**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 UsefulWork 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