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Thermodynamics, Statistical Thermodynamics, & Kinetics, Second Edition

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Fundamental Concepts of Thermodynamics

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Thermodynamics, Statistical Thermodynamics, & Kinetics, Second Edition

by Thomas Engel; Philip Reid

Publisher: Prentice Hall

Copyright Year: 2010

Publishing Date: 2009/03/12

eText ISBN-10: 0-321-63222-2

eText ISBN-13: 978-0-321-63222-7

Print ISBN-10: 0-321-61503-4

Print ISBN-13: 978-0-321-61503-9

Course: Physical Chemistry

Pages: 624

eTextbook $47.00

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Table of Contents | Description

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ABOUT THIS TITLE - TABLE OF CONTENTS

About the Authors, xii

1. Fundamental Concepts of Thermodynamics, 1

1.1. What Is Thermodynamics and Why Is It Useful?, 1

1.2. Basic Definitions Needed to Describe Thermodynamic Systems, 2

1.3. Thermometry, 4

1.4. Equations of State and the Ideal Gas Law, 6

1.5. A Brief Introduction to Real Gases, 9

2. Heat, Work, Internal Energy, Enthalpy, and the First Law of Thermodynamics, 15

2.1. The Internal Energy and the First Law of Thermodynamics, 15

2.4. Heat Capacity, 21

2.5. State Functions and Path Functions, 23

2.6. Equilibrium, Change, and Reversibility, 25

2.7. Comparing Work for Reversible and Irreversible Processes, 26

2.8. Determining ΔU and Introducing Enthalpy, a New State Function, 30

2.9. Calculating q, w, ΔU, and ΔH for Processes Involving Ideal Gases, 31

2.10. The Reversible Adiabatic Expansion and Compression of an Ideal Gas, 35

3. The Importance of State Functions: Internal Energy and Enthalpy, 41

3.1. The Mathematical Properties of State Functions, 41

3.2. The Dependence of U on V and T, 46

3.3. Does the Internal Energy Depend More Strongly on V or T?, 48

3.4. The Variation of Enthalpy with Temperature at Constant Pressure, 51

3.5. How Are C_P and C_V Related?, 53

3.6. The Variation of Enthalpy with Pressure at Constant Temperature, 54

3.7. The Joule–Thomson Experiment, 57

3.8. Liquefying Gases Using an Isenthalpic Expansion, 59

4. Thermochemistry, 63

4.1. Energy Stored in Chemical Bonds Is Released or Taken Up in Chemical Reactions, 63

4.2. Internal Energy and Enthalpy Changes Associated with Chemical Reactions, 64

4.3. Hess’s Law Is Based on Enthalpy Being a State Function, 67

4.4. The Temperature Dependence of Reaction Enthalpies, 69

4.5. The Experimental Determination of ΔU and ΔH for Chemical Reactions, 71

4.6. (Supplemental) Differential Scanning Calorimetry, 73

5. Entropy and the Second and Third Laws of Thermodynamics, 79

5.1. The Universe Has a Natural Direction of Change, 79

5.2. Heat Engines and the Second Law of Thermodynamics, 80

5.3. Introducing Entropy, 85

5.4. Calculating Changes in Entropy, 86

5.5. Using Entropy to Calculate the Natural Direction of a Process in an Isolated System, 89

5.6. The Clausius Inequality, 91

5.7. The Change of Entropy in the Surroundings and ΔS_total = ΔS + ΔS_surroundings, 92

5.8. Absolute Entropies and the Third Law of Thermodynamics, 94

5.9. Standard States in Entropy Calculations, 98

5.10. Entropy Changes in Chemical Reactions, 98

5.11. (Supplemental) Energy Efficiency: Heat Pumps, Refrigerators, and Real Engines, 100

5.12. (Supplemental) Using the Fact that S Is a State Function to Determine the Dependence of S on V and T, 107

5.13. (Supplemental) The Dependence of S on T and P, 108

5.14. (Supplemental) The Thermodynamic Temperature Scale, 109

6. Chemical Equilibrium, 115

6.1. The Gibbs Energy and the Helmholtz Energy, 116

6.2. The Differential Forms of U, H, A, and G, 120

6.3. The Dependence of the Gibbs and Helmholtz Energies on P, V, and T, 121

6.4. The Gibbs Energy of a Reaction Mixture, 124

6.5. The Gibbs Energy of a Gas in a Mixture, 125

6.6. Calculating the Gibbs Energy of Mixing for Ideal Gases, 126

6.7. Calculating ΔG°R for a Chemical Reaction, 127

6.8. Introducing the Equilibrium Constant for a Mixture of Ideal Gases, 129

6.9. Calculating the Equilibrium Partial Pressures in a Mixture of Ideal Gases, 131

6.10. The Variation of K_P with Temperature, 132

6.11. Equilibria Involving Ideal Gases and Solid or Liquid Phases, 134

6.12. Expressing the Equilibrium Constant in Terms of Mole Fraction or Molarity, 135

6.13. The Dependence of ξ_eq on T and P, 136

6.14. (Supplemental) A Case Study: The Synthesis of Ammonia, 137

6.15. (Supplemental) Expressing U and H and Heat Capacities Solely in Terms of Measurable Quantities, 142

6.16. (Supplemental) Measuring ΔG for the Unfolding of Single RNA Molecules, 146

6.17. (Supplemental) The Role of Mixing in Determining Equilibrium in a Chemical Reaction, 147

7. The Properties of Real Gases, 155

7.1. Real Gases and Ideal Gases, 155

7.2. Equations of State for Real Gases and Their Range of Applicability, 156

7.3. The Compression Factor, 160

7.4. The Law of Corresponding States, 163

7.5. Fugacity and the Equilibrium Constant for Real Gases, 166

8. Phase Diagrams and the Relative Stability of Solids, Liquids, and Gases, 173

8.1. What Determines the Relative Stability of the Solid, Liquid, and Gas Phases?, 173

8.2. The Pressure–Temperature Phase Diagram, 176

8.3. The Phase Rule, 181

8.4. The Pressure–Volume and Pressure–Volume–Temperature Phase Diagrams, 182

8.5. Providing a Theoretical Basis for the P–T Phase Diagram, 184

8.6. Using the Clausius–Clapeyron Equation to Calculate Vapor Pressure as a Function of T, 185

8.7. The Vapor Pressure of a Pure Substance Depends on the Applied Pressure, 188

8.8. Surface Tension, 189

8.9. (Supplemental) Chemistry in Supercritical Fluids, 192

8.10. (Supplemental) Liquid Crystal Displays, 193

9. Ideal and Real Solutions, 199

9.1. Defining the Ideal Solution, 200

9.2. The Chemical Potential of a Component in the Gas and Solution Phases, 201

9.3. Applying the Ideal Solution Model to Binary Solutions, 202

9.4. The Temperature–Composition Diagram and Fractional Distillation, 206

9.5. The Gibbs–Duhem Equation, 208

9.6. Colligative Properties, 210

9.7. The Freezing Point Depression and Boiling Point Elevation, 210

9.8. The Osmotic Pressure, 213

9.9. Real Solutions Exhibit Deviations from Raoult’s Law, 214

9.10. The Ideal Dilute Solution, 217

9.11. Activities Are Defined with Respect to Standard States, 219

9.12. Henry’s Law and the Solubility of Gases in a Solvent, 222

9.13. Chemical Equilibrium in Solutions, 223

9.14. Solutions Formed from Partially Miscible Liquids, 227

9.15. The Solid–Solution Equilibrium, 228

10. Electrolyte Solutions, 233

10.1. The Enthalpy, Entropy, and Gibbs Energy of Ion Formation in Solutions, 234

10.2. Understanding the Thermodynamics of Ion Formation and Solvation, 236

10.3. Activities and Activity Coefficients for Electrolyte Solutions, 238

10.4. Calculating γ± Using the Debye–Hückel Theory, 241

10.5. Chemical Equilibrium in Electrolyte Solutions, 245

11. Electrochemical Cells, Batteries, and Fuel Cells, 249

11.1. The Effect of an Electrical Potential on the Chemical Potential of Charged Species, 250

11.2. Conventions and Standard States in Electrochemistry, 251

11.3. Measurement of the Reversible Cell Potential, 254

11.4. Chemical Reactions in Electrochemical Cells and the Nernst Equation, 254

11.5. Combining Standard Electrode Potentials to Determine the Cell Potential, 256

11.6. Obtaining Reaction Gibbs Energies and Reaction Entropies from Cell Potentials, 257

11.7. The Relationship between the Cell EMF and the Equilibrium Constant, 258

11.8. Determination of E° and Activity Coefficients Using an Electrochemical Cell, 260

11.9. Cell Nomenclature and Types of Electrochemical Cells, 260

11.10. The Electrochemical Series, 262

11.11. Thermodynamics of Batteries and Fuel Cells, 263

11.12. The Electrochemistry of Commonly Used Batteries, 263

11.13. Fuel Cells, 265

11.14. (Supplemental) Electrochemistry at the Atomic Scale, 267

11.15. (Supplemental) Using Electrochemistry for Nanoscale Machining, 273

11.16. (Supplemental) Absolute Half-Cell Potentials, 274

12. Probability, 281

12.1. Why Probability?, 281

12.2. Basic Probability Theory, 282

12.3. Stirling’s Approximation, 290

12.4. Probability Distribution Functions, 291

12.5. Probability Distributions Involving Discrete and Continuous Variables, 293

12.6. Characterizing Distribution Functions, 296

13. The Boltzmann Distribution, 305

13.1. Microstates and Configurations, 305

13.2. Derivation of the Boltzmann Distribution, 311

13.3. Dominance of the Boltzmann Distribution, 316

13.4. Physical Meaning of the Boltzmann Distribution Law, 318

13.5. The Definition of β, 319

14. Ensemble and Molecular Partition Functions, 327

14.1. The Canonical Ensemble, 327

14.2. Relating Q to q for an Ideal Gas, 329

14.3. Molecular Energy Levels, 331

14.4. Translational Partition Function, 331

14.5. Rotational Partition Function: Diatomics, 334

14.6. Rotational Partition Function: Polyatomics, 342

14.7. Vibrational Partition Function, 343

14.8. The Equipartition Theorem, 349

14.9. Electronic Partition Function, 350

14.10. Review, 353

15. Statistical Thermodynamics, 359

15.1. Energy, 359

15.2. Energy and Molecular Energetic Degrees of Freedom, 363

15.3. Heat Capacity, 368

15.4. Entropy, 372

15.5. Residual Entropy, 377

15.6. Other Thermodynamic Functions, 378

15.7. Chemical Equilibrium, 382

16. Kinetic Theory of Gases, 391

16.1. Kinetic Theory of Gas Motion and Pressure, 391

16.2. Velocity Distribution in One Dimension, 394

16.3. The Maxwell Distribution of Molecular Speeds, 398

16.4. Comparative Values for Speed Distributions: v_ave, v_mp, and v_rms, 400

16.5. Gas Effusion, 402

16.6. Molecular Collisions, 404

16.7. The Mean Free Path, 408

17. Transport Phenomena, 413

17.1. What Is Transport?, 413

17.2. Mass Transport: Diffusion, 415

17.3. The Time Evolution of a Concentration Gradient, 418

17.4. (Supplemental) Statistical View of Diffusion, 420

17.5. Thermal Conduction, 422

17.6. Viscosity of Gases, 426

17.7. Measuring Viscosity, 428

17.8. Diffusion in Liquids and Viscosity of Liquids, 430

17.9. (Supplemental) Sedimentation and Centrifugation, 432

17.10. Ionic Conduction, 435

18. Elementary Chemical Kinetics, 445

18.1. Introduction to Kinetics, 446

18.2. Reaction Rates, 447

18.3. Rate Laws, 448

18.4. Reaction Mechanisms, 454

18.5. Integrated Rate Law Expressions, 455

18.6. (Supplemental) Numerical Approaches, 459

18.7. Sequential First-Order Reactions, 461

18.8. Parallel Reactions, 466

18.9. Temperature Dependence of Rate Constants, 468

18.10. Reversible Reactions and Equilibrium, 470

18.11. (Supplemental) Perturbation-Relaxation Methods, 473

18.12. (Supplemental) The Autoionization of Water: A T-Jump Example, 475

18.13. Potential Energy Surfaces, 476

18.14. Diffusion Controlled Reactions, 478

18.15. Activated Complex Theory, 480

19. Complex Reaction Mechanisms, 491

19.1. Reaction Mechanisms and Rate Laws, 491

19.2. The Preequilibrium Approximation, 493

19.3. The Lindemann Mechanism, 495

19.4. Catalysis, 497

19.5. Radical-Chain Reactions, 508

19.6. Radical-Chain Polymerization, 511

19.7. Explosions, 512

19.8. Photochemistry, 514

19.9. Electron Transfer, 525

Appendix A. Data Tables, 539

Appendix B. Math Supplement, 557

Appendix C. Answers to Selected End-of-Chapter Problems, 579

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ABOUT THIS TITLE - DESCRIPTION

For courses in Physical Chemistry.

This full-color, modern physical chemistry text offers arresting illustrations that set it apart from others of its kind. The authors focus on core topics of physical chemistry, presented within a modern framework of applications. Extensive math derivations are provided, yet the book retains the significant chemical rigor needed in physical chemistry.

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