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.

Contenu

Foreword
Chapter 1 General Kinetic Rules for Chemical Reactions
Rate of Reaction. Kinetic Types of Simple Reactions
Rate of Reaction
Kinetic Types of Simple Reactions
Chemical Equilibrium
Equilibrium Constant
The Arrhenius Equation
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
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
Stable Intermediates
Labile Intermediates
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
Free Radical Reactions
Production of Free Radicals
Reactions of Various Radicals
Complex Radicals
Chapter 3 Theory of Elementary Chemical Processes
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
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
. Potential Energy of a System of Atoms
Potential-Energy Surfaces
Numerical Calculations of Activation Energy
Relation Between Activation Energy and Heat of Reaction
. 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
. 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
. 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
. 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
. 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
. Biomolecular Dissociation Reactions
Dissociation of Diatomic Molecules
The Rate of Thermal Dissociation of Polyatomic Molecules
. Dependence of the Rate of Transfer Reactions on the Structure of the Reacting Molecules
Chapter 5 Unimolecular and Termolecular Reactions
. 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
. Experimental Data
The Pre-exponential Factor (A)
The Activation Energy of Unimolecular Reactions
Rate of Reaction at Low Pressures
Influence of Admixtures
Active Admixtures
. 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
. 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
. 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
. Photochemical Activation of Molecules
Lambert-Beer Law
The Primary Photochemical Process
. 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
. Photochemical Sensitization
Photosensitization by Halogens
Photosensitization by Mercury
. Quantum Yield of Photochemical Reactions
The Basic Photochemical Law
Dependence of Quantum Yield on Wave Length
. 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
. 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
. 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 …