|de Nevers, Noel|
Physical and Chemical Equilibrium for Chemical Engineers
2. Auflage April 2012
2012. 384 Seiten, Hardcover
ISBN 978-0-470-92710-6 - John Wiley & Sons
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Using the simplest mathematics, this resource accurately and rigorously covers physical and chemical equilibrium in depth. The second edition continues to cover topics found in the first edition, with numerous updates including: changes in naming and notation (this edition uses the more popular Gibbs Energy and Partial Molar Properties), changes in symbols (this edition only uses popular notation), and entirely new problem sets. Finally, the second edition includes an appendix about the Bridgman table and its use.
Aus dem Inhalt
Preface xiiiAbout the Author xvNomenclature xvii1 Introduction to Equilibrium 11.1 Why Study Equilibrium?, 11.2 Stability and Equilibrium, 41.3 Time Scales and the Approach to Equilibrium, 51.4 Looking Ahead, Gibbs Energy, 51.5 Units, Conversion Factors, and Notation, 61.6 Reality and Equations, 81.7 Phases and Phase Diagrams, 81.8 The Plan of this Book, 101.9 Summary, 10References, 112 Basic Thermodynamics 132.1 Conservation and Accounting, 132.2 Conservation of Mass, 142.3 Conservation of Energy; the First Law of Thermodynamics, 152.4 The Second Law of Thermodynamics, 172.5 Convenience Properties, 192.6 Using the First and Second Laws, 192.7 Datums and Reference States, 212.8 Measurable and Immeasurable Properties, 222.9 Work and Heat, 222.10 The Property Equation, 232.11 Equations of State (EOS), 242.12 Corresponding States, 262.13 Departure Functions, 282.14 The Properties of Mixtures, 282.15 The Combined First and Second Law Statement; Reversible Work, 292.16 Summary, 31References, 333 The Simplest Phase Equilibrium Examples and Some Simple Estimating Rules 353.1 Some General Statements About Equilibrium, 353.2 The Simplest Example of Phase Equilibrium, 373.3 The Next Level of Complexity in Phase Equilibrium, 373.4 Some Simple Estimating Rules: Raoult's and Henry's "Laws", 393.5 The General Two-Phase Equilibrium Calculation, 433.6 Some Simple Applications of Raoult's and Henry's Laws, 433.7 The Uses and Limits of Raoult's and Henry's Laws, 463.8 Summary, 46References, 484 Minimization of Gibbs Energy 494.1 The Fundamental Thermodynamic Criterion of Phase and Chemical Equilibrium, 494.2 The Criterion of Equilibrium Applied to Two Nonreacting Equilibrium Phases, 514.3 The Criterion of Equilibrium Applied to Chemical Reactions, 534.4 Simple Gibbs Energy Diagrams, 544.5 Le Chatelier's Principle, 584.6 Summary, 58References, 605 Vapor Pressure, the Clapeyron Equation, and Single Pure Chemical Species Phase Equilibrium 615.1 Measurement of Vapor Pressure, 615.2 Reporting Vapor-Pressure Data, 615.3 The Clapeyron Equation, 625.4 The Clausius-Clapeyron Equation, 635.5 The Accentric Factor, 645.6 The Antoine Equation and Other Data-Fitting Equations, 665.7 Applying the Clapeyron Equation to Other Kinds of Equilibrium, 675.8 Extrapolating Vapor-Pressure Curves, 685.9 Vapor Pressure of Solids, 695.10 Vapor Pressures of Mixtures, 695.11 Summary, 69References, 726 Partial Molar Properties 736.1 Partial Molar Properties, 736.2 The Partial Molar Equation, 746.3 Tangent Slopes, 746.4 Tangent Intercepts, 776.5 The Two Equations for Partial Molar Properties, 786.6 Using the Idea of Tangent Intercepts, 796.7 Partial Mass Properties, 806.8 Heats of Mixing and Partial Molar Enthalpies, 806.9 The Gibbs-Duhem Equation and the Counterintuitive Behavior of the Chemical Potential, 826.10 Summary, 84References, 877 Fugacity, Ideal Solutions, Activity, Activity Coefficient 897.1 Why Fugacity?, 897.2 Fugacity Defined, 897.3 The Use of the Fugacity, 907.4 Pure Substance Fugacities, 907.5 Fugacities of Species in Mixtures, 957.6 Mixtures of Ideal Gases, 957.7 Why Ideal Solutions?, 957.8 Ideal Solutions Defined, 967.9 Why Activity and Activity Coefficients?, 987.10 Activity and Activity Coefficients Defined, 987.11 Fugacity Coefficient for Pure Gases and Gas Mixtures, 1007.12 Estimating Fugacities of Individual Species in Gas Mixtures, 1007.13 Liquid Fugacities from Vapor-Liquid Equilibrium, 1047.14 Summary, 104References, 1058 Vapor-Liquid Equilibrium (VLE) at Low Pressures 1078.1 Measurement of VLE, 1078.2 Presenting Experimental VLE Data, 1108.3 The Mathematical Treatment of Low-Pressure VLE Data, 1108.4 The Four Most Common Types of Low-Pressure VLE, 1128.5 Gas-Liquid Equilibrium, Henry's Law Again, 1228.6 The Effect of Modest Pressures on VLE, 1228.7 Standard States Again, 1248.8 Low-Pressure VLE Calculations, 1258.9 Traditional K-Factor Methods, 1328.10 More Uses for Raoult's Law, 1328.11 Summary, 136References, 1439 Correlating and Predicting Nonideal VLE 1459.1 The Most Common Observations of Liquid-Phase Activity Coefficients, 1459.2 Limits on Activity Coefficient Correlations, the Gibbs-Duhem Equation, 1479.3 Excess Gibbs Energy and Activity Coefficient Equations, 1489.4 Activity Coefficients at Infinite Dilution, 1509.5 Effects of Pressure and Temperature on Liquid-Phase Activity Coefficients, 1519.6 Ternary and Multispecies VLE, 1539.7 Vapor-Phase Nonideality, 1559.8 VLE from EOS, 1589.9 Solubility Parameter, 1589.10 The Solubility of Gases in Liquids, Henry's Law Again, 1609.11 Summary, 163References, 16710 Vapor-Liquid Equilibrium (VLE) at High Pressures 16910.1 Critical Phenomena of Pure Species, 16910.2 Critical Phenomena of Mixtures, 17010.3 Estimating High-Pressure VLE, 17410.4 Computer Solutions, 17810.5 Summary, 178References, 17911 Liquid-Liquid, Liquid-Solid, and Gas-Solid Equilibrium 18111.1 Liquid-Liquid Equilibrium (LLE), 18111.2 The Experimental Determination of LLE, 18111.3 The Elementary Theory of LLE, 18711.4 The Effect of Pressure on LLE, 19011.5 Effect of Temperature on LLE, 19111.6 Distribution Coefficients, 19411.7 Liquid-Solid Equilibrium (LSE), 19511.8 The Elementary Thermodynamics of LSE, 20011.9 Gas-Solid Equilibrium (GSE) at Low Pressures, 20211.10 GSE at High Pressures, 20311.11 Gas-Solid Adsorption, Vapor-Solid Adsorption, 20411.12 Summary, 211References, 21512 Chemical Equilibrium 21712.1 Introduction to Chemical Reactions and Chemical Equilibrium, 21712.2 Formal Description of Chemical Reactions, 21712.3 Minimizing Gibbs Energy, 21812.4 Reaction Rates, Energy Barriers, Catalysis, and Equilibrium, 21912.5 The Basic Thermodynamics of Chemical Reactions and Its Convenient Formulations, 22012.6 Calculating Equilibrium Constants from Gibbs Energy Tables and then Using Equilibrium Constants to Calculate Equilibrium Concentrations, 22312.7 More on Standard States, 22712.8 The Effect of Temperature on Chemical Reaction Equilibrium, 22912.9 The Effect of Pressure on Chemical Reaction Equilibrium, 23412.10 The Effect of Nonideal Solution Behavior, 23812.11 Other Forms of K, 23812.12 Summary, 239References, 24213 Equilibrium in Complex Chemical Reactions 24313.1 Reactions Involving Ions, 24313.2 Multiple Reactions, 24413.3 Reactions with More Than One Phase, 24913.4 Electrochemical Reactions, 25213.5 Chemical and Physical Equilibrium in Two Phases, 25513.6 Summary, 257References, 26214 Equilibrium with Gravity or Centrifugal Force, Osmotic Equilibrium, Equilibrium with Surface Tension 26514.1 Equilibrium with Other Forms of Energy, 26514.2 Equilibrium in the Presence of Gravity, 26614.3 Semipermeable Membranes, 26914.4 Small is Interesting! Equilibrium with Surface Tension, 27114.5 Summary, 275References, 27815 The Phase Rule 27915.1 How Many Phases Can Coexist in a Given Equilibrium Situation?, 27915.2 What Does the Phase Rule Tell Us? What Does It Not Tell Us?, 28015.3 What is a Phase?, 28015.4 The Phase Rule is Simply Counting Variables, 28115.5 More On Components, 28215.6 The Phase Rule for One- and Two-Component Systems, 28515.7 Harder Phase Rule Problems, 28815.8 Summary, 288References, 29116 Equilibrium in Biochemical Reactions 29316.1 An Example, the Production of Ethanol from Sugar, 29316.2 Organic and Biochemical Reactions, 29316.3 Two More Sweet Examples, 29416.4 Thermochemical Data for Biochemical Reactions, 29516.5 Thermodynamic Equilibrium in Large Scale Biochemistry, 29616.6 Translating between Biochemical and Chemical Engineering Equilibrium Expressions, 29616.7 Equilibrium in Biochemical Separations, 29816.8 Summary, 299References, 300Appendix A Useful Tables and Charts 303A.1 Useful Property Data for Corresponding States Estimates, 303A.2 Vapor-Pressure Equation Constants, 305A.3 Henry's Law Constants, 306A.4 Compressibility Factor Chart (z Chart), 307A.5 Fugacity Coefficient Charts, 307A.6 Azeotropes, 308A.7 Van Laar Equation Constants, 312A.8 Enthalpies and Gibbs Energies of Formation from the Elements in the Standard States, at T 1/4 298.15 K 1/4 25C, and P 1/4 1.00 bar, 313A.9 Heat Capacities of Gases in the Ideal Gas State, 317Appendix B Equilibrium with other Restraints, Other Approaches to Equilibrium 319Appendix C The Mathematics of Fugacity, Ideal Solutions, Activity and Activity Coefficients 323C.1 The Fugacity of Pure Substances, 323C.2 Fugacities of Components of Mixtures, 324C.3 The Consequences of the Ideal Solution Definition, 326C.4 The Mathematics of Activity Coefficients, 326Appendix D Equations of State for Liquids and Solids Well Below their Critical Temperatures 329D.1 The Taylor Series EOS and Its Short Form, 329D.2 Effect of Temperature on Density, 330D.3 Effect of Pressure on Density, 331D.4 Summary, 332References, 333Appendix E Gibbs Energy of Formation Values 335E.1 Values "From the Elements", 335E.2 Changes in Enthalpy, Entropy, and Gibbs Energy, 335E.3 Ions, 337E.4 Presenting these Data, 337References, 337Appendix F Calculation of Fugacities from Pressure-Explicit EOSs 339F.1 Pressure-Explicit and Volume-Explicit EOSs, 339F.2 f /P of Pure Species Based on Pressure-Explicit EOSs, 339F.3 Cubic Equations of State, 340F.4 fi /Pyi for Individual Species in Mixtures, Based on Pressure-Explicit EOSs, 342F.5 Mixing Rules for Cubic EOSs, 343F.6 VLE Calculations with a Cubic EOS, 344F.7 Summary, 345References, 346Appendix G Thermodynamic Property Derivatives and the Bridgman Table 347References, 350Appendix H Answers to Selected Problems 351Index 353