Title Details

Milo D. Koretsky received his Ph.D. in Chemical Engineering from the University of California at Berkeley in 1991. He is currently of professor of Chemical Engineering at Oregon State University. His research interests in thin film materials processing, including plasma chemistry and physics, electrochemical processes and semiconductor yield prediction. His teaching interests include integration of microelectronic unit operations into the ChE curriculum and thermodynamics.

CHAPTER 1 Measured Thermodynamic Properties and Other Basic Concepts 1

Learning Objectives 1

1.1 Thermodynamics 2

1.2 Preliminary Concepts—The Language of Thermo 3

Thermodynamic Systems 3

Properties 4

Processes 5

Hypothetical Paths 6

Phases of Matter 6

Length Scales 6

Units 7

1.3 Measured Thermodynamic Properties 7

Volume (Extensive or Intensive) 7

Temperature (Intensive) 8

Pressure (Intensive) 11

The Ideal Gas 13

1.4 Equilibrium 15

Types of Equilibrium 15

Molecular View of Equilibrium 16

1.5 Independent and Dependent Thermodynamic Properties 17

The State Postulate 17

Gibbs Phase Rule 18

1.6 The PʋT Surface and Its Projections for Pure Substances 20

Changes of State During a Process 22

Saturation Pressure vs. Vapor Pressure 23

The Critical Point 24

1.7 Thermodynamic Property Tables 26

1.8 Summary 30

1.9 Problems 31

Conceptual Problems 31

Numerical Problems 34

CHAPTER 2 The First Law of Thermodynamics 36

Learning Objectives 36

2.1 The First Law of Thermodynamics 37

Forms of Energy 37

Ways We Observe Changes in U 39

Internal Energy of an Ideal Gas 40

Work and Heat: Transfer of Energy Between the System and the Surroundings 42

2.2 Construction of Hypothetical Paths 46

2.3 Reversible and Irreversible Processes 48

Reversible Processes 48

Irreversible Processes 48

Efficiency 55

2.4 The First Law of Thermodynamics for Closed Systems 55

Integral Balances 55

Differential Balances 57

2.5 The First Law of Thermodynamics for Open Systems 60

Material Balance 60

Flow Work 60

Enthalpy 62

Steady-State Energy Balances 62

Transient Energy Balance 63

2.6ThermochemicalData For U and H 67

Heat Capacity: c_ʋ and c_P 67

Latent Heats 76

Enthalpy of Reactions 80

2.7 Reversible Processes in Closed Systems 92

Reversible, Isothermal Expansion (Compression) 92

Adiabatic Expansion (Compression) with Constant Heat Capacity 93

Summary 95

2.8 Open-System Energy Balances on Process Equipment 95

Nozzles and Diffusers 96

Turbines and Pumps (or Compressors) 97

Heat Exchangers 98

Throttling Devices 101

2.9 Thermodynamic Cycles and the Carnot Cycle 102

Efficiency 104

2.10 Summary 108

2.11 Problems 110

Conceptual Problems 110

Numerical Problems 113

CHAPTER 3 Entropy and the Second Law Of Thermodynamics 127

Learning Objectives 127

3.1 Directionality of Processes/Spontaneity 128

3.2 Reversible and Irreversible Processes (Revisited) and their Relationship to Directionality 129

3.3 Entropy, the Thermodynamic Property 131

3.4 The Second Law of Thermodynamics 140

3.5 Other Common Statements of the Second Law of Thermodynamics 142

3.6 The Second Law of Thermodynamics for Closed and Open Systems 143

Calculation of Δs for Closed Systems 143

Calculation of Δs for Open Systems 147

3.7 Calculation of Δs for an Ideal Gas 151

3.8 The Mechanical Energy Balance and the Bernoulli Equation 160

3.9 Vapor-Compression Power and Refrigeration Cycles 164

The Rankine Cycle 164

The Vapor-Compression Refrigeration Cycle 169

3.10 Exergy (Availability) Analysis 172

Exergy 173

Exthalpy—Flow Exergy in Open Systems 178

3.11 Molecular View of Entropy 182

Maximizing Molecular Confi gurations over Space 185

Maximizing Molecular Confi gurations over Energy 186

3.12 Summary 190

3.13 Problems 191

Conceptual Problems 191

Numerical Problems 195

CHAPTER 4 Equations of State and Intermolecular Forces 209

Learning Objectives 209

4.1 Introduction 210

Motivation 210

The Ideal Gas 211

4.2 Intermolecular Forces 211

Internal (Molecular) Energy 211

The Electric Nature of Atoms and Molecules 212

Attractive Forces 213

Intermolecular Potential Functions and Repulsive Forces 223

Principle of Corresponding States 226

Chemical Forces 228

4.3 Equations of State 232

The van der Waals Equation of State 232

Cubic Equations of State (General) 238

The Virial Equation of State 240

Equations of State for Liquids and Solids 245

4.4 Generalized Compressibility Charts 246

4.5 Determination of Parameters for Mixtures 249

Cubic Equations of State 250

Virial Equation of State 251

Corresponding States 252

4.6 Summary 254

4.7 Problems 255

Conceptual Problems 255

Numerical Problems 257

CHAPTER 5 The Thermodynamic Web 265

Learning Objectives 265

5.1 Types of Thermodynamic Properties 265

Measured Properties 265

Fundamental Properties 266

Derived Thermodynamic Properties 266

5.2 Thermodynamic Property Relationships 267

Dependent and Independent Properties 267

Hypothetical Paths (revisited) 268

Fundamental Property Relations 269

Maxwell Relations 271

Other Useful Mathematical Relations 272

Using the Thermodynamic Web to Access Reported Data 273

5.3 Calculation of Fundamental and Derived Properties Using Equations of State and Other Measured Quantities 276

Relation of ds in Terms of Independent Properties T and ʋ and Independent Properties T and P 276

Relation of du in Terms of Independent Properties T and ʋ 277

Relation of dh in Terms of Independent Properties T and P 281

Alternative Formulation of the Web using T and P as Independent Properties 287

5.4 Departure Functions 290

Enthalpy Departure Function 290

Entropy Departure Function 293

5.5 Joule-Thomson Expansion and Liquefaction 298

Joule-Thomson Expansion 298

Liquefaction 301

5.6 Summary 304

5.7 Problems 305

Conceptual Problems 305

Numerical Problems 307

CHAPTER 6 Phase Equilibria I: Problem Formulation 315

Learning Objectives 315

6.1 Introduction 315

The Phase Equilibria Problem 316

6.2 Pure Species Phase Equilibrium 318

Gibbs Energy as a Criterion for Chemical

Equilibrium 318

Roles of Energy and Entropy in Phase Equilibria 321

The Relationship Between Saturation Pressure and Temperature: The Clapeyron Equation 327

Pure Component Vapor–Liquid Equilibrium: The Clausius–Clapeyron Equation 328

6.3 Thermodynamics of Mixtures 334

Introduction 334

Partial Molar Properties 335

The Gibbs–Duhem Equation 340

Summary of the Different Types of Thermodynamic Properties 342

Property Changes of Mixing 343

Determination of Partial Molar Properties 357

Relations Among Partial Molar Quantities 366

6.4 Multicomponent Phase Equilibria 367

The Chemical Potential—The Criteria for Chemical Equilibrium 367

Temperature and Pressure Dependence of μi 370

6.5 Summary 372

6.6 Problems 373

Conceptual Problems 373

Numerical Problems 377

CHAPTER 7 Phase Equilibria II: Fugacity 391

Learning Objectives 391

7.1 Introduction 391

7.2 The Fugacity 392

Definition of Fugacity 392

Criteria for Chemical Equilibria in Terms of Fugacity 395

7.3 Fugacity in the Vapor Phase 396

Fugacity and Fugacity Coefficient of Pure Gases 396

Fugacity and Fugacity Coefficient of Species i in a Gas Mixture 403

The Lewis Fugacity Rule 411

Property Changes of Mixing for Ideal Gases 412

7.4 Fugacity in the Liquid Phase 414

Reference States for the Liquid Phase 414

Thermodynamic Relations Between γ_i 422

Models for γ_i Using g^E 428

Equation of State Approach to the Liquid Phase 449

7.5 Fugacity in the Solid Phase 449

Pure Solids 449

Solid Solutions 449

Interstitials and Vacancies in Crystals 450

7.6 Summary 450

7.7 Problems 452

Conceptual Problems 452

Numerical Problems 454

CHAPTER 8 Phase Equilibria III: Applications 466

Learning Objectives 466

8.1 Vapor–Liquid Equilibrium (VLE) 467

Raoult’s Law (Ideal Gas and Ideal Solution) 467

Nonideal Liquids 475

Azeotropes 484

Fitting Activity Coeffi cient Models with VLE Data 490

Solubility of Gases in Liquids 495

Vapor–Liquid Equilibrium Using the Equations of State Method 501

8.2 Liquid 1a2—Liquid 1b2 Equilibrium: LLE 511

8.3 Vapor–Liquid 1a2— Liquid 1b2 Equilibrium: VLLE 519

8.4 Solid–Liquid and Solid–Solid Equilibrium:

SLE and SSE 523

Pure Solids 523

Solid Solutions 529

8.5 Colligative Properties 531

Boiling Point Elevation and Freezing Point Depression 531

Osmotic Pressure 535

8.6 Summary 538

8.7 Problems 540

Conceptual Problems 540

Numerical Problems 544

CHAPTER 9 Chemical Reaction Equilibria 562

Learning Objectives 562

9.1 Thermodynamics and Kinetics 563

9.2 Chemical Reaction and Gibbs Energy 565

9.3 Equilibrium for a Single Reaction 568

9.4 Calculation of K from Thermochemical Data 572

Calculation of K from Gibbs Energy of Formation 572

The Temperature Dependence of K 574

9.5 Relationship Between the Equilibrium Constant and the Concentrations of Reacting Species 579

The Equilibrium Constant for a Gas-Phase Reaction 579

The Equilibrium Constant for a Liquid-Phase (or Solid-Phase) Reaction 586

The Equilibrium Constant for a Heterogeneous Reaction 587

9.6 Equilibrium in Electrochemical Systems 589

Electrochemical Cells 590

Shorthand Notation 591

Electrochemical Reaction Equilibrium 592

Thermochemical Data: Half-Cell Potentials 594

Activity Coeffi cients in Electrochemical Systems 597

9.7 Multiple Reactions 599

Extent of Reaction and Equilibrium Constant for R Reactions 599

Gibbs Phase Rule for Chemically Reacting Systems and Independent Reactions 601

Solution of Multiple Reaction Equilibria by Minimization of Gibbs Energy 610

9.8 Reaction Equilibria of Point Defects in Crystalline Solids 612

Atomic Defects 613

Electronic Defects 616

Effect of Gas Partial Pressure on Defect Concentrations 619

9.9 Summary 624

9.10 Problems 626

Conceptual Problems 626

Numerical Problems 628

APPENDIX A Physical Property Data 639

APPENDIX B Steam Tables 647

APPENDIX C Lee–Kesler Generalized Correlation Tables 660

APPENDIX D Unit Systems 676

APPENDIX E ThermoSolver Software 680

APPENDIX F References 685

Index 687