Throughout its previous four editions, Combustion has made a very complex subject both enjoyable and understandable to its student readers and a pleasure for instructors to teach. With its clearly articulated physical and chemical processes of flame combustion and smooth, logical transitions to engineering applications, this new edition continues that tradition. Greatly expanded end-of-chapter problem sets and new areas of combustion engineering applications make it even easier for students to grasp the significance of combustion to a wide range of engineering practice, from transportation to energy generation to environmental impacts. Combustion engineering is the study of rapid energy and mass transfer usually through the common physical phenomena of flame oxidation. It covers the physics and chemistry of this process and the engineering applications-including power generation in internal combustion automobile engines and gas turbine engines. Renewed concerns about energy efficiency and fuel costs, along with continued concerns over toxic and particulate emissions, make this a crucial area of engineering.* New chapter on new combustion concepts and technologies, including discussion on nanotechnology as related to combustion, as well as microgravity combustion, microcombustion, and catalytic combustion-all interrelated and discussed by considering scaling issues (e.g., length and time scales)* New information on sensitivity analysis of reaction mechanisms and generation and application of reduced mechanisms* Expanded coverage of turbulent reactive flows to better illustrate real-world applications* Important new sections on stabilization of diffusion flames-for the first time, the concept of triple flames will be introduced and discussed in the context of diffusion flame stabilization
Preface xv
Chapter 1 Chemical thermodynamics and flame 1 (40)
temperatures
1.1 Introduction 1 (1)
1.2 Heats of Reaction and Formation 1 (7)
1.3 Free Energy and the Equilibrium Constants 8 (8)
1.4 Flame Temperature Calculations 16 (15)
1.4.1 Analysis 16 (5)
1.4.2 Practical Considerations 21 (10)
1.5 Sub and Supersonic Combustion 31 (3)
Thermodynamics
1.5.1 Comparisons 31 (1)
1.5.2 Stagnation Pressure Considerations 32 (2)
Problems 34 (5)
References 39 (2)
Chapter 2 Chemical kinetics 41 (30)
2.1 Introduction 41 (1)
2.2 Rates of Reactions and their Temperature 41 (9)
Dependence
2.2.1 The Arrhenius Rate Expression 43 (2)
2.2.2 Transition State and Recombination 45 (5)
Rate Theories
2.3 Simultaneous Interdependent Reactions 50 (1)
2.4 Chain Reactions 51 (3)
2.5 Pseudo-First-Order Reactions and the 54 (3)
"Falloff" Range
2.6 The Partial Equilibrium Assumption 57 (1)
2.7 Pressure Effect in Fractional Conversion 58 (1)
2.8 Chemical Kinetics of Large Reaction 59 (6)
Mechanisms
2.8.1 Sensitivity Analysis 60 (2)
2.8.2 Rate-of-Production Analysis 62 (1)
2.8.3 Coupled Thermal and Chemical Reacting 62 (2)
Systems
2.8.4 Mechanism Simplification 64 (1)
Problems 65 (4)
References 69 (2)
Chapter 3 Explosive and general oxidative 71 (76)
characteristics of fuels
3.1 Introduction 71 (1)
3.2 Chain Branching Reactions and Criteria 71 (7)
for Explosion
3.3 Explosion Limits and Oxidation 78 (8)
Characteristics of Hydrogen
3.4 Explosion Limits and Oxidation 86 (5)
Characteristics of Carbon Monoxide
3.5 Explosion Limits and Oxidation 91 (14)
Characteristics of Hydrocarbons
3.5.1 Organic Nomenclature 92 (4)
3.5.2 Explosion Limits 96 (3)
3.5.3 "Low-Temperature" Hydrocarbon 99 (6)
Oxidation Mechanisms
3.6 The Oxidation of Aldehydes 105(1)
3.7 The Oxidation of Methane 106(5)
3.7.1 Low-Temperature Mechanism 106(2)
3.7.2 High-Temperature Mechanism 108(3)
3.8 The Oxidation of Higher-Order Hydrocarbons 111(30)
3.8.1 Aliphatic Hydrocarbons 111(9)
3.8.2 Alcohols 120(3)
3.8.3 Aromatic Hydrocarbons 123(9)
3.8.4 Supercritical Effects 132(3)
3.8.5 Biofuels 135(6)
Problems 141(2)
References 143(4)
Chapter 4 Flame phenomena in premixed 147(108)
combustible gases
4.1 Introduction 147(4)
4.2 Laminar Flame Structure 151(2)
4.3 Laminar Flame Speed 153(36)
4.3.1 Theory of Mallard and Le Chatelier 155(5)
4.3.2 Theory of Zeldovich, 160(6)
Frank-Kamenetskii, and Semenov
4.3.3 Comprehensive Theory and Laminar 166(8)
Flame Structure Analysis
4.3.4 Laminar Flame and Energy Equation 174(1)
4.3.5 Flame Speed Measurements 174(8)
4.3.6 Experimental Results猶hysical and 182(7)
Chemical Effects
4.4 Stability Limits of Laminar Flames 189(19)
4.4.1 Flammability Limits 189(8)
4.4.2 Quenching Distance 197(1)
4.4.3 Flame Stabilization (Low Velocity) 198(7)
4.4.4 Stability Limits and Design 205(3)
4.5 Flame Progagation through Stratified 208(2)
Combustible Mixtures
4.6 Turbulent Reacting Flows and Turbulent 210(21)
Flames
4.6.1 Rate of Reaction in a Turbulent Field 212(3)
4.6.2 Regimes of Turbulent Reacting Flows 215(12)
4.6.3 Turbulent Flame Speed 227(4)
4.7 Stirred Reactor Theory 231(4)
4.8 Flame Stabilization in High-Velocity 235(10)
Streams
4.9 Combustion in Small Volumes 245(3)
Problems 248(3)
References 251(4)
Chapter 5 Detonation 255(46)
5.1 Introduction 255(3)
5.1.1 Premixed and Diffusion Flames 255(1)
5.1.2 Explosion, Deflagration, and 255(1)
Detonation
5.1.3 The Onset of Detonation 256(2)
5.2 Detonation Phenomena 258(1)
5.3 Hugoniot Relations and the Hydrodynamic 259(18)
Theory of Detonations
5.3.1 Characterization of the Hugoniot 260(9)
Curve and the Uniqueness of the Chapman
Jouguet Point
5.3.2 Determination of the Speed of Sound 269(4)
in the Burned Gases for Conditions above
the C憂 Point
5.3.3 Calculation of the Detonation Velocity 273(4)
5.4 Comparison of Detonation Velocity 277(7)
Calculations with Experimental Results
5.5 The ZND Structure of Detonation Waves 284(4)
5.6 The Structure of the Cellular Detonation 288(8)
Front and Other Detonation Phenomena
Parameters
5.6.1 The Cellular Detonation Front 288(4)
5.6.2 The Dynamic Detonation Parameters 292(1)
5.6.3 Detonation Limits 293(3)
5.7 Detonations in Nongaseous Media 296(1)
Problems 297(1)
References 298(3)
Chapter 6 Diffusion flames 301(62)
6.1 Introduction 301(1)
6.2 Gaseous Fuel Jets 301(21)
6.2.1 Appearance 302(4)
6.2.2 Structure 306(3)
6.2.3 Theoretical Considerations 309(3)
6.2.4 The Burke祐chumann Development 312(7)
6.2.5 Conserved Scalars and Mixture Fraction 319(1)
6.2.6 Turbulent Fuel Jets 320(2)
6.3 Burning of Condensed Phases 322(28)
6.3.1 General Mass Burning Considerations 323(4)
and the Evaporation Coefficient
6.3.2 Single Fuel Droplets in Quiescent 327(23)
Atmospheres
6.4 Burning of Droplet Clouds 350(1)
6.5 Burning in Convective Atmospheres 351(8)
6.5.1 The Stagnant Film Case 351(2)
6.5.2 The Longitudinally Burning Surface 353(2)
6.5.3 The Flowing Droplet Case 355(2)
6.5.4 Burning Rates of Plastics: The Small 357(2)
B Assumption and Radiation Effects
Problems 359(2)
References 361(2)
Chapter 7 Ignition 363(30)
7.1 Concepts 363(3)
7.2 Chain Spontaneous Ignition 366(2)
7.3 Thermal Spontaneous Ignition 368(10)
7.3.1 Semenov Approach of Thermal Ignition 368(5)
7.3.2 Frank-Kamenetskii Theory of Thermal 373(5)
Ignition
7.4 Forced Ignition 378(7)
7.4.1 Spark Ignition and Minimum Ignition 379(5)
Energy
7.4.2 Ignition by Adiabatic Compression and 384(1)
Shock Waves
7.5 Other Ignition Concepts 385(5)
7.5.1 Hypergolicity and Pyrophoricity 386(3)
7.5.2 Catalytic Ignition 389(1)
Problems 390(1)
References 391(2)
Chapter 8 Environmental combustion 393(84)
considerations
8.1 Introduction 393(1)
8.2 The Nature of Photochemical Smog 394(6)
8.2.1 Primary and Secondary Pollutants 395(1)
8.2.2 The Effect of NOx 395(3)
8.2.3 The Effect of SOx 398(2)
8.3 Formation and Reduction of Nitrogen Oxides 400(24)
8.3.1 Structure of Nitrogen Oxides 402(1)
8.3.2 Effect of Flame Structure 403(1)
8.3.3 Reaction Mechanisms of Oxides of 403(16)
Nitrogen
8.3.4 Reduction of NOx 419(5)
8.4 SO, Emissions 424(14)
8.4.1 Product Composition and Structure of 425(1)
Sulfur Compounds
8.4.2 Oxidative Mechanisms of Sulfur Fuels 426(12)
8.5 Particulate Formation 438(28)
8.5.1 Characteristics of Soot 439(1)
8.5.2 Soot Formation Processes 440(1)
8.5.3 Experimental Systems and Soot 441(2)
Formation
8.5.4 Sooting Tendencies 443(12)
8.5.5 Detailed Structure of Sooting Flames 455(5)
8.5.6 Chemical Mechanisms of Soot Formation 460(3)
8.5.7 Influence of Physical and Chemical 463(3)
Parameters on Soot Formation
8.6 Stratospheric Ozone 466(5)
8.6.1 The HOx Catalytic Cycle 467(1)
8.6.2 The NOx Catalytic Cycle 468(2)
8.6.3 The ClOx Catalytic Cycle 470(1)
Problems 471(1)
References 472(5)
Chapter 9 Combustion of nonvolatile fuels 477(60)
9.1 Carbon Char, Soot, and Metal Combustion 477(1)
9.2 Metal Combustion Thermodynamics 478(23)
9.2.1 The Criterion for Vapor-Phase 478(1)
Combustion
9.2.2 Thermodynamics of Metal涌xygen Systems 478(13)
9.2.3 Thermodynamics of Metal輸ir Systems 491(4)
9.2.4 Combustion Synthesis 495(6)
9.3 Diffusional Kinetics 501(2)
9.4 Diffusion-Controlled Burning Rate 503(11)
9.4.1 Burning of Metals in Nearly Pure 504(2)
Oxygen
9.4.2 Burning of Small Particles優iffusion 506(4)
versus Kinetic Limits
9.4.3 The Burning of Boron Particles 510(1)
9.4.4 Carbon Particle Combustion (C.R. 511(3)
Shaddix)
9.5 Practical Carbonaceous Fuels (C.R. 514(13)
Shaddix)
9.5.1 Devolatilization 514(5)
9.5.2 Char Combustion 519(1)
9.5.3 Pulverized Coal Char Oxidation 520(2)
9.5.4 Gasification and Oxycombustion 522(5)
9.6 Soot Oxidation (C.R. Shaddix) 527(3)
9.7 Catalytic Combustion 530(4)
Problems 534(1)
References 534(3)
Appendixes 537(210)
Appendix A Thermochemical data and conversion 539(112)
factors
Appendix B Adiabatic flame temperatures of 651(4)
hydrocarbons
Appendix C Specific reaction rate constants 655(26)
Appendix D Bond dissociation energies of 681(8)
hydrocarbons
Appendix E Flammability limits in air 689(8)
Appendix F Laminar flame speeds 697(8)
Appendix G Spontaneous ignition temperature 705(26)
data
Appendix H Minimum spark ignition energies 731(4)
and quenching distances
Appendix I Programs for combustion kinetics 735(12)
Index 747
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