Introduction to Modern Thermodynamics

INTRODUCTION TO MODERN THERMODYNAMICS......Page 5
CONTENTS......Page 13
PREFACE......Page 9
PART I: THE FORMALISM OF MODERN THERMODYNAMICS......Page 19
Introduction......Page 21
1.1 Thermodynamic Systems......Page 22
1.2 Equilibrium and Nonequilibrium Systems......Page 24
1.3 Biological and Other Open Systems......Page 27
1.4 Temperature, Heat and Quantitative Laws of Gases......Page 29
1.5 States of Matter and the van der Waals Equation......Page 37
1.6 An Introduction to Kinetic Theory of Gases......Page 47
Appendix 1.1 Partial Derivatives......Page 55
Appendix 1.2 Elementary Concepts in Probability Theory......Page 57
Appendix 1.3 Mathematica Codes......Page 59
Examples......Page 62
Exercises......Page 63
The Idea of Energy Conservation amidst New Discoveries......Page 67
2.1 The Nature of Heat......Page 68
2.2 The First Law of Thermodynamics: The Conservation of Energy......Page 73
2.3 Elementary Applications of the First Law......Page 82
2.4 Thermochemistry: Conservation of Energy in Chemical Reactions......Page 86
2.5 Extent of Reaction: A State Variable for Chemical Systems......Page 94
2.6 Conservation of Energy in Nuclear Reactions and Some General Remarks......Page 97
2.7 Energy Flows and Organized States......Page 99
Appendix 2.1 Mathematica Codes......Page 105
Examples......Page 106
Exercises......Page 110
3.1 The Birth of the Second Law......Page 115
3.2 The Absolute Scale of Temperature......Page 124
3.3 The Second Law and the Concept of Entropy......Page 126
3.4 Entropy, Reversible and Irreversible Processes......Page 134
3.5 Examples of Entropy Changes due to Irreversible Processes......Page 143
3.6 Entropy Changes Associated with Phase Transformations......Page 146
3.7 Entropy of an Ideal Gas......Page 147
3.8 Remarks about the Second Law and Irreversible Processes......Page 148
Appendix 3.1 The Hurricane as a Heat Engine......Page 150
Appendix 3.2 Entropy Production in Continuous Systems......Page 153
References......Page 154
Examples......Page 155
Exercises......Page 157
4.1 Chemical Potential and Affinity: The Thermodynamic Force for Chemical Reactions......Page 159
4.2 General Properties of Affinity......Page 168
4.3 Entropy Production Due to Diffusion......Page 171
4.4 General Properties of Entropy......Page 173
References......Page 176
Examples......Page 177
Exercises......Page 178
5.1 Extremum Principles Associated with the Second Law......Page 181
5.2 General Thermodynamic Relations......Page 191
5.3 Gibbs Energy of Formation and Chemical Potential......Page 194
5.4 Maxwell Relations......Page 197
5.5 Extensivity with Respect to N and Partial Molar Quantities......Page 199
5.6 Surface Tension......Page 201
Examples......Page 205
Exercises......Page 207
PART II: APPLICATIONS: EQUILIBRIUM AND\nNONEQUILIBRIUM SYSTEMS......Page 211
6.1 Thermodynamics of Ideal Gases......Page 213
6.2 Thermodynamics of Real Gases......Page 217
6.3 Thermodynamics Quantities for Pure Liquids and Solids......Page 226
Reference......Page 229
Examples......Page 230
Exercises......Page 231
7.1 Phase Equilibrium and Phase Diagrams......Page 233
7.2 The Gibbs Phase Rule and Duhem’s Theorem......Page 239
7.3 Binary and Ternary Systems......Page 241
7.4 Maxwell’s Construction and the Lever Rule......Page 247
7.5 Phase Transitions......Page 249
Examples......Page 253
Exercises......Page 254
8.1 Ideal and Nonideal Solutions......Page 257
8.2 Colligative Properties......Page 261
8.3 Solubility Equilibrium......Page 268
8.4 Thermodynamic Mixing and Excess Functions......Page 273
8.5 Azeotropy......Page 277
Examples......Page 278
Exercises......Page 280
9.1 Transformations of Matter......Page 283
9.2 Chemical Reaction Rates......Page 284
9.3 Chemical Equilibrium and the Law of Mass Action......Page 291
9.4 The Principle of Detailed Balance......Page 296
9.5 Entropy Production due to Chemical Reactions......Page 298
9.6 Elementary Theory of Chemical Reaction Rates......Page 303
9.7 Coupled Reactions and Flow Reactors......Page 306
Appendix 9.1 Mathematica Codes......Page 313
Examples......Page 316
Exercises......Page 318
10.1 Chemical Potential in a Field......Page 323
10.2 Membranes and Electrochemical Cells......Page 329
10.3 Isothermal Diffusion......Page 337
Examples......Page 342
Exercises......Page 343
Introduction......Page 345
11.1 Local Equilibrium......Page 346
11.2 Local Entropy Production, Thermodynamic Forces and Flows......Page 349
11.3 Linear Phenomenological Laws and Onsager Reciprocal Relations......Page 351
11.4 Symmetry-Breaking Transitions and Dissipative Structures......Page 357
11.5 Chemical Oscillations......Page 363
Appendix 11.1 Mathematica Codes......Page 370
References......Page 373
Further Reading......Page 374
Exercises......Page 375
PART III: ADDITIONAL TOPICS......Page 377
12.1 Energy Density and Intensity of Thermal Radiation......Page 379
12.2 The Equation of State......Page 383
12.3 Entropy and Adiabatic Processes......Page 386
12.4 Wien’s Theorem......Page 387
12.5 Chemical Potential of Thermal Radiation......Page 389
12.6 Matter-Antimatter in Equilibrium with Thermal Radiation: The State of Zero Chemical Potential......Page 391
Exercises......Page 395
13.1 The Nonequilibrium Nature of Life......Page 397
13.2 Gibbs Energy Change in Chemical Transformations......Page 400
13.3 Gibbs Energy Flow in Biological Systems......Page 403
13.4 Biochemical Kinetics......Page 417
Examples......Page 424
Exercises......Page 427
14.1 Chemical Potential of Small Systems......Page 429
14.2 Size-Dependent Properties......Page 432
14.3 Nucleation......Page 436
14.4 Fluctuations and Stability......Page 439
Exercises......Page 448
15.2 Thermal Stability......Page 451
15.3 Mechanical Stability......Page 453
15.4 Stability with Respect to Fluctuations in N......Page 455
Exercises......Page 457
16.1 Stability and Critical Phenomena......Page 459
16.2 Stability and Critical Phenomena in Binary Solutions......Page 461
16.3 Configurational Heat Capacity......Page 465
Further Reading......Page 466
Exercises......Page 467
Introduction......Page 469
17.1 Fundamentals and Overview......Page 470
17.2 Partition Function Factorization......Page 472
17.3 The Boltzmann Probability Distribution and Average Values......Page 473
17.4 Microstates, Entropy and the Canonical Ensemble......Page 475
17.6 Calculating Partition Functions......Page 480
17.7 Equilibrium Constants......Page 487
Appendix 17.1 Approximations and Integrals......Page 489
Examples......Page 490
Exercises......Page 491
LIST OF VARIABLES......Page 493
STANDARD THERMODYNAMIC PROPERTIES......Page 495
PHYSICAL CONSTANTS AND DATA......Page 503
NAME INDEX......Page 505
SUBJECT INDEX......Page 507