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 [...].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 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 (¿-¿ 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...