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CHAPTER 1 INTRODUCTION 1

1.1 The Central Problems of Thermodynamics 1

1.2 A System of Units 3

1.3 The Equilibrium State 5

1.4 Pressure,Temperature,and Equilibrium 7

1.5 Heat,Work,and the Conservation of Energy 12

1.6 Specification of the Equilibrium State;Intensive and Extensive Variables;Equations of State 15

1.7 A Summary of Important Experimental Observations 18

1.8 A Comment on the Development of Thermodynamics 20

Problems 20

CHAPTER 2 CONSERVATION OF MASS AND ENERGY 22

2.1 A General Balance Equation and Conserved Quantities 23

2.2 Conservation of Mass 27

2.3 Conservation of Energy 30

2.4 The Thermodynamic Properties of Matter 43

2.5 Applications of the Mass and Energy Balances 51

2.6 Conservation of Momentum 75

2.7 The Microscopic Equations of Change for Thermodynamics and Fluid Mechanics(Optional) 76

Problems 82

CHAPTER 3 ENTROPY:AN ADDITIONAL BALANCE EQUATION 89

3.1 Entropy:A New Concept 90

3.2 The Entropy Balance and Reversibility 97

3.3 Heat,Work,Engines,and Entropy 103

3.4 Entropy Changes of Matter 112

3.5 Applications of the Entropy Balance 115

3.6 Liquefaction 128

3.7 Power Generation and Refrigeration Cycles 132

3.8 The Thermodynamics of Mechanical Explosions 154

3.9 The Microscopic Entropy Balance(Optional) 163

Problems 165

4.1 Some Mathematical Preliminaries 175

CHAPTER 4 THE THERMODYNAMIC PROPERTIES OF REAL SUBSTANCES 175

4.2 The Evaluation of Thermodynamic Partial Derivatives 179

4.3 The Ideal Gas and Absolute-Temperature Scales 194

4.4 The Evaluation of Changes in the Thermodynamic Properties of Real Substances Accompanying a Change of State 195

4.5 An Example Involving the Change of State of a Real Gas 219

4.6 The Principle of Corresponding States 225

4.7 Generalized Equations of State 238

4.8 The Third Law of Thermodynamics 242

4.9 More About Thermodynamic Partial Derivatives(Optional) 243

Appendix A4.1 A Program for Thermodynamic Properties Calculations Using the Peng-Robinson Cubic Equation of State,PR1 249

Problems 251

CHAPTER 5 EQUILIBRIUM AND STABILITY IN ONE-COMPONENT SYSTEMS 260

5.1 The Criteria for Equilibrium 260

5.2 Stability of Thermodynamic Systems 265

5.3 Phase Equilibria:Application of the Equilibrium and Stability Criteria to the Equation of State 272

5.4 The Molar Gibbs Free Energy and Fugacity of a Pure Component 279

5.5 The Calculation of Pure Fluid-Phase Equilibrium:The Computation of Vapor Pressure from an Equation of State 295

5.6 The Specification of the Equilibrium Thermodynamic State of a System of Several Phases:The Gibbs Phase Rule for a One-Component System 303

5.7 Thermodynamic Properties of Phase Transitions 307

Problems 313

CHAPTER 6 THE THERMODYNAMICS OF MULTICOMPONENT MIXTURES 324

6.1 The Thermodynamic Description of Mixtures 324

6.2 The Partial Molar Gibbs Free Energy and the Generalized Gibbs-Duhem Equation 333

6.3 A Notation for Chemical Reactions 337

6.4 The Equations of Change for a Multicomponent System 340

6.5 The Heat of Reaction and a Convention for the Thermodynamic Properties of Reacting Mixtures 349

6.6 The Experimental Determination of the Partial Molar Volume and Enthalpy 354

6.7 Criteria for Phase Equilibrium in Multicomponent Systems 364

6.8 The Criteria for Chemical Equilibrium,and Combined Chemical and Phase Equilibrium 368

6.9 The Specification of the Equilibrium Thermodynamic State of a Multicomponent,Multiphase System;the Gibbs Phase Rule 373

Problems 377

6.10 Some Concluding Remarks 377

CHAPTER 7 THE ESTIMATION OF THE GIBBS FREE ENERGY AND FUGACITY OF A COMPONENT IN A MIXTURE 388

7.1 The Ideal Gas Mixture 388

7.2 The Partial Molar Gibbs Free Energy and Fugacity 392

7.3 The Ideal Mixture and Excess Mixture Properties 396

7.4 The Fugacity of Species in Gaseous,Liquid,and Solid Mixtures 406

7.5 Several Correlative Liquid Mixture(Activity Coefficient)Models 414

7.6 Two Predictive Activity Coefficient Models 428

7.7 A Corresponding States Principle for Mixtures;The Pseudocritical Constant Method 437

7.8 The Fugacity of Species in Nonsimple Mixtures 444

7.9 Some Comments on Reference and Standard States 451

7.10 A Combined Equation-of-State—Excess Gibbs Free Energy Models 452

7.11 Electrolyte Solutions 455

7.12 Concluding Remarks 461

Appendix A7.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture 464

Appendix A7.2 A Program for Multicomponent Vapor-Liquid Equilibrium Calculations Using the Peng-Robinson Cubic Equation of State,VLMU 467

Appendix A7.3 Multicomponent Excess Gibbs Free Energy(Activity Coefficient)Models 468

Appendix A7.4 A Program for the Prediction of Activity Coefficients and Low Pressure Vapor-Liquid Equilibrium Using the UNIFAC Model,UNIFAC. 470

Problems 471

CHAPTER 8 PHASE EQUILIBRIUM IN MIXTURES 478

8.1 Vapor-Liquid Equilibria Using Activity Coefficient Models 478

Problems for Section 8.1 511

8.2 Vapor-Liquid Equilibria Using Equations of State 518

Problems for Section 8.2 534

8.3 The Solubility of a Gas in a Liquid 536

Problems for Section 8.3 547

8.4 The Solubility of a Liquid in a Liquid and Vapor-Liquid-Liquid Equilibrium 550

Problems for Section 8.4 571

8.5 The Solubility of a Solid in a Liquid,Gas,or Supercritical Fluid 575

Problems for Section 8.5 585

8.6 The Partitioning of a Solute Among Two Coexisting Liquid Phases;The Distribution Coefficient 586

Problems for Section 8.6 597

8.7 Freezing-Point Depression of a Solvent Due to the Presence of a Solute;the Freezing Point of Liquid Mixtures 598

Problems for Section 8.7 602

8.8 Osmotic Equilibrium and Osmotic Pressure 603

Problems for Section 8.8 606

8.9 The Phase Behavior Modeling of Chemicals in the Environment 608

Problems for Section 8.9 613

8.10 The Phase Behavior of Solid Mixtures 614

Problems for Section 8.10 622

8.11 Concluding Remarks 623

Additional Phase Equilibrium Problems 624

CHAPTER 9 CHEMICAL EQUILIBRIUM AND THE BALANCE EQUATIONS FOR CHEMICALLY REACTING SYSTEMS 630

9.1 Chemical Equilibrium in a Single-Phase System 630

9.2 Heterogeneous Chemical Reactions 663

9.3 Chemical Equilibrium When Several Reactions Occur in a Single Phase 676

9.4 Combined Chemical and Phase Equilibrium 683

9.5 The Balance Equations for a Tank-Type Chemical Reactor 691

9.6 The Balance Equations for a Tubular Reactor 699

9.7 Overall Reactor Balance Equations and the Adiabatic Reaction Temperature 702

9.8 The Thermodynamics of Chemical Explosions 711

9.9 Introduction to Electrochemical Processes 717

9.10 Coupled Chemical Reactions 727

Appendix A9.1 A Program for the Calculation of Chemical Equilibrium Constants As a Function of Temperature,CHEMEQ 730

Problems 731

APPENDIXES 744

Appendix Ⅰ Conversion Factors for SI Units 744

Appendix Ⅱ The Molar Heat Capacities of Gases in the Ideal Gas(Zero Pressure)State 745

Appendix Ⅲ The Thermodynamic Properties of Water and Steam 748

Appendix Ⅳ Enthalpies and Free Energies of Formation 758

Appendix Ⅴ Heats of Combustion 761

INDEX 763