Thermodynamics of Non-Equilibrium Processes for Chemists with a Particular Application to Catalysis

Thermodynamics of Non-Equilibrium Processes for Chemists with a Particular Application to Catalysis consists of materials adapted from lectures on the thermodynamics of nonequilibrium processes that have been taught at the Department of Natural Sciences of Novosibirsk State University since 1995. The thermodynamics of nonequilibrium processes traditionally required students to have a strong background in physics. However, the materials featured in this volume allow anyone with knowledge in classical thermodynamics of equilibrium processes and traditional chemical kinetics to understand the subject. Topics discussed include systems in the thermodynamics of irreversible processes; thermodynamics of systems that are close to and far from equilibrium; thermodynamics of catalysts; the application of nonequilibrium thermodynamics to material science; and the relationship between entropy and information. This book will be helpful for research into complex chemical transformations, particularly catalytic transformations.

• Applies simple approaches of non-equilibrium thermodynamics to analyzing properties of chemically reactive systems
• Covers systems far from equilibrium, allowing the consideration of most chemically reactive systems of a chemical or biological nature
• This approach resolves many complicated problems in the teaching of chemical kinetics

Undergraduate and PhD students in chemical, chemical engineering or biological departments and researchers engaged in chemical kinetics, catalysis, chemical engineering and biophysics

List of Main Symbols

An Introduction to the Problems under Discussion

Chapter 1. Systems in Thermodynamics of Nonequilibrium Processes

1.1. Definitions

1.2. The Second Law of Thermodynamics as Applied to Open Systems

1.2.1. Entropy Changes in an Open System

1.2.2. Nonequilibrium Systems with Uniform and Time-Constant Temperature and Pressure

1.2.3. Fluxes of Thermodynamic Parameters

1.2.4. The Thermodynamic Conjugation of Processes

1.3. Fluxes and Thermodynamic Forces in Spatially Homogeneous Chemically Reactive Systems

1.3.1. The “Thermodynamic” Form of Kinetic Equations

1.3.2. The Relationship between the Stationary Rate and the Thermodynamic Forces of a Stepwise Stoichiometric Process

1.3.3. Chemical Potentials of Intermediates

1.4. The Kinetic-Thermodynamic Analysis of the Stationary Mode of Noncatalytic Stepwise Reactions

1.4.1. Independence of the Stationary Rate of the Standard Thermodynamic Parameters of the Reaction Intermediates

1.4.2. Criteria of Kinetic Irreversibility of Chemical Reactions

1.4.3. Rate-Limiting, Rate-Determining, and Rate-Controlling Steps

1.4.4. Rate-Determining Parameters of a Sequence of Monomolecular Reactions

1.4.5. Apparent Activation Energy of a Stepwise Process

1.4.6. Rate-Limiting Steps, Rate-Determining Parameters, and Apparent Activation Energy of Simple Schemes of Chemical Transformations

1.4.7. Qualitative Analysis of Some Peculiarities of Stationary States of Stepwise Processes

1.5. Thermodynamic Forces in Spatially Nonuniform Systems

1.5.1. Calculating the Thermodynamic Forces in Spatially Nonuniform Systems

1.5.2. Calculating the Thermodynamic Forces in Spatially Inhomogeneous Systems

1.6. Chapter Exercises

References

Chapter 2. Thermodynamics of Systems Close to Equilibrium

2.1. The Relationship between the Values of Flux and Thermodynamic Force Close to Thermodynamic Equilibrium

2.2. The Interaction between Thermodynamic Processes and Linear Onsager Relations

2.3. Thermodynamic Conjugation of the Processes

2.3.1. The Transport of Matter through a Membrane during Osmosis

2.3.2. The Active Transport of Matter through a Membrane

2.3.3. Conjugate Processes in Spatially Inhomogeneous Systems

2.3.4. Thermodynamic Conjugation of Cocurrent Chemical Reactions

2.3.5. The Onsager Reciprocal Relations for Cocurrent Stepwise Processes with Common Intermediates

2.4. Thermodynamic Criteria of Achievement and Stability of Stationary States

2.4.1. The Prigogine Criterion (Theorem) of the Evolution for Systems that Are Close to Their Thermodynamic Equilibrium

2.4.2. Stability of the Stationary State near Equilibrium

2.5. The Thermodynamics of Metabolic Cycles and the Direction of the Evolution of Living Systems

2.6. Chapter Exercises

Bibliography

Chapter 3. Thermodynamics of Systems that Are Far from Equilibrium

3.1. Thermodynamic and Kinetic Approaches

3.2. Evolution in Nonlinear Thermodynamics

3.3. Thermodynamic Criteria of the Stability of Stationary States that Are Far from Equilibrium

3.4. Reactive Systems that Are Far from Thermodynamic Equilibrium

3.4.1. Stationary State Functionals of Reactive Systems that Are Far from Equilibrium

3.4.2. The Lyapunov's Functions for Simple Kinetic Schemes

3.5. Thermodynamics and Stability of Nonlinear Kinetic Systems

3.5.1. One-Parameter Systems

3.5.2. Schemes of Transformations with Several Intermediates and Their Stability According to Lyapunov

3.6. Physicochemical Behavior of Dissipative Structures

3.6.1. Spatial Dissipative Structures

3.7. Chapter Exercises

References

Bibliography

Chapter 4. Catalytic Processes and the Thermodynamics of Operating Catalysts

4.1. Operating Catalysts as Objects of the Thermodynamics

4.2. “Microkinetic” Descriptions of Stationary Catalytic Reactions

4.2.1. Stationary Catalytic Reactions

4.2.2. Stationary Microkinetics and Rate-Determining Parameters of the Simplest Intermediate-Linear Catalytic Reactions

4.2.3. Stationary Microkinetics of the Simplest Catalytic Reactions with Nonlinear Catalytic Intermediates

4.3. Stability of the Stationary State of the Operating Catalyst

4.3.1. The Lyapunov Function for Catalytic Transformations with Linear Catalytic Intermediates

4.3.2. Stability of the Catalyst Stationary State of Transformations with Nonlinear Catalytic Intermediates

4.4. Energy Correlations in Catalysis

4.4.1. Energy Parameters of Intermediates and the Rate of the Catalytic Process

4.4.2. Energy Correlations and the Conditions of Maximal Activity of the Catalyst Reaction Center

4.4.3. The Effect of the Active Component Size on the Rate of Catalytic Reactions

4.5. Conjugation of Catalytic Processes

4.5.1. The Horiuti-Boreskov-Onsager Relations for Parallel Catalytic Reactions with Common Intermediates

4.5.2. Application of the Horiuti-Boreskov-Onsager Equations for Identifying the Conditions of Reversal of a Catalytic Transformation

4.5.3 Using the Horiuti-Boreskov-Onsager Equations for the Approximate Kinetic Description of Complex Catalytic Transformations

4.5.4. Conclusions

4.6. Specific Properties of the Nonequilibrium State of Operating Catalysts

4.6.1. Specific Features of Nonequilibrium Stable States of the Operating Catalyst

4.6.2. Temporal and Spatio-Temporal Dissipative Structures in Catalytic Systems

4.7. Chapter Exercises

References

Bibliography

Chapter 5. Application of Nonequilibrium Thermodynamics to Material Science

5.1. Features of Thermodynamics of Material Synthesis

5.2. Synthesis of Thermodynamically Unstable Compounds and Materials

5.3. The Ostwald Step Rule for the Phase Transformations

5.4. Synthesis of Carbon Nanofilaments, Nanofibers, and Nanotubes

5.5. Chapter Exercises

References

Bibliography

Chapter 6. Entropy and Information

6.1. Timing Hierarchy of Processes in Complex Dynamic Systems

6.2. The Relationship between Entropy and Dynamic Stability of a System

6.3. The Relationship between Entropy and Information

6.4. The Quantity of Biological Information

6.5. The Value of Information

6.6. Reception and Expression of Information in Dynamic Systems

6.7. Bioinformatics and Its Application to Biology and Biochemistry

6.8. Chapter Exercises

References

Bibliography

Literature

General Bibliography on Thermodynamics of Non-Equilibrium and Irreversible Processes

Index