Modern Thermodynamics E-Book

Dilip Kondepudi

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1045

Veröffentlichungsjahr: 2014

Beschreibung

Modern Thermodynamics: From Heat Engines to Dissipative Structures, Second Edition presents a comprehensive introduction to 20th century thermodynamics that can be applied to both equilibrium and non-equilibrium systems, unifying what was traditionally divided into ‘thermodynamics’ and ‘kinetics’ into one theory of irreversible processes.

This comprehensive text, suitable for introductory as well as advanced courses on thermodynamics, has been widely used by chemists, physicists, engineers and geologists.  Fully revised and expanded, this new edition includes the following updates and features:

• Includes a completely new chapter on Principles of Statistical Thermodynamics.
• Presents new material on solar and wind energy flows and energy flows of interest to engineering.
• Covers new material on self-organization in non-equilibrium systems and the thermodynamics of small systems.
• Highlights a wide range of applications relevant to students across physical sciences and engineering courses.
• Introduces students to computational methods using updated Mathematica codes.
• Includes problem sets to help the reader understand and apply the principles introduced throughout the text.
• Solutions to exercises and supplementary lecture material provided online at http://sites.google.com/site/modernthermodynamics/.

Modern Thermodynamics: From Heat Engines to Dissipative Structures, Second Edition is an essential resource for undergraduate and graduate students taking a course in thermodynamics.

Leseprobe

Modern Thermodynamics

From Heat Engines to Dissipative Structures

Second Edition

DILIP KONDEPUDI

Wake Forest University, USA

ILYA PRIGOGINE

Formerly Director, International Solvay Institutes, Belgium

This edition first published 2015 © 2015 John Wiley & Sons, Ltd

Registered officeJohn Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex, PO19 8SQ, United Kingdom

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Library of Congress Cataloging-in-Publication Data

Kondepudi, Dilip, 1952– author. Modern thermodynamics : from heat engines to dissipative structures / Dilip Kondepudi, Ilya Prigogine. – Second edition. pages cm Includes index. ISBN 978-1-118-37181-7 (pbk.) 1. Thermodynamics. I. Prigogine, I. (Ilya), author. II. Title. QC311.K66 2015 536′.7–dc23

2014021349

A catalogue record for this book is available from the British Library.

ISBN: 9781118371817

To all who contributed to our knowledge of Dissipative Structures

and

to Shelley and Maryna

CONTENTS

Preface to the Second Edition

Preface to the First Edition: Why Thermodynamics?

Acknowledgments

Notes

Notes for Instructors

Notes

List of Variables

Part I: Historical Roots: From Heat Engines to Cosmology

Chapter 1: Basic Concepts and the Laws of Gases

Introduction

1.1 Thermodynamic Systems

1.2 Equilibrium and Nonequilibrium Systems

1.3 Biological and Other Open Systems

1.4 Temperature, Heat and Quantitative Laws of Gases

1.5 States of Matter and the van der Waals Equation

1.6 An Introduction to the Kinetic Theory of Gases

Appendix 1.1 Partial Derivatives

Appendix 1.2 Elementary Concepts in Probability Theory

Appendix 1.3

Mathematica

Codes

References

Examples

Exercises

Note

Chapter 2: The First Law of Thermodynamics

The Idea of Energy Conservation Amidst New Discoveries

2.1 The Nature of Heat

2.2 The First Law of Thermodynamics: The Conservation of Energy

2.3 Elementary Applications of the First Law

2.4 Thermochemistry: Conservation of Energy in Chemical Reactions

2.5 Extent of Reaction: A State Variable for Chemical Systems

2.6 Conservation of Energy in Nuclear Reactions and Some General Remarks

2.7 Energy Flows and Organized States

Appendix 2.1

Mathematica

Codes

Appendix 2.2 Energy Flow in the USA for the Year 2013

References

Examples

Exercises

Notes

Chapter 3: The Second Law of Thermodynamics and the Arrow of Time

3.1 The Birth of the Second Law

3.2 The Absolute Scale of Temperature

3.3 The Second Law and the Concept of Entropy

3.4 Modern Formulation of the Second Law

3.5 Examples of Entropy Changes due to Irreversible Processes

3.6 Entropy Changes Associated with Phase Transformations

3.7 Entropy of an Ideal Gas

3.8 Remarks about the Second Law and Irreversible Processes

Appendix 3.1 The Hurricane as a Heat Engine

Appendix 3.2 Entropy Production in Continuous Systems

References

Examples

Exercises

Note

Chapter 4: Entropy in the Realm of Chemical Reactions

4.1 Chemical Potential and Affinity: The Thermodynamic Force for Chemical Reactions

4.2 General Properties of Affinity

4.3 Entropy Production Due to Diffusion

4.4 General Properties of Entropy

Appendix 4.1 Thermodynamics Description of Diffusion

References

Example

Exercises

Part II: Equilibrium Thermodynamics

Chapter 5: Extremum Principles and General Thermodynamic Relations

Extremum Principles in Nature

5.1 Extremum Principles Associated with the Second Law

5.2 General Thermodynamic Relations

5.3 Gibbs Energy of Formation and Chemical Potential

5.4 Maxwell Relations

5.5 Extensivity with Respect to

N

and Partial Molar Quantities

5.6 Surface Tension

References

Examples

Exercises

Note

Chapter 6: Basic Thermodynamics of Gases, Liquids and Solids

Introduction

6.1 Thermodynamics of Ideal Gases

6.2 Thermodynamics of Real Gases

6.3 Thermodynamics Quantities for Pure Liquids and Solids

Reference

Examples

Exercises

Note

Chapter 7: Thermodynamics of Phase Change

Introduction

7.1 Phase Equilibrium and Phase Diagrams

7.2 The Gibbs Phase Rule and Duhem's Theorem

7.3 Binary and Ternary Systems

7.4 Maxwell's Construction and the Lever Rule

7.5 Phase Transitions

References

Examples

Exercises

Chapter 8: Thermodynamics of Solutions

8.1 Ideal and Nonideal Solutions

8.2 Colligative Properties

8.3 Solubility Equilibrium

8.4 Thermodynamic Mixing and Excess Functions

8.5 Azeotropy

References

Examples

Exercises

Notes

Chapter 9: Thermodynamics of Chemical Transformations

9.1 Transformations of Matter

9.2 Chemical Reaction Rates

9.3 Chemical Equilibrium and the Law of Mass Action

9.4 The Principle of Detailed Balance

9.5 Entropy Production due to Chemical Reactions

9.6 Elementary Theory of Chemical Reaction Rates

9.7 Coupled Reactions and Flow Reactors

Appendix 9.1

Mathematica

Codes

References

Examples

Exercises

Notes

Chapter 10: Fields and Internal Degrees of Freedom

The Many Faces of Chemical Potential

10.1 Chemical Potential in a Field

10.2 Membranes and Electrochemical Cells

10.3 Isothermal Diffusion

10.4 Chemical Potential for an Internal Degree of Freedom

References

Examples

Exercises

Chapter 11: Thermodynamics of Radiation

Introduction

11.1 Energy Density and Intensity of Thermal Radiation

11.2 The Equation of State

11.3 Entropy and Adiabatic Processes

11.4 Wien's Theorem

11.5 Chemical Potential of Thermal Radiation

11.6 Matter–Antimatter in Equilibrium with Thermal Radiation: The State of Zero Chemical Potential

11.7 Chemical Potential of Radiation not in Thermal Equilibrium with Matter

11.8 Entropy of Nonequilibrium Radiation

References

Example

Exercises

Part III: Fluctuations and Stability

Chapter 12: The Gibbs Stability Theory

12.1 Classical Stability Theory

12.2 Thermal Stability

12.3 Mechanical Stability

12.4 Stability and Fluctuations in

N

k

References

Exercises

Note

Chapter 13: Critical Phenomena and Configurational Heat Capacity

Introduction

13.1 Stability and Critical Phenomena

13.2 Stability and Critical Phenomena in Binary Solutions

13.3 Configurational Heat Capacity

Further Reading

Exercises

Chapter 14: Entropy Production, Fluctuations and Small Systems

14.1 Stability and Entropy Production

14.2 Thermodynamic Theory of Fluctuations

14.3 Small Systems

14.4 Size-Dependent Properties

14.5 Nucleation

References

Example

Exercises

Part IV: Linear Nonequilibrium Thermodynamics

Chapter 15: Nonequilibrium Thermodynamics: The Foundations

15.1 Local Equilibrium

15.2 Local Entropy Production

15.3 Balance Equation for Concentration

15.4 Energy Conservation in Open Systems

15.5 The Entropy Balance Equation

Appendix 15.1 Entropy Production

References

Exercises

Notes

Chapter 16: Nonequilibrium Thermodynamics: The Linear Regime

16.1 Linear Phenomenological Laws

16.2 Onsager Reciprocal Relations and the Symmetry Principle

16.3 Thermoelectric Phenomena

16.4 Diffusion

16.5 Chemical Reactions

16.6 Heat Conduction in Anisotropic Solids

16.7 Electrokinetic Phenomena and the Saxen Relations

16.8 Thermal Diffusion

References

Further Reading

Exercises

Notes

Chapter 17: Nonequilibrium Stationary States and Their Stability: Linear Regime

17.1 Stationary States under Nonequilibrium Conditions

17.2 The Theorem of Minimum Entropy Production

17.3 Time Variation of Entropy Production and the Stability of Stationary States

References

Exercises

Note

Part V: Order Through Fluctuations

Chapter 18: Nonlinear Thermodynamics

18.1 Far-from-Equilibrium Systems

18.2 General Properties of Entropy Production

18.3 Stability of Nonequilibrium Stationary States

18.4 Linear Stability Analysis

Appendix 18.1 A General Property of d

F

P

/d

t

Appendix 18.2 General Expression for the Time Derivative of

δ

2

S

References

Exercises

Note

Chapter 19: Dissipative Structures

19.1 The Constructive Role of Irreversible Processes

19.2 Loss of Stability, Bifurcation and Symmetry Breaking

19.3 Chiral Symmetry Breaking and Life

19.4 Chemical Oscillations

19.5 Turing Structures and Propagating Waves

19.6 Dissipative Structures and Machines

19.7 Structural Instability and Biochemical Evolution

Appendix 19.1 

Mathematica

Codes

References

Further Reading

Exercises

Notes

Chapter 20: Elements of Statistical Thermodynamics

Introduction

20.1 Fundamentals and Overview

20.2 Partition Function Factorization

20.3 The Boltzmann Probability Distribution and Average Values

20.4 Microstates, Entropy and the Canonical Ensemble

20.5 Canonical Partition Function and Thermodynamic Quantities

20.6 Calculating Partition Functions

20.7 Equilibrium Constants

20.8 Heat Capacities of Solids

20.9 Planck's Distribution Law for Thermal Radiation

Appendix 20.1 Approximations and Integrals

Reference

Example

Exercises

Notes

Chapter 21: Self-Organization and Dissipative Structures in Nature

21.1 Dissipative Structures in Diverse Disciplines

21.2 Towards a Thermodynamic Theory of Organisms

References

Epilogue