CHAPTER 1 Chemical thermodynamics and flame temperatures 1
1.1 Introduction 1
1.2 Heats of Reaction and Formation 1
1.3 Free Energy and the Equilibrium Constants 8
1.4 Flame Temperature Calculations 16
1.4.1 Analysis 16
1.4.2 Practical Considerations 21
1.5 Sub and Supersonic Combustion Thermodynamics 31
1.5.1 Comparisons 31
1.5.2 Stagnation Pressure Considerations 32
Problems 34
References 39
CHAPTER 2 Chemical kinetics 41
2.1 Introduction 41
2.2 Rates of Reactions and their Temperature Dependence 41
2.2.1 The Arrhenius Rate Expression 43
2.2.2 Transition State and Recombination Rate Theories 45
2.3 Simultaneous Interdependent Reactions 50
2.4 Chain Reactions 51
2.5 Pseudo-First-Order Reactions and the “Falloff” Range 54
2.6 The Partial Equilibrium Assumption 57
2.7 Pressure Effect in Fractional Conversion 58
2.8 Chemical Kinetics of Large Reaction Mechanisms 59
2.8.1 Sensitivity Analysis 60
2.8.2 Rate-of-Production Analysis 62
2.8.3 Coupled Thermal and Chemical Reacting Systems 62
2.8.4 Mechanism Simplification 64
Problems 65
References 69
CHAPTER 3 Explosive and general oxidative characteristics of fuels 71
3.1 Introduction 71
3.2 Chain Branching Reactions and Criteria for Explosion 71
3.3 Explosion Limits and Oxidation Characteristics of Hydrogen 78
3.4 Explosion Limits and Oxidation Characteristics of Carbon Monoxide 86
3.5 Explosion Limits and Oxidation Characteristics of Hydrocarbons 91
3.5.1 Organic Nomenclature 92
3.5.2 Explosion Limits 96
3.5.3 “Low-Temperature” Hydrocarbon Oxidation Mechanisms 99
3.6 The Oxidation of Aldehydes 105
3.7 The Oxidation of Methane 106
3.7.1 Low-Temperature Mechanism 106
3.7.2 High-Temperature Mechanism 108
3.8 The Oxidation of Higher-Order Hydrocarbons 111
3.8.1 Aliphatic Hydrocarbons 111
3.8.2 Alcohols 120
3.8.3 Aromatic Hydrocarbons 123
3.8.4 Supercritical Effects 132
3.8.5 Biofuels 135
Problems 141
References 143
CHAPTER 4 Flame phenomena in premixed combustible gases 147
4.1 Introduction 147
4.2 Laminar Flame Structure 151
4.3 Laminar Flame Speed 153
4.3.1 Theory of Mallard and Le Chatelier 155
4.3.2 Theory of Zeldovich，Frank-Kamenetskii，and Semenov 160
4.3.3 Comprehensive Theory and Laminar Flame Structure Analysis 166
4.3.4 Laminar Flame and Energy Equation 174
4.3.5 Flame Speed Measurements 174
4.3.6 Experimental Results—Physical and Chemical Effects 182
4.4 Stability Limits of Laminar Flames 189
4.4.1 Flammability Limits 189
4.4.2 Quenching Distance 197
4.4.3 Flame Stabilization （Low Velocity） 198
4.4.4 Stability Limits and Design 205
4.5 Flame Progagation through Stratified Combustible Mixtures 208
4.6 Turbulent Reacting Flows and Turbulent Flames 210
4.6.1 Rate of Reaction in a Turbulent Field 212
4.6.2 Regimes of Turbulent Reacting Flows 215
4.6.3 Turbulent Flame Speed 227
4.7 Stirred Reactor Theory 231
4.8 Flame Stabilization in High-Velocity Streams 235
4.9 Combustion in Small Volumes 245
Problems 248
References 251
CHAPTER 5 Detonation 255
5.1 Introduction 255
5.1.1 Premixed and Diffusion Flames 255
5.1.2 Explosion，Deflagration，and Detonation 255
5.1.3 The Onset of Detonation 256
5.2 Detonation Phenomena 258
5.3 Hugoniot Relations and the Hydrodynamic Theory of Detonations 259
5.3.1 Characterization of the Hugoniot Curve and the Uniqueness of the Chapman Jouguet Point 260
5.3.2 Determination of the Speed of Sound in the Burned Gases for Conditions above the C-J Point 269
5.3.3 Calculation of the Detonation Velocity 273
5.4 Comparison of Detonation Velocity Calculations with Experimental Results 277
5.5 The ZND Structure of Detonation Waves 284
5.6 The Structure of the Cellular Detonation Front and Other Detonation Phenomena Parameters 288
5.6.1 The Cellular Detonation Front 288
5.6.2 The Dynamic Detonation Parameters 292
5.6.3 Detonation Limits 293
5.7 Detonations in Nongaseous Media 296
Problems 297
References 298
CHAPTER 6 Diffusion flames 301
6.1 Introduction 301
6.2 Gaseous Fuel Jets 301
6.2.1 Appearance 302
6.2.2 Structure 306
6.2.3 Theoretical Considerations 309
6.2.4 The Burke-Schumann Development 312
6.2.5 Conserved Scalars and Mixture Fraction 319
6.2.6 Turbulent Fuel Jets 320
6.3 Burning of Condensed Phases 322
6.3.1 General Mass Burning Considerations and the Evaporation Coefficient 323
6.3.2 Single Fuel Droplets in Quiescent Atmospheres 327
6.4 Burning of Droplet Clouds 350
6.5 Burning in Convective Atmospheres 351
6.5.1 The Stagnant Film Case 351
6.5.2 The Longitudinally Burning Surface 353
6.5.3 The Flowing Droplet Case 355
6.5.4 Burning Rates of Plastics：The Small B Assumption and Radiation Effects 357
Problems 359
References 361
CHAPTER 7 Ignition 363
7.1 Concepts 363
7.2 Chain Spontaneous Ignition 366
7.3 Thermal Spontaneous Ignition 368
7.3.1 Semenov Approach of Thermal Ignition 368
7.3.2 Frank-Kamenetskii Theory of Thermal Ignition 373
7.4 Forced Ignition 378
7.4.1 Spark Ignition and Minimum Ignition Energy 379
7.4.2 Ignition by Adiabatic Compression and Shock Waves 384
7.5 Other Ignition Concepts 385
7.5.1 Hypergolicity and Pyrophoricity 386
7.5.2 Catalytic Ignition 389
Problems 390
References 391
CHAPTER 8 Environmental combustion considerations 393
8.1 Introduction 393
8.2 The Nature of Photochemical Smog 394
8.2.1 Primary and Secondary Pollutants 395
8.2.2 The Effect of NOx 395
8.2.3 The Effect of SOx 398
8.3 Formation and Reduction of Nitrogen Oxides 400
8.3.1 Structure of Nitrogen Oxides 402
8.3.2 Effect of Flame Structure 403
8.3.3 Reaction Mechanisms of Oxides of Nitrogen 403
8.3.4 Reduction of NO x 419
8.4 SOx Emissions 424
8.4.1 Product Composition and Structure of Sulfur Compounds 425
8.4.2 Oxidative Mechanisms of Sulfur Fuels 426
8.5 Particulate Formation 438
8.5.1 Characteristics of Soot 439
8.5.2 Soot Formation Processes 440
8.5.3 Experimental Systems and Soot Formation 441
8.5.4 Sooting Tendencies 443
8.5.5 Detailed Structure of Sooting Flames 455
8.5.6 Chemical Mechanisms of Soot Formation 460
8.5.7 Influence of Physical and Chemical Parameters on Soot Formation 463
8.6 Stratospheric Ozone 466
8.6.1 The HOx Catalytic Cycle 467
8.6.2 The NOx Catalytic Cycle 468
8.6.3 The ClOx Catalytic Cycle 470
Problems 471
References 472
CHAPTER 9 Combustion of nonvolatile fuels 477
9.1 Carbon Char，Soot，and Metal Combustion 477
9.2 Metal Combustion Thermodynamics 478
9.2.1 The Criterion for Vapor-Phase Combustion 478
9.2.2 Thermodynamics of Metal-Oxygen Systems 478
9.2.3 Thermodynamics of Metal-Air Systems 491
9.2.4 Combustion Synthesis 495
9.3 Diffusional Kinetics 501
9.4 Diffusion-Controlled Burning Rate 503
9.4.1 Burning of Metals in Nearly Pure Oxygen 504
9.4.2 Burning of Small Particles—Diffusion versus Kinetic Limits 506
9.4.3 The Burning of Boron Particles 510
9.4.4 Carbon Particle Combustion （C.R.Shaddix） 511
9.5 Practical Carbonaceous Fuels （C.R.Shaddix） 514
9.5.1 Devolatilization 514
9.5.2 Char Combustion 519
9.5.3 Pulverized Coal Char Oxidation 520
9.5.4 Gasification and Oxycombustion 522
9.6 Soot Oxidation （C.R.Shaddix） 527
9.7 Catalytic Combustion 530
Problems 534
References 534
Appendixes 537
Appendix A：Thermochemical data and conversion factors 539
Appendix B：Adiabatic flame temperatures of hydrocarbons 651
Appendix C：Specific reaction rate constants 655
Appendix D：Bond dissociation energies of hydrocarbons 681
Appendix E：Flammability limits in air 689
Appendix F：Laminar flame speeds 697
Appendix G：Spontaneous ignition temperature data 705
Appendix H：Minimum spark ignition energies and quenching distances 731
Appendix I：Programs for combustion kinetics 735
Index 747