Chemical Kinetics of Gas Reactions

Chemical Kinetics of Gas Reactions

1st Edition - January 1, 1964

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  • Author: V. N. Kondrat'Ev
  • eBook ISBN: 9781483225180

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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

  • Foreword

    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

Product details

  • No. of pages: 826
  • Language: English
  • Copyright: © Pergamon 1964
  • Published: January 1, 1964
  • Imprint: Pergamon
  • eBook ISBN: 9781483225180

About the Author

V. N. Kondrat'Ev

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