.11 Distillation and Relative Volatility of Nonideal Solutions 442 11.12 Lewis-Randall Rule and Henry,s Law 443 11.13 Osmotic Pressure 449 11.14 Summary 454 11.15 Practice Problems 455 11.16 Homework Problems 455 Chapter 12: van der Waals Activity Models 465 12.1 The van der Waals Perspective for Mixtures 466 12.2 The van Laar Model 469 12.3 Scatchard-Hildebrand Theory 471 12.4 The Flory-Huggins Model 474 12.5 MOSCED and SSCED Theories 479 12.6 Molecular Perspective and VLE Predictions 483 12.7 Multicomponent Extensions of van der Waals, Models 486 12.8 Flory-Huggins and van der Waals Theories 491 12.9 Summary 492 12.10 Practice Problems 494 12.11 Homework Problems 495 Chapter 13: Local Composition Activity Models 499 13.1 Local Composition Theory 501 13.2 Wilson,s Equation 505 13.3 NRTL 508 13.4 UNIQUAC 509 13.5 UNIFAC 514 13.6 COSMO-RS Methods 520 13.7 The Molecular Basis of Solution Models 526 13.8 Summary 532 13.9 Important Equations 533 13.10 Practice Problems 533 13.11 Homework Problems 534 Chapter 14: Liquid-Liquid and Solid-Liquid Phase Equilibria 539 14.1 The Onset of Liquid-Liquid Instability 539 14.2 Stability and Excess Gibbs Energy 542 14.3 Binary LLE by Graphing the Gibbs Energy of Mixing 543 14.4 LLE Using Activities 545 14.5 VLLE with Immiscible Components 548 14.6 Binary Phase Diagrams 549 14.7 Plotting Ternary LLE Data 551 14.8 Critical Points in Binary Liquid Mixtures 552 14.9 Numerical Procedures for Binary, Ternary LLE 556 14.10 Solid-Liquid Equilibria 556 14.11 Summary 569 14.12 Practice Problems 570 14.13 Homework Problems 570 Chapter 15: Phase Equilibria in Mixtures by an Equation of State 579 15.1 Mixing Rules for Equations of State 580 15.2 Fugacity and Chemical Potential from an EOS 582 15.3 Differentiation of Mixing Rules 588 15.4 VLE Calculations by an Equation of State 594 15.5 Strategies for Applying VLE Routines 603 15.6 Summary 603 15.7 Practice Problems 604 15.8 Homework Problems 606 Chapter 16: Advanced Phase Diagrams 613 16.1 Phase Behavior Sections of 3D Objects 613 16.2 Classification of Binary Phase Behavior 617 16.3 Residue Curves 630 16.4 Practice Problems 636 16.5 Homework Problems 636 Unit IV: Reaction Equilibria 639 Chapter 17: Reaction Equilibria 641 17.1 Introduction 642 17.2 Reaction Equilibrium Constraint 644 17.3 The Equilibrium Constant 646 17.4 The Standard State Gibbs Energy of Reaction 647 17.5 Effects of Pressure, Inerts, and Feed Ratios 649 17.6 Determining the Spontaneity of Reactions 652 17.7 Temperature Dependence of Ka 652 17.8 Shortcut Estimation of Temperature Effects 655 17.9 Visualizing Multiple Equilibrium Constants 656 17.10 Solving Equilibria for Multiple Reactions 658 17.11 Driving Reactions by Chemical Coupling 662 17.12 Energy Balances for Reactions 664 17.13 Liquid Components in Reactions 667 17.14 Solid Components in Reactions 669 17.15 Rate Perspectives in Reaction Equilibria 671 17.16 Entropy Generation via Reactions 672 17.17 Gibbs Minimization 673 17.18 Reaction Modeling with Limited Data 677 17.19 Simultaneous Reaction and VLE 677 17.20 Summary 683 17.21 Practice Problems 684 17.22 Homework Problems 686 Chapter 18: Electrolyte Solutions 693 18.1 Introduction to Electrolyte Solutions 693 18.2 Colligative Properties 695 18.3 Speciation and the Dissociation Constant 697 18.4 Concentration Scales and Standard States 699 18.5 The Definition of pH 701 18.6 Thermodynamic Network for Electrolyte Equilibria 702 18.7 Perspectives on Speciation 703 18.8 Acids and Bases 704 18.9 Sillen Diagram Solution Method712 18.10 Applications 723 18.11 Redox Reactions 727 18.12 Biological Reactions 731 18.13 Nonideal Electrolyte Solutions: Background 739 18.14 Overview of Model Development 740 18.15 The Extended Debye-Huckel Activity Model 742 18.16 Gibbs Energies for Electrolytes 743 18.17 Transformed Biological Gibbs Energies and Apparent Equilibrium Constants 745 18.18 Coupled Multireaction and Phase Equilibria 749 18.19 Mean Ionic Activity Coefficients 753 18.20 Extending Activity Calculations to High Concentrations 755 18.21 Summary 755 18.22 Supplement 1: Interconversion of Concentration Scales 757 18.23 Supplement 2: Relation of Apparent Chemical Potential to Species Potentials 758 18.24 Supplement 3: Standard States 759 18.25 Supplement 4: Conversion of Equilibrium Constants 760 18.26 Practice Problems 761 18.27 Homework Problems 761 Chapter 19: Molecular Association and Solvation 767 19.1 Introducing the Chemical Contribution 768 19.2 Equilibrium Criteria 772 19.3 Balance Equations for Binary Systems 775 19.4 Ideal Chemical Theory for Binary Systems 776 19.5 Chemical-Physical Theory 779 19.6 Wertheim,s Theory for Complex Mixtures 782 19.7 Mass Balances for Chain Association 792 19.8 The Chemical Contribution to the Fugacity Coefficient and Compressibility Factor 793 19.9 Wertheim,s Theory of Polymerization 795 19.10 Statistical Associating Fluid Theory (The SAFT Model) 799 19.11 Fitting the Constants for an Associating Equation of State 802 19.12 Summary 804 19.13 Practice Problems 806 19.14 Homework Problems 806 Appendix A: Summary of Computer Programs 811 A.1 Programs for Pure Component Properties 811 A.2 Programs for Mixture Phase Equilibria 812 A.3 Reaction Equilibria 813 A.4 Notes on Excel Spreadsheets 813 A.5 Notes on MATLAB 814 A.6 Disclaimer 815 Appendix B: Mathematics 817 B.1 Important Relations 817 B.2 Solutions to Cubic Equations 822 B.3 The Dirac Delta Function 825 Appendix C: Strategies for Solving VLE Problems 831 C.1 Modified Raoult,s Law Methods 832 C.2 EOS Methods 835 C.3 Activity Coefficient (Gamma-Phi) Methods 838 Appendix D: Models for Process Simulators 839 D.1 Overview 839 D.2 Equations of State 839 D.3 Solution Models 840 D.4 Hybrid Models 840 D.5 Recommended Decision Tree 841 Appendix E: Themodynamic Properties 843 E.1 Thermochemical Data 843 E.2 Latent Heats 846 E.3 Antoine Constants 847 E.4 Henry,s Constant with Water as Solvent 847 E.5 Dielectric Constant for Water 848 E.6 Dissociation Constants of Polyprotic Acids 849 E.7 Standard Reduction Potentials 849 E.8 Biochemical Data 852 E.9 Properties of Water 854 E.10 Pressure-Enthalpy Diagram for Methane 865 E.11 Pressure-Enthalpy Diagram for Propane 866 E.12 Pressure-Enthalpy Diagram for R134a (1,1,1,2-Tetraflouroethane) 867 Index 869