Table of Contents
Chapter 1 Introduction 1
Instructional Objectives for Chapter 1 3
Important Notation Introduced in This Chapter 4
1.1 The Central Problems of Thermodynamics 4
1.2 A System of Units 5
1.3 The Equilibrium State 7
1.4 Pressure, Temperature, and Equilibrium 10
1.5 Heat, Work, and the Conservation of Energy 15
1.6 Specification of the Equilibrium State; Intensive and Extensive Variables; Equations of State 18
1.7 A Summary of Important Experimental Observations 21
1.8 A Comment on the Development of Thermodynamics 23
Problems 23
Chapter 2 Conservation of Mass 25
Instructional Objectives for Chapter 2 25
Important Notation Introduced in This Chapter 26
2.1 A General Balance Equation and Conserved Quantities 26
2.2 Conservation of Mass for a Pure Fluid 30
2.3 The Mass Balance Equations for a Multicomponent System with a Chemical Reaction 35
2.4 The Microscopic Mass Balance Equations in Thermodynamics and Fluid Mechanics (Optional - only on the website for this book) 43
Problems 44
Chapter 3 Conservation of Energy 45
Instructional Objectives for Chapter 3 46
Notation Introduced in This Chapter 46
3.1 Conservation of Energy 47
3.2 Several Examples of Using the Energy Balance 54
3.3 The Thermodynamic Properties of Matter 59
3.4 Applications of the Mass and Energy Balances 69
3.5 Conservation of Momentum 93
3.6 The Microscopic Energy Balance (Optional - only on website for this book) 93
Problems 93
Chapter 4 Entropy: An Additional Balance Equation 99
Instructional Objectives for Chapter 4 99
Notation Introduced in This Chapter 100
4.1 Entropy: A New Concept 100
4.2 The Entropy Balance and Reversibility 108
4.3 Heat, Work, Engines, and Entropy 114
4.4 Entropy Changes of Matter 125
4.5 Applications of the Entropy Balance 128
4.6 Availability and the Maximum Useful Shaft Work that can be obtained In a Change of State 140
4.7 The Microscopic Entropy Balance (Optional - only on website for this book) 145
Problems 145
Chapter 5 Liquefaction, Power Cycles, and Explosions 152
Instructional Objectives for Chapter 5 152
Notation Introduced in this Chapter 152
5.1 Liquefaction 153
5.2 Power Generation and Refrigeration Cycles 158
5.3 Thermodynamic Efficiencies 181
5.4 The Thermodynamics of Mechanical Explosions 185
Problems 194
Chapter 6 The Thermodynamic Properties of Real Substances 200
Instructional Objectives for Chapter 6 200
Notation Introduced in this Chapter 201
6.1 Some Mathematical Preliminaries 201
6.2 The Evaluation of Thermodynamic Partial Derivatives 205
6.3 The Ideal Gas and Absolute Temperature Scales 219
6.4 The Evaluation of Changes in the Thermodynamic Properties of Real Substances Accompanying a Change of State 220
6.5 An Example Involving the Change of State of a Real Gas 245
6.6 The Principle of Corresponding States 250
6.7 Generalized Equations of State 263
6.8 The Third Law of Thermodynamics 267
6.9 Estimation Methods for Critical and Other Properties 268
6.10 Sonic Velocity 272
6.11 More About Thermodynamic Partial Derivatives (Optional - only on website for this book) 275
Problems 275
Chapter 7 Equilibrium and Stability in One-Component Systems 285
Instructional Objectives for Chapter 7 285
Notation Introduced in This Chapter 285
7.1 The Criteria for Equilibrium 286
7.2 Stability of Thermodynamic Systems 293
7.3 Phase Equilibria: Application of the Equilibrium and Stability Criteria to the Equation of State 300
7.4 The Molar Gibbs Energy and Fugacity of a Pure Component 307
7.5 The Calculation of Pure Fluid-Phase Equilibrium: The Computation of Vapor Pressure from an Equation of State 322
7.6 Specification of the Equilibrium Thermodynamic State of a System of Several Phases: The Gibbs Phase Rule for a One-Component System 330
7.7 Thermodynamic Properties of Phase Transitions 334
7.8 Thermodynamic Properties of Small Systems, or Why Subcooling and Superheating Occur 341
Problems 344
Chapter 8 The Thermodynamics of Multicomponent Mixtures 353
Instructional Objectives for Chapter 8 353
Notation Introduced in this chapter 353
8.1 The Thermodynamic Description of Mixtures 354
8.2 The Partial Molar Gibbs Energy and the Generalized Gibbs-Duhem Equation 363
8.3 A Notation for Chemical Reactions 367
8.4 The Equations of Change for a Multicomponent System 370
8.5 The Heat of Reaction and a Convention for the Thermodynamic Properties of Reacting Mixtures 378
8.6 The Experimental Determination of the Partial Molar Volume and Enthalpy 385
8.7 Criteria for Phase Equilibrium in Multicomponent Systems 396
8.8 Criteria for Chemical Equilibrium, and Combined Chemical and Phase Equilibrium 399
8.9 Specification of the Equilibrium Thermodynamic State of a Multicomponent, Multiphase System; the Gibbs Phase Rule 404
8.10 A Concluding Remark 408
Problems 408
Chapter 9 Estimation of The Gibbs Energy and Fugacity of A Component in a Mixture 416
Instructional Objectives for Chapter 9 416
Notation Introduced in this Chapter 417
9.1 The Ideal Gas Mixture 417
9.2 The Partial Molar Gibbs Energy and Fugacity 421
9.3 Ideal Mixture and Excess Mixture Properties 425
9.4 Fugacity of Species in Gaseous, Liquid, and Solid Mixtures 436
9.5 Several Correlative Liquid Mixture Activity Coefficient Models 446
9.6 Two Predictive Activity Coefficient Models 460
9.7 Fugacity of Species in Nonsimple Mixtures 468
9.8 Some Comments on Reference and Standard States 478
9.9 Combined Equation-of-State and Excess Gibbs Energy Model 479
9.10 Electrolyte Solutions 482
9.11 Choosing the Appropriate Thermodynamic Model 490
Appendix A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture (Optional - only on the website for this book) 493
Appendix A9.2 Multicomponent Excess Gibbs Energy (Activity Coefficient) Models 493
Appendix A9.3 The Activity Coefficient of a Solvent in an Electrolyte Solution 495
Problems 499
Chapter 10 Vapor-Liquid Equilibrium in Mixtures 507
Instructional Objectives for Chapter 10 507
Notation Introduced in this Chapter 508
10.0 Introduction to Vapor-Liquid Equilibrium 508
10.1 Vapor-Liquid Equilibrium in Ideal Mixtures 510
Problems for Section 10.1 536
10.2 Low-Pressure Vapor-Liquid Equilibrium in Nonideal Mixtures 538
Problems for Section 10.2 568
10.3 High-Pressure Vapor-Liquid Equilibria Using Equations of State (φ-φ Method) 578
Problems for Section 10.3 595
Chapter 11 Other Types of Phase Equilibria in Fluid Mixtures 599
Instructional Objectives for Chapter 11 599
Notation Introduced in this Chapter 600
11.1 The Solubility of a Gas in a Liquid 600
Problems for Section 11.1 615
11.2 Liquid-Liquid Equilibrium 617
Problems for Section 11.2 646
11.3 Vapor-Liquid-Liquid Equilibrium 652
Problems for Section 11.3 661
11.4 The Partitioning of a Solute Among Two Coexisting Liquid Phases; The Distribution Coefficient 665
Problems for Section 11.4 675
11.5 Osmotic Equilibrium and Osmotic Pressure 677
Problems for Section 11.5 684
Chapter 12 Mixture Phase Equilibria Involving Solids 688
Instructional Objectives for Chapter 12 688
Notation Introduced in this Chapter 688
12.1 The Solubility of a Solid in a Liquid, Gas, or Supercritical Fluid 689
Problems for Section 12.1 699
12.2 Partitioning of a Solid Solute Between Two Liquid Phases 701
Problems for Section 12.2 703
12.3 Freezing-Point Depression of a Solvent Due to the Presence of a Solute; the Freezing Point of Liquid Mixtures 704
Problems for Section 12.3 709
12.4 Phase Behavior of Solid Mixtures 710
Problems for Section 12.4 718
12.5 The Phase Behavior Modeling of Chemicals in the Environment 720
Problems for Section 12.5 726
12.6 Process Design and Product Design 726
Problems for Section 12.6 732
12.7 Concluding Remarks on Phase Equilibria 732
Chapter 13 Chemical Equilibrium 734
Instructional Objectives for Chapter 13 734
Important Notation Introduced in This Chapter 734
13.1 Chemical Equilibrium in a Single-Phase System 735
13.2 Heterogeneous Chemical Reactions 768
13.3 Chemical Equilibrium When Several Reactions Occur in a Single Phase 781
13.4 Combined Chemical and Phase Equilibrium 791
13.5 Ionization and the Acidity of Solutions 799
13.6 Ionization of Biochemicals 817
13.7 Partitioning of Amino Acids and Proteins Between Two Liquids 831
Problems 834
Chapter 14 The Balance Equations For Chemical Reactors, Availability, and Electrochemistry 848
Instructional Objectives for Chapter 14 848
Notation Introduced in this Chapter 849
14.1 The Balance Equations for a Tank-Type Chemical Reactor 849
14.2 The Balance Equations for a Tubular Reactor 857
14.3 Overall Reactor Balance Equations and the Adiabatic Reaction Temperature 860
14.4 Thermodynamics of Chemical Explosions 869
14.5 Maximum Useful Work and Availability in Chemically Reacting Systems 875
14.6 Introduction to Electrochemical Processes 882
14.7 Fuel Cells and Batteries 891
Problems 897
Chapter 15 Some Additional Biochemical Applications of Thermodynamics 900
Instructional Objectives for Chapter 15 900
Notation Introduced in this Chapter 901
15.1 Solubilities of Weak Acids, Weak Bases, and Amino Acids as a Function of pH 901
15.2 The Solubility of Amino Acids and Proteins as a function of Ionic Strength and Temperature 911
15.3 Binding of a Ligand to a Substrate 917
15.4 Some Other Examples of Biochemical Reactions 922
15.5 The Denaturation of Proteins 925
15.6 Coupled Biochemical Reactions: The ATP-ADP Energy Storage and Delivery Mechanism 932
15.7 Thermodynamic Analysis of Fermenters and Other Bioreactors 937
15.8 Gibbs-Donnan Equilibrium and Membrane Potentials 960
15.9 Protein Concentration in an Ultracentrifuge 967
Problems 970
Appendix A Thermodynamic Data 973
Appendix A.I Conversion Factors for SI Units 973
Appendix A.II The Molar Heat Capacities of Gases in the Ideal Gas (Zero Pressure) State 974
Appendix A.III The Thermodynamic Properties of Water and Steam 977
Appendix A.IV Enthalpies and Free Energies of Formation 987
Appendix A.V Heats of Combustion 990
Appendix B Brief Descriptions of Computer Aids for Use with This Book 992
Appendix B (On Website Only) Descriptions of Computer Programs and Computer Aids for Use with This Book B1
Appendix B.I Windows-based Visual Basic Programs B1
Appendix B.II DOS-based Basic Programs B9
Appendix B.III MATHCAD Worksheets B12
Appendix B.IV MATLAB Programs B14
Appendix C Aspen Illustration Input Files. These are on The Website for This Book 994
Appendix D Answers To Selected Problems 995
Index 998
