Chemical Kinetics of Gas Reactions - 1st Edition - ISBN: 9781483200156, 9781483225180

Chemical Kinetics of Gas Reactions

1st Edition

Authors: V. N. Kondrat'Ev
eBook ISBN: 9781483225180
Imprint: Pergamon
Published Date: 1st January 1964
Page Count: 826
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Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions.
This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The remaining chapters examine gas reactions, such as molecular collisions, photochemical reactions, chemical reactions in electrical discharge, chain reactions, and combustion. This book will be of value to reaction kinetics engineers and researchers.

Table of Contents


Chapter 1 General Kinetic Rules for Chemical Reactions

§1. Rate of Reaction. Kinetic Types of Simple Reactions

Rate of Reaction

Kinetic Types of Simple Reactions

§2. Chemical Equilibrium

Equilibrium Constant

The Arrhenius Equation

§3. Complex Reactions

Reactions with Consecutive Steps

Steady State Method

Parallel Reactions

Coupled Reactions. Chemical Induction

Homogeneous Catalysis

Catalysis by End Products

Chapter 2 Chemical Mechanism of Reactions

§4. Experimental Methods for Studying Chemical Reaction Mechanisms

Homogeneous and Heterogeneous Stages of Chemical Reactions

Labelled Atom (Tracer) Method

Overall Formulae and Chemical Mechanisms of Reactions

Intermediate Substances

§5. Stable Intermediates

Labile Intermediates

§6. Reactions of Free Atoms

Reactions in Highly-Rarefied Flames

The Reaction M + HgX2

The Reaction M +X2

The Reaction M +HX

The Reaction M +RX and Other Reactions

Reactions of Atomic Hydrogen

Reactions of Atomic Oxygen

Reactions of Atomic Halogens

Reactions of Active and Atomic Nitrogen

§7. Free Radical Reactions

Production of Free Radicals

Reactions of Various Radicals

Complex Radicals

Chapter 3 Theory of Elementary Chemical Processes

§8. Elements of the Statistical Theory of Elementary Chemical Processes

Basic Ideas of Quantum Mechanics

Adiabatic and Non-adiabatic Processes

Classical Treatment of Nuclear Motion

Conditions for Conservation of the Maxwell-Boltzmann Distribution in a Reacting System

§9. Gas-Kinetic Collision Theory

Effective Cross-Section

Number of Elastic Collisions in Unit Time

Rate of Elementary Bimolecular Reaction

Allowance for Internal Degrees of Freedom

§10. Potential Energy of a System of Atoms

Potential-Energy Surfaces

Numerical Calculations of Activation Energy

Relation Between Activation Energy and Heat of Reaction

§11. Qualitative Consideration of Energy Changes in Three-Atom Reactions

Introduction of Skewed Coordinates

The Reaction Between a Diatomic Molecule and an Atom

Three-Atom Collisions

§12. Transition-State (Activated-Complex) Method

Derivation of the Basic Equation

Introduction of Experimental Activation Energy

Formulae for Calculating the Pre-exponential Factor

Dependence of Reaction Rate on the Isotopie composition of the Reacting Molecules

The Transmission Coefficient

Comparison of Formulae from Gas-Kinetic Theory and from the Transition-State Method

§13. Quantum-Mechanical Treatment of the Rate of Elementary Processes

Methods for Calculating the Probability of a Change of State on Collision

Rate of a Metathetical Reaction

The Role of the Tunnel Effect

Non-intersection of Potential Curves

Probability of Non-adiabatic Transitions

Effect of Non-adiabatic Transitions on the Reaction Rate

Chapter 4 Bimolecular Reactions

§14. Addition Reactions A + B = AB

Stabilization of the Quasi-Molecule

Recombination of Atoms

Recombination of Radicals

Addition of Atoms and Radicals to Multiple or Conjugated Bonds

The Association of Saturated Molecules

§15. Metathetical or Transfer Reactions A + BC = AB + C and Exchange (Double Transfer) Reactions AB + CD = AC + BD

Reactions of Atoms with Molecules

Reactions of Radicals with Molecules

Transfer Reactions Between Radicals or Radical-Like Molecules

Exchange Reactions AB + CD = AC + BD

§16. Biomolecular Dissociation Reactions

Dissociation of Diatomic Molecules

The Rate of Thermal Dissociation of Polyatomic Molecules

§17. Dependence of the Rate of Transfer Reactions on the Structure of the Reacting Molecules

Chapter 5 Unimolecular and Termolecular Reactions

§18. Theory of Unimolecular Reactions

Rate of Reaction at High and Low Rressures

Hinshelwood's Theory

Kassel's Theory

Landau's Theory

"Equilibrium Theory" of Unimolecular Reactions

Slater's Theory

§19. Experimental Data

The Pre-exponential Factor (A)

The Activation Energy of Unimolecular Reactions

Rate of Reaction at Low Pressures

Influence of Admixtures

Active Admixtures

§20. Termolecular Reactions

Number of Ternary Collisions

Reactions Involving a Termolecular Acyclic Complex

Reactions Involving a Termolecular Cyclic Complex

Recombination and Addition to a Multiple Bond

Chapter 6 Energy Conversion During Molecular Collisions

§21. Transformation of Translational and Rotational Energy

Conversion of Translational Energy into Translational and Internal Energy

Conversion of Translational and Rotational Energy

Spectroscopic Method of Studying Energy Conversion Processes in Molecular Collisions

§22. Transformation of Vibrational Energy

The Conversion of Translational into Vibrational Energy and Vice Versa

Experimental Studies of Vibrational-Energy Conversion. Dispersion and Absorption of Ultrasonic Waves

Temperature Dependence of the Probability of Vibrational-Energy Conversion

Dissipation of Vibrational Energy Under Electrical Discharge Conditions

Conversion of the Vibrational Energy of Electronically Excited Molecules

Energy Conversion in Unimolecular Reactions

Stabilization of Molecules During Ternary Collisions

Probability of Vibrational Energy Conversion in Strongly Vibrating Molecules and in Molecules Possessing One Vibrational Quantum

Chapter 7 Photochemical Reactions

§23. Photochemical Activation of Molecules

Lambert-Beer Law

The Primary Photochemical Process

§24. Secondary Processes During Photochemical Reactions

Secondary Processes in the Case of Atoms and Radicals

Secondary Processes Involving Excited Molecules

Fluorescence. Metastable Molecules

Quenching of Fluorescence

Theory of Quenching of Fluorescence

§25. Photochemical Sensitization

Photosensitization by Halogens

Photosensitization by Mercury

§26. Quantum Yield of Photochemical Reactions

The Basic Photochemical Law

Dependence of Quantum Yield on Wave Length

§27. Temperature Coefficient and Mechanism of Photochemical Reactions

Temperature Coefficient

Examples of Reactions with a Temperature Coefficient of Unity

Formation of HBr from H2 + Br2

The Limit of a Photochemical Reaction

Chapter 8 Chemical Reactions in Electrical Discharge

§28. Activation in Electrical Discharge

Excitation of Atoms and Molecules by Electron Impact. The Excitation Function

Ionization of Atoms and Molecules by Electron Impact

Excitation of Molecular Vibration and Rotation by Electron Impact

Formation of Negative Ions on Electron Impact

§29. Activation by Bombardment with Fast Ions and Atoms

Excitation of Atoms and Molecules by Collisions with Fast Ions and Atoms

Ionization of Atoms and Molecules by Collisions with Fast Ions and Atoms

Mechanism of Excitation and Ionization by the Impact of Fast Ions and Atoms

Charge (Electron) Transfer Processes

Dissociation of Molecules by the Impact of Fast Ions

Processes Connected with Proton or H Atom Transfer

§30. Types of Electrical Discharge

Silent Discharge. Spark Discharge

Glow Discharge

Arc Discharge

§31. Chemical Reactions in Electrical Discharge and Yields of these Reactions

Ozone Production

Synthesis of Ammonia from Nitrogen and Hydrogen

Production of Acetylene from Methane

§32. Chemical Reactions Taking Place Under the Action of Penetrating Radiations (Radiation-Induced Chemical Reactions)

Activating Action of Alpha-Particles




Hot Particles

Ionic Yields of Radiation-Chemical Reactions

Chapter 9 Chain Reactions

§33. Simple Chain Reactions

Two Types of Complex Reactions: Non-chain and Chain Reactions

Reaction of Chlorine with Hydrogen

§34 Formal Kinetics of Chain Reactions

Mean Chain Length

Development of Chains with Time

§35. Chain Initiation

Thermal Generation of Active Centres in the Gas Phase

Generation of Active Centres in the Gas Phase as a Result of Chemical Interaction

Chain Initiation at the Wall

§36. Chain Breaking

Chain Breaking in the Gas Phase

Chain Breaking at the Wall. Diffusion and Kinetic Region of the Reaction

Rate of the Steady Chain Reaction

§37. Branching Chains

Branched Chain Length

Limiting Phenomena. Ignition Peninsula

Temperature Dependence of the Rate of Chain Reactions

Interaction of Chains. Degenerate Branching

§38. Macroscopic Stages in Chain Reactions

§39. The Combustion of Hydrogen as a Model Reaction

Mechanism of the Reaction

Kinetics of the Reaction at Low Pressures

Upper and Lower Ignition Limits

Induction Period

Reaction Kinetics Taking Account of Fuel Consumption. Overall Law of the Reaction

Third Ignition Limit

The Mechanism of Oxidation and Combustion of Hydrocarbons

Chapter 10 Combustion Processes

§40. Spontaneous Combustion

Chain Explosion

Thermal Explosion

Ignition of a Gas Mixture by a Heated Surface

Two-Stage Self-Ignition

Adiabatic Explosion

Allowance for Incomplete Combustion

§41. Flames Burning without Preliminary Mixing of the Gases

Highly Rarefied Flames

The Cool Flame of Carbon Disulphide

Hot Diffusion Flames

§42. Flames Burning in Previously Prepared Mixtures

Rarefied Flames

Hot Flames

Thermodynamic Equilibrium in Flames

Cool Flames

§43. Flame Propagation

Normal Rate of Combustion

Similarity of Temperature and Concentration Fields

First Theories of the Thermal Propagation of Flames

Theory of Lewis and von Elbe

Theory of Zel'dovich and Frank-Kamenetskii

Further Development in the Theory of Flame Propagation

Diffusion Propagation of Flames

Diffusion Propagation of Flames Under Isothermal Conditions

Theory of Tanford and Pease

Theory of van Tiggelen

Limits of Flame Propagation

§44. Detonation


Author Index

Subject Index


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About the Author

V. N. Kondrat'Ev

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