Chemical, Biochemical, and Engineering Thermodynamics

STANLEY I. SANDLER is the H. B. du Pont Professor of Chemical Engineering at the University of Delaware as well as professor of chemistry and biochemistry. He is also the founding director of its Center for Molecular and Engineering Thermodynamics. In addition to this book, Sandler is the author of 235 research papers and a monograph, and is the editor of a book on thermodynamic modeling and five conference proceedings. He earned his B.Ch.E. degree in 1962 from the City College of New York, and his Ph.D. in chemical engineering from the University of Minnesota in 1966.

• Chapter 1 Introduction 1Instructional Objectives for Chapter 1 3Important Notation Introduced in This Chapter 41.1 The Central Problems of Thermodynamics 41.2 A System of Units 51.3 The Equilibrium State 71.4 Pressure, Temperature, and Equilibrium 101.5 Heat, Work, and the Conservation of Energy 151.6 Specification of the Equilibrium State; Intensive and Extensive Variables; Equations of State 181.7 A Summary of Important Experimental Observations 211.8 A Comment on the Development of Thermodynamics 23Problems 23Chapter 2 Conservation of Mass 25Instructional Objectives for Chapter 2 25Important Notation Introduced in This Chapter 262.1 A General Balance Equation and Conserved Quantities 262.2 Conservation of Mass for a Pure Fluid 302.3 The Mass Balance Equations for a Multicomponent System with a Chemical Reaction 352.4 The Microscopic Mass Balance Equations in Thermodynamics and Fluid Mechanics (Optional - only on the website for this book) 43Problems 44Chapter 3 Conservation of Energy 45Instructional Objectives for Chapter 3 46Notation Introduced in This Chapter 463.1 Conservation of Energy 473.2 Several Examples of Using the Energy Balance 543.3 The Thermodynamic Properties of Matter 593.4 Applications of the Mass and Energy Balances 693.5 Conservation of Momentum 933.6 The Microscopic Energy Balance (Optional - only on website for this book) 93Problems 93Chapter 4 Entropy: An Additional Balance Equation 99Instructional Objectives for Chapter 4 99Notation Introduced in This Chapter 1004.1 Entropy: A New Concept 1004.2 The Entropy Balance and Reversibility 1084.3 Heat, Work, Engines, and Entropy 1144.4 Entropy Changes of Matter 1254.5 Applications of the Entropy Balance 1284.6 Availability and the Maximum Useful Shaft Work that can be obtained In a Change of State 1404.7 The Microscopic Entropy Balance (Optional - only on website for this book) 145Problems 145Chapter 5 Liquefaction, Power Cycles, and Explosions 152Instructional Objectives for Chapter 5 152Notation Introduced in this Chapter 1525.1 Liquefaction 1535.2 Power Generation and Refrigeration Cycles 1585.3 Thermodynamic Efficiencies 1815.4 The Thermodynamics of Mechanical Explosions 185Problems 194Chapter 6 The Thermodynamic Properties of Real Substances 200Instructional Objectives for Chapter 6 200Notation Introduced in this Chapter 2016.1 Some Mathematical Preliminaries 2016.2 The Evaluation of Thermodynamic Partial Derivatives 2056.3 The Ideal Gas and Absolute Temperature Scales 2196.4 The Evaluation of Changes in the Thermodynamic Properties of Real Substances Accompanying a Change of State 2206.5 An Example Involving the Change of State of a Real Gas 2456.6 The Principle of Corresponding States 2506.7 Generalized Equations of State 2636.8 The Third Law of Thermodynamics 2676.9 Estimation Methods for Critical and Other Properties 2686.10 Sonic Velocity 2726.11 More About Thermodynamic Partial Derivatives (Optional - only on website for this book) 275Problems 275Chapter 7 Equilibrium and Stability in One-Component Systems 285Instructional Objectives for Chapter 7 285Notation Introduced in This Chapter 2857.1 The Criteria for Equilibrium 2867.2 Stability of Thermodynamic Systems 2937.3 Phase Equilibria: Application of the Equilibrium and Stability Criteria to the Equation of State 3007.4 The Molar Gibbs Energy and Fugacity of a Pure Component 3077.5 The Calculation of Pure Fluid-Phase Equilibrium: The Computation of Vapor Pressure from an Equation of State 3227.6 Specification of the Equilibrium Thermodynamic State of a System of Several Phases: The Gibbs Phase Rule for a One-Component System 3307.7 Thermodynamic Properties of Phase Transitions 3347.8 Thermodynamic Properties of Small Systems, or Why Subcooling and Superheating Occur 341Problems 344Chapter 8 The Thermodynamics of Multicomponent Mixtures 353Instructional Objectives for Chapter 8 353Notation Introduced in this chapter 3538.1 The Thermodynamic Description of Mixtures 3548.2 The Partial Molar Gibbs Energy and the Generalized Gibbs-Duhem Equation 3638.3 A Notation for Chemical Reactions 3678.4 The Equations of Change for a Multicomponent System 3708.5 The Heat of Reaction and a Convention for the Thermodynamic Properties of Reacting Mixtures 3788.6 The Experimental Determination of the Partial Molar Volume and Enthalpy 3858.7 Criteria for Phase Equilibrium in Multicomponent Systems 3968.8 Criteria for Chemical Equilibrium, and Combined Chemical and Phase Equilibrium 3998.9 Specification of the Equilibrium Thermodynamic State of a Multicomponent, Multiphase System; the Gibbs Phase Rule 4048.10 A Concluding Remark 408Problems 408Chapter 9 Estimation of The Gibbs Energy and Fugacity of A Component in a Mixture 416Instructional Objectives for Chapter 9 416Notation Introduced in this Chapter 4179.1 The Ideal Gas Mixture 4179.2 The Partial Molar Gibbs Energy and Fugacity 4219.3 Ideal Mixture and Excess Mixture Properties 4259.4 Fugacity of Species in Gaseous, Liquid, and Solid Mixtures 4369.5 Several Correlative Liquid Mixture Activity Coefficient Models 4469.6 Two Predictive Activity Coefficient Models 4609.7 Fugacity of Species in Nonsimple Mixtures 4689.8 Some Comments on Reference and Standard States 4789.9 Combined Equation-of-State and Excess Gibbs Energy Model 4799.10 Electrolyte Solutions 4829.11 Choosing the Appropriate Thermodynamic Model 490Appendix A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture (Optional – only on the website for this book) 493Appendix A9.2 Multicomponent Excess Gibbs Energy (Activity Coefficient) Models 493Appendix A9.3 The Activity Coefficient of a Solvent in an Electrolyte Solution 495Problems 499Chapter 10 Vapor-Liquid Equilibrium in Mixtures 507Instructional Objectives for Chapter 10 507Notation Introduced in this Chapter 50810.0 Introduction to Vapor-Liquid Equilibrium 50810.1 Vapor-Liquid Equilibrium in Ideal Mixtures 510Problems for Section 10.1 53610.2 Low-Pressure Vapor-Liquid Equilibrium in Nonideal Mixtures 538Problems for Section 10.2 56810.3 High-Pressure Vapor-Liquid Equilibria Using Equations of State (φ-φ Method) 578Problems for Section 10.3 595Chapter 11 Other Types of Phase Equilibria in Fluid Mixtures 599Instructional Objectives for Chapter 11 599Notation Introduced in this Chapter 60011.1 The Solubility of a Gas in a Liquid 600Problems for Section 11.1 61511.2 Liquid-Liquid Equilibrium 617Problems for Section 11.2 64611.3 Vapor-Liquid-Liquid Equilibrium 652Problems for Section 11.3 66111.4 The Partitioning of a Solute Among Two Coexisting Liquid Phases; The Distribution Coefficient 665Problems for Section 11.4 67511.5 Osmotic Equilibrium and Osmotic Pressure 677Problems for Section 11.5 684Chapter 12 Mixture Phase Equilibria Involving Solids 688Instructional Objectives for Chapter 12 688Notation Introduced in this Chapter 68812.1 The Solubility of a Solid in a Liquid, Gas, or Supercritical Fluid 689Problems for Section 12.1 69912.2 Partitioning of a Solid Solute Between Two Liquid Phases 701Problems for Section 12.2 70312.3 Freezing-Point Depression of a Solvent Due to the Presence of a Solute; the Freezing Point of Liquid Mixtures 704Problems for Section 12.3 70912.4 Phase Behavior of Solid Mixtures 710Problems for Section 12.4 71812.5 The Phase Behavior Modeling of Chemicals in the Environment 720Problems for Section 12.5 72612.6 Process Design and Product Design 726Problems for Section 12.6 73212.7 Concluding Remarks on Phase Equilibria 732Chapter 13 Chemical Equilibrium 734Instructional Objectives for Chapter 13 734Important Notation Introduced in This Chapter 73413.1 Chemical Equilibrium in a Single-Phase System 73513.2 Heterogeneous Chemical Reactions 76813.3 Chemical Equilibrium When Several Reactions Occur in a Single Phase 78113.4 Combined Chemical and Phase Equilibrium 79113.5 Ionization and the Acidity of Solutions 79913.6 Ionization of Biochemicals 81713.7 Partitioning of Amino Acids and Proteins Between Two Liquids 831Problems 834Chapter 14 The Balance Equations For Chemical Reactors, Availability, and Electrochemistry 848Instructional Objectives for Chapter 14 848Notation Introduced in this Chapter 84914.1 The Balance Equations for a Tank-Type Chemical Reactor 84914.2 The Balance Equations for a Tubular Reactor 85714.3 Overall Reactor Balance Equations and the Adiabatic Reaction Temperature 86014.4 Thermodynamics of Chemical Explosions 86914.5 Maximum Useful Work and Availability in Chemically Reacting Systems 87514.6 Introduction to Electrochemical Processes 88214.7 Fuel Cells and Batteries 891Problems 897Chapter 15 Some Additional Biochemical Applications of Thermodynamics 900Instructional Objectives for Chapter 15 900Notation Introduced in this Chapter 90115.1 Solubilities of Weak Acids, Weak Bases, and Amino Acids as a Function of pH 90115.2 The Solubility of Amino Acids and Proteins as a function of Ionic Strength and Temperature 91115.3 Binding of a Ligand to a Substrate 91715.4 Some Other Examples of Biochemical Reactions 92215.5 The Denaturation of Proteins 92515.6 Coupled Biochemical Reactions: The ATP-ADP Energy Storage and Delivery Mechanism 93215.7 Thermodynamic Analysis of Fermenters and Other Bioreactors 93715.8 Gibbs-Donnan Equilibrium and Membrane Potentials 96015.9 Protein Concentration in an Ultracentrifuge 967Problems 970Appendix A Thermodynamic Data 973Appendix A.I Conversion Factors for SI Units 973Appendix A.II The Molar Heat Capacities of Gases in the Ideal Gas (Zero Pressure) State 974Appendix A.III The Thermodynamic Properties of Water and Steam 977Appendix A.IV Enthalpies and Free Energies of Formation 987Appendix A.V Heats of Combustion 990Appendix B Brief Descriptions of Computer Aids for Use with This Book 992Appendix B (On Website Only) Descriptions of Computer Programs and Computer Aids for Use with This Book B1Appendix B.I Windows-based Visual Basic Programs B1Appendix B.II DOS-based Basic Programs B9Appendix B.III MATHCAD Worksheets B12Appendix B.IV MATLAB Programs B14Appendix C Aspen Illustration Input Files. These are on The Website for This Book 994Appendix D Answers To Selected Problems 995Index 998