Chemical Kinetics of Gas Reactions

ForewordChapter 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 ProductsChapter 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 RadicalsChapter 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 RateChapter 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 MoleculesChapter 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 BondChapter 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 QuantumChapter 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 ReactionChapter 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 Beta-Radiation Gamma-Radiation Neutrons Hot Particles Ionic Yields of Radiation-Chemical ReactionsChapter 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 HydrocarbonsChapter 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. DetonationReferencesAuthor IndexSubject Index