Introduction to Modern Thermodynamics

by Dilip Kondepudi (Wake Forest University)

• ISBN13: 9780470015988
• ISBN10: 0470015985
• Format: Hardcover
• Copyright: 2008-06-01
• Publisher: WILEY

Summary

This is the first modern approach to thermodynamics written specifically for a first undergraduate course. It covers the fundamental formalism with some attention given to its history; describes basic applications of the formalism and continues with a number of additional applications that instructors can use according to their particular degree program - these chapters cover thermal radiation, biological systems, nano systems, classical stability theory, and principles of statistical thermodynamics. A wide range of examples appear throughout the book from biological, engineering and atmospheric systems.Each chapter contains a bibliography and numerous examples and exercises. An accompanying web site will provide students with information and links to data sources and other thermodynamics-related sites, and instructors will be able to download complete solutions to exercises.

Author Biography

Dilip Kondepudi is Thurman D. Kitchin Professor of Chemistry, Wake Forest University, where his main research interest is chiral asymmetry in nature. He has, in addition, many years teaching experience to both under- and postgraduate students. he is the author, with the late Ilya Prigogine, of the highly successful book Modern thermodynamics: From Heat engines to Dissipative Structures.

Table of Contents

Preface	p. xiii
The Formalism of Modern Thermodynamics
Basic Concepts and the Laws of Gases	p. 3
Introduction	p. 3
Thermodynamic Systems	p. 4
Equilibrium and Nonequilibrium Systems	p. 6
Biological and Other Open Systems	p. 9
Temperature, Heat and Quantitative Laws of Gases	p. 11
States of Matter and the van der Waals Equation	p. 19
An Introduction to Kinetic Theory of Gases	p. 29
Partial Derivatives	p. 37
Elementary Concepts in Probability Theory	p. 39
Mathematica Codes	p. 41
References	p. 44
Examples	p. 44
Exercises	p. 45
The First Law of Thermodynamics	p. 49
The Idea of Energy Conservation amidst New Discoveries	p. 49
The Nature of Heat	p. 50
The First Law of Thermodynamics: The Conservation of Energy	p. 55
Elementary Applications of the First Law	p. 64
Thermochemistry: Conservation of Energy in Chemical Reactions	p. 68
Extent of Reaction: A State Variable for Chemical Systems	p. 76
Conservation of Energy in Nuclear Reactions and Some General Remarks	p. 79
Energy Flows and Organized States	p. 81
Mathematica Codes	p. 87
References	p. 88
Examples	p. 88
Exercises	p. 92
The Second Law of Thermodynamics and the Arrow of Time	p. 97
The Birth of the Second Law	p. 97
The Absolute Scale of Temperature	p. 106
The Second Law and the Concept of Entropy	p. 108
Entropy, Reversible and Irreversible Processes	p. 116
Examples of Entropy Changes due to Irreversible Processes	p. 125
Entropy Changes Associated with Phase Transformations	p. 128
Entropy of an Ideal Gas	p. 129
Remarks about the Second Law and Irreversible Processes	p. 130
The Hurricane as a Heat Engine	p. 132
Entropy Production in Continuous Systems	p. 135
References	p. 136
Examples	p. 137
Exercises	p. 139
Entropy in the Realm of Chemical Reactions	p. 141
Chemical Potential and Affinity: The Thermodynamic Force for Chemical Reactions	p. 141
General Properties of Affinity	p. 150
Entropy Production Due to Diffusion	p. 153
General Properties of Entropy	p. 155
Thermodynamics Description of Diffusion	p. 158
References	p. 158
Examples	p. 159
Exercises	p. 160
Extremum Principles and General Thermodynamic Relations	p. 163
Extremum Principles in Nature	p. 163
Extremum Principles Associated with the Second Law	p. 163
General Thermodynamic Relations	p. 173
Gibbs Energy of Formation and Chemical Potential	p. 176
Maxwell Relations	p. 179
Extensivity with Respect to N and Partial Molar Quantities	p. 181
Surface Tension	p. 183
References	p. 187
Examples	p. 187
Exercises	p. 189
Applications: Equilibrium and Nonequilibrium Systems
Basic Thermodynamics of Gases, Liquids and Solids	p. 195
Introduction	p. 195
Thermodynamics of Ideal Gases	p. 195
Thermodynamics of Real Gases	p. 199
Thermodynamics Quantities for Pure Liquids and Solids	p. 208
Equations of State	p. 211
Reference	p. 211
Examples	p. 212
Exercises	p. 213
Thermodynamics of Phase Change	p. 215
Introduction	p. 215
Phase Equilibrium and Phase Diagrams	p. 215
The Gibbs Phase Rule and Duhem's Theorem	p. 221
Binary and Ternary Systems	p. 223
Maxwell's Construction and the Lever Rule	p. 229
Phase Transitions	p. 231
References	p. 235
Examples	p. 235
Exercises	p. 236
Thermodynamics of Solutions	p. 239
Ideal and Nonideal Solutions	p. 239
Colligative Properties	p. 243
Solubility Equilibrium	p. 250
Thermodynamic Mixing and Excess Functions	p. 255
Azeotropy	p. 259
References	p. 260
Examples	p. 260
Exercises	p. 262
Thermodynamics of Chemical Transformations	p. 265
Transformations of Matter	p. 265
Chemical Reaction Rates	p. 266
Chemical Equilibrium and the Law of Mass Action	p. 273
The Principle of Detailed Balance	p. 278
Entropy Production due to Chemical Reactions	p. 280
Elementary Theory of Chemical Reaction Rates	p. 285
Coupled Reactions and Flow Reactors	p. 288
Mathematica Codes	p. 295
References	p. 298
Examples	p. 298
Exercises	p. 300
Fields and Internal Degrees of Freedom	p. 305
The Many Faces of Chemical Potential	p. 305
Chemical Potential in a Field	p. 305
Membranes and Electrochemical Cells	p. 311
Isothermal Diffusion	p. 319
Reference	p. 324
Examples	p. 324
Exercises	p. 325
Introduction to Nonequilibrium Systems	p. 327
Introduction	p. 327
Local Equilibrium	p. 328
Local Entropy Production, Thermodynamic Forces and Flows	p. 331
Linear Phenomenological Laws and Onsager Reciprocal Relations	p. 333
Symmetry-Breaking Transitions and Dissipative Structures	p. 339
Chemical Oscillations	p. 345
Mathematica Codes	p. 352
References	p. 355
Further Reading	p. 356
Exercises	p. 357
Additional Topics
Thermodynamics of Radiation	p. 361
Introduction	p. 361
Energy Density and Intensity of Thermal Radiation	p. 361
The Equation of State	p. 365
Entropy and Adiabatic Processes	p. 368
Wien's Theorem	p. 369
Chemical Potential of Thermal Radiation	p. 371
Matter-Antimatter in Equilibrium with Thermal Radiation: The State of Zero Chemical Potential	p. 373
References	p. 377
Examples	p. 377
Exercises	p. 377
Biological Systems	p. 379
The Nonequilibrium Nature of Life	p. 379
Gibbs Energy Change in Chemical Transformations	p. 382
Gibbs Energy Flow in Biological Systems	p. 385
Biochemical Kinetics	p. 399
References	p. 406
Further Reading	p. 406
Examples	p. 406
Exercises	p. 409
Thermodynamics of Small Systems	p. 411
Introduction	p. 411
Chemical Potential of Small Systems	p. 411
Size-Dependent Properties	p. 414
Nucleation	p. 418
Fluctuations and Stability	p. 421
References	p. 430
Examples	p. 430
Exercises	p. 430
Classical Stability Theory	p. 433
Stability of Equilibrium States	p. 433
Thermal Stability	p. 433
Mechanical Stability	p. 435
Stability with Respect to Fluctuations in N	p. 437
References	p. 439
Exercises	p. 439
Critical Phenomena and Configurational Heat Capacity	p. 441
Introduction	p. 441
Stability and Critical Phenomena	p. 441
Stability and Critical Phenomena in Binary Solutions	p. 443
Configurational Heat Capacity	p. 447
Further Reading	p. 448
Exercises	p. 449
Elements of Statistical Thermodynamics	p. 451
Introduction	p. 451
Fundamentals and Overview	p. 452
Partition Function Factorization	p. 454
The Boltzmann Probability Distribution and Average Values	p. 455
Microstates, Entropy and the Canonical Ensemble	p. 457
Canonical Partition Function and Thermodynamic Quantities	p. 462
Calculating Partition Functions	p. 462
Equilibrium Constants	p. 469
Approximations and Integrals	p. 471
Reference	p. 472
Examples	p. 472
Exercises	p. 473
List of Variables	p. 475
Standard Thermodynamic Properties	p. 477
Physical Constants and Data	p. 485
Name Index	p. 487
Subject Index	p. 489
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