Combustion, 2nd edition

Chapter One Chemical Thermodynamics and Flame Temperatures A. Introduction B. Heats of Reaction and Formation C. Free Energy and the Equilibrium Constants D. Flame Temperature Calculations Problems References Chapter Two Chemical Kinetics A. Introduction B. The Rates of Reactions and Their Temperature Dependency 1. The Anhenius Rate Expression 2. Transition State and Recombmation Rate Theories C. Simultaneous Interdependent Reactions D. Chain Reactions E. Pseudo-First-Order Reactions and the "Fall-Off" Range E The Partial Equilibrium Assumption G. Pressure Effect in Fractional Conversion Problems References xv xvii xix xxi CONTENTS Chapter Three Explosive and General Oxidative Characteristics of Fuels A. Introduction B. Chain Branching Reactions and Criteria for Explosion C. Explosion Limits and Oxidation Characteristics of Hydrogen D. Explosion L i t s and Oxidation Characteristics of Carbon Monoxide E. Explosion L i t s and Oxidation Characteristics of Hydrocarbons 1. Organic Nomenclature 2. Explosion L i t s a. The Negative Coefficients of Reaction Rate b. Cool Flames 3. "Low-Temperature" Hydrocarbon Oxidation Mechanisms a. Competition Between Chain Branching and Steady Reaction Steps b. Importance of Isomerization in Large Hydrocarbon Radicals E The Oxidation of Aldehydes G. The Oxidation of Methane H. The Oxidation of Higher-Order Hydrocarbons 1. Alliphatic Hydrocarbons a. Overall View b. Paraffin Oxidation c. Olefin and Acetylene Oxidation 2. Alcohols 3. Aromatic Hydrocarbons a. Benzene Oxidation h. Oxidation of Akylated Aromatics Problems References Chapter Four Flame Phenomena in Premixed Combustible Gases A. Introduction B. Laminar Flame Structure C. The Laminar Flame Speed 1. The Theory of Mallard and Le Chatelier 2. The Theory of Zeldovich, Frank-Kamenetskii, and Semenov 3. The Laminar Flame and the Energy Equation 4. Flame Speed Measurements a. Burner Method b. Cylindrical Tube Method c. Soap Bubble Method d. Closed Spherical Bomb Method e. Flat Flame Burner Method 5. Experimental Results-Physical and Chemical Effects D. Stability Limits of Laminar Flames 1. Hammability Limits 2. Quenching Distance 3. Flame Stabilization (Low Velocity) CONTENTS a. Flashback and Blowoff b. Analysis and Results 4. Stability Limits and Design E. Turbulent Reacting Flows and Turbulent Flames 1. The Rate of Reaction in a Turbulent Field 2. Regimes of Turbulent Reacting Flows 3. The Turbulent Flame Speed E Stirred Reactor Theory G. Flame Stabilization in High-Velocity Streams Problems References Chapter Five Detonation A. Introduction 1. Premixed and Diffusion Flames 2. Explosion, Deflagration, and Detonation 3. The Onset of Detonation B. Detonation Phenomena C. Hugoniot Relations and the Hydrodynamic Theory of Detonations 1. Characterization of the Hugoniot Curve and the Uniqueness of the Chapman-Jouguet Point 2. Determination of the Speed of Sound in the Burned Gases for Conditions above the Chapman-Jouguet Point a. Behavior of the Entropy along the Hugoniot Curve b. The Concavity of the Hugoniot Curve c. The Burned Gas Speed 3. Calculation of the Detonation Velocity D. Comparison of Detonation Velocity Calculations with Experimental Results E. The ZND Structure of Detonation Waves E The Structure of the Cellular Detonation Front and other Detonation Phenomena Parameters 1. The Cellular Detonation Front 2. The Dynamic Detonation Parameters 3. Detonation K i t s G. Detonations in Nongaseous Media Problems References Chapter Six Diffusion Flames A. Introduction B. Gaseous Fuel Jets 1. Appearance 2. Smcture 3. Theoretical Considerations 4. The Burke-Schumann Development 5. Turbulent Fuel Jets C. Buming of Condensed Phases 1. General Mass Buming Considerations and the Evaporation Coefficient xii CONTENTS 2. Single Fuel Droplets in Quiescent Atmospheres a. Heat and Mass Transfer without Chemical Reaction (Evaporation)- the Transfer Number B b. Heat and Mass Transfer with Chemical Reaction (Droplet Burning Rates) c. Refinements of the Mass Burning Rate Expression D. Burning of Droplet Clouds E. Burning in Convective Atmospheres 1. The Stagnant Film Case 2. The Longitudiially Burning Surface 3. The Flowing Droplet Case 4. Burning Rates of Plastics; The Small B Assumption and Radiation Effects Problems References Chapter Seven Ignition A. Concepts B. Chain Spontaneous Ignition C. Thermal Spontaneous Ignition 1. Semenov Approach to Thermal Ignition ' 2. Frank-Kamenetskii Theory of Thermal Ignition a. The Stationary Solution-The Critical Mass and Spontaneous Ignition Problems b. The Nonstationary Solution D. Forced Ignition 1. Spark Ignition and Minimum Ignition Energy 2. Ignition by Adiabatic Compression and Shock Waves Problems References Chapter Eight Environmental Combustion Considerations A. Introduction B. The Nature of Photochemical Smog 1. Primary and Secondary Pollutants 2. The Effect of NO, 3. The Effect of SO, C. NO, Formation and Reduction 1. The Structure of the Nitrogen Oxides 2. The Effect of Flame Structure 3. Atmospheric Nitrogen Kinetics 4. Fuel-Bound Nitrogen Kinetics 5. The Formation of NOz 6. The Reduction of NOx D. SO, Emissions 1. The Product Composition and Structure of Sulfur Compounds 2. Oxidative Mechanisms of Sulfur Fuels a. H2S CONTENTS xiii b. COS and CS2 c. Elemental Sulfur d. Organic Sulfur Compounds e. Sulfur Trioxide and Sulfates f. SO,-NO, Interactions E. Particulate Formation 1. Characteristics of Soot 2. Soot Formation Processes 3. The Use of Flames in Soot Formation Analyses a. Premixed Flames b. Diffusion Flames 4. The Influence of Physical and Chemical Parameters on Soot Formation 5. Particulates from Liquid Hydrocarbon Pyrolysis E Stratospheric Ozone 1. The HO, Catalytic Cycle 2. The NO, Catalytic Cycle 3. The C10, Catalytic Cycle Problems References Chapter Nine The Combustion of Nonvolatile Fuels A. Carbon Char and Metal Combustion B. Diffusion Kinetics C. Diffusion Controlled Burning Rate 1. The Burning of Carbon Char Particles 2. The Burning of Boron Particles 3. The Role of Gaseous Inverts in Heterogeneous Diffusion Burning 4. Oxidation of Very Small Particles-Pulverized Coal and Soot D. The Burning of Porous Chars E. The Burning Rate of Ash-Forming Coal Problems References Appendixes Appendix A. Thennochemical Data and Conversion Factors Appendix B. Specific Reaction Rate Constants Appendix C. Bond Dissociation Energies of Hydrocarbons Appendix D. Laminar Flame Speeds Appendix E. Flammability L i t s in Air Appendix E Spontaneous Ignition Temperature Data Appendix G. Minimum Spark Ignition Energies and Quenching Distances Indexes