Gas-Phase Reactions

I. General Kinetic Rules for Chemical Reactions.- 1. Kinetic Equations. Rate Constants.- 2. Kinetic Classification of Reactions. Simple and Complex Reactions.- 2.1 Kinetic Types of Simple Reactions.- 2.2 Consecutive Reactions.- 2.3 Steady-State Method.- 2.4 Parallel Reactions.- 2.5 Coupled Reactions. Chemical Induction.- 2.6 Homogeneous Catalysis.- 2.7 Catalysis by Products (Autocatalysis).- 3. Chemical Equilibrium.- II. Mechanisms of Chemical Reactions.- 4. Macroscopic Manifestation of a Complex Reaction Mechanism.- 5. Intermediates.- 6. Atomic Reactions.- 6.1 Reactions in Highly-Rarefied and Diffusion Flames Reaction M + X2.- 6.2 Reaction M + RX and Other Reactions.- 6.3 Atomic Hydrogen Reactions.- 6.4 Atomic Oxygen Reactions.- 6.5 Reactions of Atomic Halogens.- 6.6 Atomic Nitrogen Reactions.- 7. Radical Reactions.- 7.1 Production of Radicals.- 7.2 Reactions of Certain Radicals.- III. Theory of Elementary Processes.- 8. Microscopic Formulation of Reaction Kinetics.- 8.1 Cross Sections, Transition Probabilities and Rate Constants of Elementary Processes.- 8.2 Kinetic Equations for Unreactive Processes.- 8.3 Translational, Rotational and Vibrational Relaxation.- 8.4 Kinetics of Reactive Processes.- 8.5 Relation Between Rate Constants of Forward and Reverse Non-Equilibrium Reactions.- 9. Dynamics of Elementary Processes.- 9.1 Adiabatic Approximation.- 9.2 Probabilities of Electronically Adiabatic Processes.- 9.3 Probabilities of Electronically Non-Adiabatic Processes.- 10. Various Types of Potential Energy Surfaces.- 10.1 Rectangular and Skewed Coordinates.- 10.2 Unreactive Interactions A + BC.- 10.3 Reactive Interactions A + BC.- 11. Equilibrium Rate Constants. Transition-State Method.- 11.1 Assumptions and Derivation of the Basic Transition-State Method Expressions.- 11.2 Activation Energy and Pre-Exponential Factors in the Reaction Rate Constant Expression.- IV. Energy Exchange in Molecular Collisions.- 12. Experimental Methods of Studying Vibrational Relaxation.- 12.1 Dispersion and Absorption of Ultrasounds.- 12.2 The Shock-Wave Method.- 12.3 Spectroscopic Methods.- 12.4 Molecular Beams.- 13. Transfer of Translational and Rotational Energy.- 13.1 Translational-Translational (TT) Energy Transfer.- 13.2 Rotational-Translational (RT) Energy Transfer.- 14. Transfer of Vibrational Energy.- 14.1 Exchange of Translational and Vibrational Energy (VT Process).- 14.2 Exchange of Rotational and Vibrational Energy (VR and VRT Processes).- 14.3 Effect of Non-Adiabatic Coupling on Vibrational Energy Transfer.- 14.4 Vibrational Relaxation via Long-Lived Complexes and in Symmetric Exchange Reactions.- 14.5 Intermolecular Quasi-Resonant Vibrational Energy Exchange (Intermolecular VV Process).- 14.6 Intramolecular Quasi-Resonant Vibrational Energy Exchange (Intramolecular VV Process).- 15. Kinetics of the Vibrational Relaxation of Diatomic Molecules.- 16. Energy Exchange with Electronically Excited Molecules.- 16.1 VRT Energy Transfer.- 16.2 Electronic Energy Transfer.- V. Unimolecular Reactions.- 17. The Theory of Unimolecular Reactions.- 17.1 Definition of Unimolecular Reactions.- 17.2 Molecular Activation and Deactivation.- 17.3 Unimolecular Conversion.- 17.4 Pressure Dependence of Rate-Constant of Polyatomic Molecules.- 17.5 Thermal Dissociation of Diatomic Molecules.- 18. Experimental.- 18.1 Pre-Exponential Factor in the k? Expression.- 18.2 Pre-Exponential Factor in the k0 Expression.- 18.3 Energy Exchange in Unimolecular Reactions.- 18.4 Activation Energy for Unimolecular Reactions.- 18.5 Boundary between High-and Low-Pressure Domains (p1/2) (Fall-Off Pressure).- VI. Combination Reactions.- 19. Atomic and Radical Recombination and Addition Reactions.- 19.1 Radiative Stabilization.- 19.1.1 Recombination on a Repulsive Potential Curve.- 19.1.2 Recombination on an Attractive Potential Curve.- 19.1.3 Recombination via Inverse Predissociation.- 19.2 Collisional Stabilization.- 20. Termolecular Reactions.- 20.1 Number of Three-Body Collisions.- VII. Bimolecular Exchange Reactions.- 21. Theory of Bimolecular Exchange Reactions.- 21.1 Classification of Exchange Reactions.- 21.2 Cross Sections of Exchange Reactions.- 21.3 Energy Requirements.- 21.4 Energy Disposal.- 21.5 Temperature Dependence of Rate Constants of Equilibrium Bimolecular Reactions.- 21.6 Non-Equilibrium Effects in Thermal Bimolecular Reactions.- 22. Certain Types of Bimolecular Exchange Reactions.- 22.1 Abstraction of Atoms and Radicals.- 22.2 Isotope Exchange Reactions.- 22.3 Reactions between Atoms, Radicals and Unsaturated Molecules.- 23. Bimolecular Reaction Rates as a Function of Molecular Structure.- 23.1 Reactions of Atomic Sodium with Halogenated Hydrocarbons.- 23.2 Reactions of Hydrogen and Chlorine Atoms, and of Hydroxyl and Methyl Radicals with Hydrocarbons.- 23.3 Bimolecular Reactions of Electronically Excited Species.- VIII. Photochemical Reactions.- 24. Photochemical Activation of Molecules.- 24.1 The Lambert-Beer Law.- 24.2 Primary Photochemical Step. Quantum Yield.- 24.3 Quantum Yield a as Function of the Wavelength.- 24.4 The Nature of Primary Centers of a Photochemical Reaction.- 24.5 Hot Particles.- 25. Secondary Processes in Photochemical Reactions.- 25.1 Secondary Processes Involving Atoms and Radicals.- 25.2 Secondary Processes Involving Excited Molecules.- 25.3 Fluorescence. Metastable Molecules.- 25.4 Fluorescence Quenching.- 26. Photochemical Sensitization.- 26.1 Photosensitization with Halogens.- 26.2 Photosensitization with Mercury.- 27. Temperature Dependence and Photochemical Reaction Mechanisms.- 27.1 Temperature Coefficient.- 27.2 Formation of Hydrogen Bromide from Hydrogen and Bromine Molecules.- 27.3 The Photochemical Reaction Limit.- IX. Chemical Reactions in Electric Discharge.- 28. Activation in Electric Discharge.- 28.1 Excitation of Atoms and Molecules by Electron Impact. The Excitation Function.- 28.2 Excitation of Molecular Vibrations and Rotations by Electron Impact.- 29. Types of Electric Discharge. Low-Temperature Plasma.- 30. Certain Reactions in Electric Discharge and Their Yields.- 30.1 Ozone Production.- 30.2 Ammonia Synthesis from Nitrogen and Hydrogen.- 30.3 Acetylene Production from Methane.- X. Radiation Chemical Reactions.- 31. Primary Processes.- 31.1 Electron Impact Ionization. Generation of Positive Ions.- 31.2 Generation of Negative Ions.- 32. Secondary Processes Specific of Radiation Chemistry.- 32.1 Ion-Molecule Reactions.- 32.2 Recombination of Charged Species.- 32.3 Reactions Involving Highly-Excited Neutral Particles. Hot Atoms.- 33. The Sequence of Elementary Processes in Gas Radiolysis.- 33.1 Examples of Complex Reactions.- 33.2 Radiolysis of Hydrocarbons.- 33.3 Ammonia Radiolysis.- 33.4 Radiolysis of Nitrogen — Oxygen Mixtures.- XI. Chain Reactions.- 34. Non-chain and Chain Reactions.- 35. Stationary Chain Reactions.- 35.1 Mean Chain Length.- 35.2 Time Dependence of Chain Propagation.- 36. Chain Generation.- 36.1 Thermal Gas-Phase Generation of Active Centers.- 36.2 Gas-Phase Generation of Active Centers as a Result of Chemical Interactions.- 36.3 Chain Generation at the Wall.- 37. Chain Termination.- 37.1 Homogeneous Chain Termination.- 37.2 Heterogeneous Chain Termination. Diffusion and Kinetic Regions.- 37.3 Stationary Chain Reaction Rates.- 38. Branched Chains.- 38.1 Limiting Phenomena. Self-Ignition Peninsula.- 38.2 Temperature Dependence of the Chain Reaction Rates.- 38.3 The Role of Impurities in Chain Reactions.- 39. Hydrogen Combustion as Model Reaction.- 39.1 Reaction Mechanism.- 39.2 Low-Pressure Reaction Kinetics.- 39.3 Upper and Lower Ignition Limits.- 39.4 Induction Period.- 39.5 General Solution of Kinetic Problems.- 40. Hydrocarbon Oxidation and Combustion Mechanisms.- 40.1 Combustion Reactions.- 40.2 Slow Oxidations.- 41. Fluorination Reactions.- 42. Radiation-Chemical Initiation of Chain Reactions.- XII. Combustion Processes.- 43. Self-Ignition.- 43.1 Chain Explosion.- 43.2 Two-Stage Self-Ignition.- 43.3 Adiabatie Explosion.- 43.4 Account for Incomplete Combustion.- 44. Non-Premixed Flames.- 44.1 Highly Rarefied Flames.- 44.2 Hot Diffusion Flames.- 45. Premixed Flames.- 45.1 Rarefied Flames.- 45.2 Hot Flames.- 45.3 Cool Flames.- 46. Flame Propagation.- 46.1 Normal Burning Rate.- 46.2 Diffusion Flame Propagation.- 46.3 Thermal Flame Propagation.- 46.4 Flammability Limits.- 47. Detonation.- References.