Nonequilibrium Thermodynamics

Natural phenomena consist of simultaneously occurring transport processes and chemical reactions. These processes may interact with each other and may lead to self-organized structures, fluctuations, instabilities, and evolutionary systems. Nonequilibrium Thermodynamics, Third Edition emphasizes the unifying role of thermodynamics in analyzing the natural phenomena.

This third edition updates and expands on the first and second editions by focusing on the general balance equations for coupled processes of physical, chemical, and biological systems. The new edition contains a new chapter on stochastic approaches to include the statistical thermodynamics, mesoscopic nonequilibrium thermodynamics, fluctuation theory, information theory, and modeling the coupled biochemical systems in thermodynamic analysis. This new addition also comes with more examples and practice problems.

• Informs and updates on all the latest developments in the field
• Contributions from leading authorities and industry experts
• A useful text for seniors and graduate students from diverse engineering and science programs to analyze some nonequilibrium, coupled, evolutionary, stochastic, and dissipative processes
• Highlights fundamentals of equilibrium thermodynamics, transport processes and chemical reactions
• Expands the theory of nonequilibrium thermodynamics and its use in coupled transport processes and chemical reactions in physical, chemical, and biological systems
• Presents a unified analysis for transport and rate processes in various time and space scales
• Discusses stochastic approaches in thermodynamic analysis including fluctuation and information theories
• Has 198 fully solved examples and 287 practice problems
• An Instructor Resource containing the Solution Manual can be obtained from the author: ydemirel2@unl.edu

Graduate students in chemical, biological, mechanical, biomedical, environmental, and systems engineering programs, and in biophysical and biochemical science programs. Advanced students in diverse engineering programs

Dedication

Preface to the Third Edition

List of Symbols

Greek letters

Subscripts

Superscripts

Chapter 1. Fundamentals of Equilibrium Thermodynamics

Abstract

1.1 Introduction

1.2 Basic definitions

1.3 Reversible and irreversible processes

1.4 Equilibrium

1.5 The thermodynamic laws

1.6 Balance equations

1.7 Entropy and entropy production

1.8 The Gibbs equation

1.9 Fluid phase equilibrium

Problems

References

Further Reading

Chapter 2. Transport and Rate Processes

Abstract

2.1 Introduction

2.2 Nonequilibrium systems

2.3 Kinetic approach

2.4 Transport phenomena

2.5 The Maxwell–Stefan equations

2.6 Transport coefficients

2.7 Electric charge flow

2.8 The relaxation theory

2.9 Chemical reactions

2.10 Coupled processes

Problems

References

Further Reading

Chapter 3. Fundamentals of Nonequilibrium Thermodynamics

Abstract

3.1 Introduction

3.2 Local thermodynamic equilibrium

3.3 The second law of thermodynamics

3.4 Balance equations and entropy production

3.5 Entropy production equation

3.6 Phenomenological equations

3.7 Onsager’s Relations

3.8 Transformation of forces and flows

3.9 Chemical reactions

3.10 Heat conduction

3.11 Diffusion

3.12 Validity of linear phenomenological equations

3.13 Curie–Prigogine principle

3.14 Time variation of entropy production

3.15 Minimum entropy production

3.16 Entropy production in an electrical circuit

Problems

References

Further Reading

Chapter 4. Using the Second Law: Thermodynamic Analysis

Abstract

4.1 Introduction

4.2 Second law analysis

4.3 Equipartition principle

4.4 Exergy analysis

4.5 Applications of exergy analysis

4.6 Pinch analysis

4.7 Optimization problem

Problems

References

Further Reading

Chapter 5. Thermoeconomics

Abstract

5.1 Introduction

5.2 Thermodynamic cost

5.3 Ecological cost

5.4 Availability

5.5 Thermodynamic optimum

5.6 Equipartition and optimization in separation systems

Problems

References

Further Reading

Chapter 6. Diffusion

Abstract

6.1 Introduction

6.2 Maxwell–Stefan equation

6.3 Diffusion in electrolyte systems

6.4 Diffusion without shear forces

6.5 Diffusion of biological solutes in liquids

Problems

References

Further Reading

Chapter 7. Heat and Mass Transfer

Abstract

7.1 Introduction

7.2 Coupled heat and mass transfer

7.3 Heat of transport

7.4 Degree of coupling

7.5 Efficiency of coupling

7.6 Coupled mass and energy balances

7.7 Separation by thermal diffusion

7.8 Heat and mass transfer in discontinuous systems

7.9 Thermoelectric effects

Problems

References

Further Reading

Chapter 8. Chemical Reactions

Abstract

8.1 Introduction

8.2 Chemical reaction equilibrium constant

8.3 The principle of detailed balance

8.4 Dissipation for chemical reactions

8.5 Reaction velocity (flow)

8.6 Multiple chemical reactions

8.7 Stationary states

8.8 Biochemical reaction networks

8.9 Energy conversion in coupled chemical reactions

Problems

References

Further Reading

Chapter 9. Coupled Systems of Chemical Reactions and Transport Processes

Abstract

9.1 Introduction

9.2 Nonisothermal reaction-diffusion systems

9.3 Chemical reaction with coupled heat and mass flows

9.4 Coupled system of chemical reaction and transport processes

9.5 Evolution of coupled systems

9.6 Nonlinear macrokinetics in a reaction-diffusion system

Problems

References

Further Reading

Chapter 10. Membrane Transport

Abstract

10.1 Introduction

10.2 Membrane equilibrium

10.3 Passive transport

10.4 Facilitated and active transport in membranes

10.5 Biomembranes

Problems

References

Further Reading

Chapter 11. Thermodynamics and Biological Systems

Abstract

11.1 Introduction

11.2 Simplified analysis in living systems

11.3 Bioenergetics

11.4 Proper pathways

11.5 Coupling in mitochondria

11.6 Regulation in bioenergetics

11.7 Reaction-mass transport in bioenergetics

11.8 Exergy use in bioenergetics

11.9 Molecular machines

11.10 Molecular evolution

11.11 Evolutionary criterion

Problems

References

Further Reading

Chapter 12. Stability Analysis

Abstract

12.1 Introduction

12.2 The Gibbs stability theory

12.3 Stability and entropy production

12.4 Thermodynamic fluctuations

12.5 Stability in nonequilibrium systems

12.6 Linear stability analysis

Problems

References

Further Reading

Chapter 13. Organized Structures

Abstract

13.1 Introduction

13.2 Equilibrium and nonequilibrium structures

13.3 Bifurcation

13.4 Limit cycle

13.5 Order in physical structures

13.6 Order in chemical systems

13.7 Biological structures

Problems

References

Further Reading

Chapter 14. Nonequilibrium Thermodynamics Approaches

Abstract

14.1 Introduction

14.2 Network thermodynamics with bond-graph methodology

14.3 Mosaic nonequilibrium thermodynamics

14.4 Rational thermodynamics

14.5 Extended nonequilibrium thermodynamics

14.6 GENERIC formulations

14.7 Matrix model

14.8 Internal variables

References

Further Reading

Chapter 15. Probabilistic Approach in Thermodynamics

Abstract

15.1 Introduction

15.2 Statistical thermodynamics

15.3 Stochastic thermodynamics

15.4 Fluctuation theorems

15.5 Information theory

15.6 Applications: biomolecules and biochemical cycles

15.7 Statistical rate theory

15.8 Mesoscopic nonequilibrium thermodynamics

References

Further Reading

Appendix A. Tensors

Appendix B. Thermochemical Parameters

Appendix C. Some Biochemical Reaction Properties

Appendix D. Steam Tables

Appendix E. Gas Properties

Appendix F. The Lee/Kesler Generalized-Correlation Tables

Index