The book presents “three kinetics”: (a) detailed, oriented to the elucidation of a detailed reaction mechanism according to its kinetic laws; (b) applied, with the aim of obtaining kinetic relationships for the further design of chemical reactors; and (c) mathematical kinetics whose purpose is the analysis of mathematical models for heterogeneous catalytic reactions taking place under steady- or unsteady state conditions

Besides establishing a general theory permitting us to investigate the dependence of kinetic characteristics for complex reactions on the structure of detailed mechanism, the book provides a comprehensive analysis of some concrete typical mechanisms for catalytic reactions, in particular for the oxidation of carbon monoxide on platinum metals. This reaction is a long-standing traditional object of catalysis study, “Mona Lisa” of heterogeneous catalysis.

Contents

Preface

Authors’ preface

Introduction

References

Chapter 1 (PDF Preface-Intro-Ch1)

Minimum minumorum

1. Introduction

2. Chemical kinetics and linear algebra

3. Unsteady- and steady-state kinetic models

4 Steady-state reaction theory

5. Elements of qualitative theory of differential equations

6. Relaxation in catalytic reactions

References

Chapter 2 (PDF Ch2)

The development of basic concepts of chemical kinetics in heterogeneous catalysis

1. Steps in development of general chemical kinetics

2. The development of the kinetics of heterogeneous catalysis

2.1 Ideal adsorbed layer model

2.2 Real adsorbed layer models

2.3 Models accounting for phase and structural transformations of catalysts

2.3.1 Phenomenological model

2.3.2 Lattice gas model

2.3.3 Topochemical models

2.4 Model accounting for diffusional mass transfer

2.5 Heterogeneous-homogeneous catalytic reaction models

2.6 Phenomenological model of branched-chain reactions on a catalyst surface

3. Conclusion

References

Chapter 3 (PDF Ch3, part 1)

Formalism of chemical kinetics

1. Main concepts of chemical kinetics

1.1 Linear laws of conservation

1.2 Stoichiometry of complex reactions

1.3 Graphical representations of reaction mechanisms

1.4 Chemical kinetics equations

1.5 Reaction polyhedron

1.6 Reaction rate

1.7 Concentration equations

1.8 Non-ideal systems

2. Principle of detailed equilibrium and its consequences

2.1 Principle of detailed equilibrium

2.2 The uniqueness and stability of equilibrium in closed systems

2.3 Thermodynamic limitations on non-steady state kinetic behaviour

2.4 Limitations on non-steady state kinetic behaviour imposed by reaction mechanism

3. Formalism of chemical kinetics for open systems (PDF, Ch2, part 2)

3.1 Kinetic equations for open systems

3.2 “Weakly open” systems

3.3 Stabilization at high flow rates

4. Quasi-stationarity

5. Uniqueness, multiplicity and stability of steady states

5.1 Linear mechanisms

5.2 Mechanisms without intermediate interactions

5.3 Quasi-thermodynamic Horn and Jackson systems

5.4 Criterion for uniqueness and multiplicity associated with the mechanism structure

5.5 Some conclusions

References

Chapter 4 (PDF, Ch.4)

Graphs in chemical kinetics

1. General description and main concepts

1.1 Simple example

1.2 Two formalisms. Formalism of enzyme kinetics and of steady-state reaction theory

1.3 Non-linear mechanisms on graphs

2. Graphs for steady-state kinetic equations

2.1 Substantiation of the “Mason rule”

2.2 General form of steady-state kinetic equation for complex catalytic reactions with multi-route linear mechanisms

2.3 Analysis of properties for the general steady-state kinetic equation of complex catalytic reactions

2.4 How to find the kinetic equation for reverse reactions

2.5 Matching of reactions and the representation of the kinetic equation of complex catalytic reactions in the Horiuti-Boreskov form

2.6 Observed kinetic regularities and characteristics of detailed mechanisms

2.6.1 Observed reaction order

2.6.2 Observed activation energy

3. Graphs for the analysis of the number of independent parameters

3.1 Simple example

3.2 Reasons for dependence and the impossibility of determining parameters

3.3 Indeterminacy of parameters and graph structure

3.4 The number of determinable parameters and graph colour

3.5 Brutto-reaction, detailed mechanism and the number of parameters under determination

3.5.1 Brutto-equation and the number of steps

3.5.2 Graph colours and kinetic equation structure

4. Graphs to analyze relaxations. General form of characteristic polynomial

5. Conclusion

References

Chapter 5 (PDF Ch5)

Simplest non-linear mechanisms of catalytic reactions producing critical phenomena

1. Critical phenomena in heterogeneous catalytic reactions

2. The “parallel” adsorption mechanism

3. Steady-state characteristics of the simplest mechanism permitting multiplicity of catalyst steady states

4. Relaxation characteristics of the “parallel” adsorption mechanism

5. Analysis of “consecutive” adsorption mechanisms

6. Models of kinetic self-oscillations in heterogeneous catalytic reactions

References

Chapter 6 (PDF, Ch6)

Studies of kinetic models for oxidation reactions over metals (exemplified by CO oxidation)

1. Mechanism and model

2. Modelling of kinetic dependences

3. Dynamic studies of CO oxidation

4. “General” kinetic model and prediction of critical effects

References

Chapter 7 (PDF, Ch7)

Critical retardation effects and slow relaxations

1. The problem of slow relaxations

2. The limit behaviour of dynamic systems

3. Relaxation times. Definition of slow relaxations

4. Bifurcations (explosions) of limit sets

5. Dynamic factors for slow relaxations

6. Taking into account small perturbations and errors of models

7. Conclusion

References

Chapter 8 (PDF, Ch8)

Conclusion

1. Forecast for tomorrow

2. Afterthoughts to the conclusion

References

Comment: This book was prepared for publication in late 1980s. At that time we lived deeply in Siberia. This distance caused some problems. The translation is not perfect (translation is never perfect J): sometimes we can find in the text determination instead of definition, “strong” instead of “exact”, “detailed equilibrium” instead of “detailed balance”, and so on. We can also mention one global formatting mistake: in almost all equations there is a vector sign (an arrow above a letter) instead of bold font. Sometimes this is fine (for vectors), and sometimes this is funny (for matrices, spaces and sets). Nevertheless, the book seems to be readable, and all this noise could be filtered. At least one reader was impressed enough to write a review: W. Henry Weinberg, Review on the book "Comprehensive Chemical Kinetics", Volume 32, Kinetic Models of Catalytic Reactions, Elsevier, 1991). Journal of American Chemical Society (JAChS), V.114, n 13, 1992, 5484-5485.