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Copyright, iv
About the Authors, xii
Preface, xiii
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
2.2. Work, 16
2.3. Heat, 19
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
Index, 591

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