This book differs from its out of print 1984 predecessorl primarily by lacking theoretical chapters on combustion modeling and elementary reaction rate coeffi­ cients. While noteworthy advances in these subjects have been made since 1984, it was decided to mention theory in this book only where appropriate in chap­ ters describing combustion chemistry itself. Otherwise, space limitation would have forced us to discuss only new developments in theoretical areas, thereby abandoning our goal of keeping this book readable by newcomers to the field of combustion modeling. Contemporary modeling and rate coefficient theory as applied to combustion deserve a book of their own. A second omission is a chapter devoted to reviewing the elementary reactions that contribute to the combustion chemistry of hydrogen, carbon monoxide, and hydrocarbon or alternate fuels. Readers looking for guidance to the current knowledge we have in this area will find a broad outline and extensive references to the review and archival literature in Chapter 1, where the essential features of combustion chemistry modeling are surveyed.

This book differs from its out of print 1984 predecessorl primarily by lacking theoretical chapters on combustion modeling and elementary reaction rate coefficients. While noteworthy advances in these subjects have been made since 1984, it was decided to mention theory in this book only where appropriate in chapters describing combustion chemistry itself. Otherwise, space limitation would have forced us to discuss only new developments in theoretical areas, thereby abandoning our goal of keeping this book readable by newcomers to the field of combustion modeling. Contemporary modeling and rate coefficient theory as applied to combustion deserve a book of their own.
A second omission is a chapter devoted to reviewing the elementary reactions that contribute to the combustion chemistry of hydrogen, carbon monoxide, and hydrocarbon or alternate fuels. Readers looking for guidance to the current knowledge we have in this area will find a broad outline and extensive references to the review and archival literature in Chapter 1, where the essential features of combustion chemistry modeling are surveyed.
The heart of this book is its chapters on the combustion chemistry of nitrogen, sulfur, and chlorine. Nitrogen and sulfur draw interest mostly because their oxides are the primary pollutants formed in combustion, chlorine because it is the prototype flame inhibitor and because incineration of toxic waste faces the challenge of reducing the concentrations of chlorine-containing organic compounds in waste streams to extremely low levels. It will be clear to all readers that while many molecular-level details have been discovered about the high-temperature chemistry of these elements, our ability to describe in combustion simulations what has been measured in combustion experiments is still limited by the incompleteness of our chemical understanding.
Like most basic combustion research, this book deals with what happens in the gas phase. Condensed phase chemistry relevant to explosives and propellants is not specifically addressed, although many elementary reactions relevant to that chemistry also play roles in gas-phase combustion. Two-phase combustion reactions, including formation and oxidation of soot, combustion of coal char and formation of inorganic ash, and the influence of chamber walls on nearby flames are likewise not described. These are certainly important chemical processes, but, aside from soot particle nucleation, modeling of two-phase combustion has so far been mostly limited to empirical descriptions that do not attempt to capture chemical detail in a fundamental way. On the other hand, there are some high temperature gas-phase reactions-such as chemiluminescence, ion formation, and reactions of metals-for which we do have molecular-level knowledge but which have remained at the periphery of combustion science. Readers interested in topics like these can readily gain entrance to the relatively limited literature 1 on them; thoughtful reading of Chapter I will provide all the background needed to place such special interests in context with the mainstream of combustion chemistry modeling.
Combustion Chemistry, W.C. Gardiner, Ed., Springer-Verlag, New York 1984.
Beginning with the biennial International Combustion Symposium volumes published by the Combustion Institute in Pittsburgh.
Much of the content found here can be supplemented with resources on the Internet and the World Wide Web. We have tried to include URLs for all of the relevant sites that we know about, but some have surely been overlooked and many new ones will be established before this book becomes obsolete. Despite the limited lifetimes and uncertain reliability of Internet resources, creators and users of combustion chemistry knowledge generally have such Internet-friendly personalities that we expect to see essentially all of the combustion chemistry database and most of the computational resources one needs to utilize it on-line before this book is out of print.
Austin, Texas William C. Gardiner, Jr.

Preface v

Contributors xiii

Chapter 1. Combustion Chemistry Modeling 1

Vitali V. Lissianski, Vladimir M. Zaman sky, and William C. Gardiner, Jr.

1.1. Introduction 1

      1.1.1 Terms used in dynamic modeling of chemical reaction 2

      1.1.2 Chain reactions 3

      1.1.3 Reaction rates, rate laws, and rate coefficients 5

      1.1.4 Model constraints 6

      1.1.5 Differential equations of chemical reaction without transport 8

      1.1.6 Methods of numerical integration 17

      1.1.7 Sensitivity and flux analysis of reaction profiles 17

1.2. Oxidation of hydrogen and carbon monoxide 21

      1.2.1 Hydrogen oxidation at high temperatures 21

      1.2.2 Role of peroxides at low temperatures 28

      1.2.3 Carbon monoxide oxidation 29

      1.2.4 Rate coefficients of the rate-limiting steps of H2 and CO oxidation 30

1.3. Hydrocarbon combustion chemistry 31

      1.3.1 General features of hydrocarbon oxidation 31

      1.3.2 Low- and intermediate-temperature oxidation 32

      1.3.3 High-temperature oxidation 33

      1.3.4 Combustion of higher hydrocarbons 40

1.4. Nitrogen, sulfur, and halogens in flames 42

      1.4.1 Oxidation of ammonia and hydrogen cyanide 42

      1.4.2 Formation and destruction of nitrogen oxides in flames 46

      1.4.3 Chemistry of NOx control methods 51

      1.4.4 Sulfur 61

      1.4.5 Halogens 62

1.5. Combustion of alternative fuels 67

      1.5.1 Methanol 67

      1.5.2 Ethanol 69

      1.5.3 Higher alcohols and MTBE 71

1.6. Combustion inhibitors 73

1.7. Combustion promoters 78

1.8. Reduced chemistry models of combustion 83

      1.8.1 One-step chemistry 84

      1.8.2 The steady-state approximation and global reaction models 84

      1.8.3 Empirically derived global mechanisms 86

      1.8.4 Automated mechanism reduction by sensitivity analysis 861.8.5 Generalized mechanisms: Combustion chemistry in outline form 87

      1.8.6 Local linearization and eigenvalue analysis 90

      1.8.7 Algebraic representation of databases

      generated from detailed models: Repro-models 92

      1.8.8 Chemical lumping methods 93

1.9. Resources for combustion chemistry modeling 94

      1.9.1 Elementary reaction rate coefficient data 95

      1.9.2 Validated reaction mechanisms 96

      1.9.3 Combustion modeling software 102

      1.9.4 Notes on the mechanism used in this chapter 103

1.10. References 104

Chapter 2. Combustion Chemistry of Nitrogen 125

Anthony M. Dean and Joseph W. Bozzelli

2.1. Introduction 125

2.2. Overview of nitrogen chemistry 126

      2.2.1 Thermal, or Zeldovich, NO 126

      2.2.2 Prompt, or Fenimore, NO 127

      2.2.3 The N20 pathway 127

      2.2.4 Fuel nitrogen 128

      2.2.5 The NNH mechanism 128

      2.2.6 Effects of temperature and pressure 129

      2.2.7 NO reduction 129

2.3. Unimolecular and chemically activated bimolecular reactions 130

      2.3.1 Unimolecular reactions 130

      2.3.2 Pressure-dependent bimolecular reactions 133

      2.3.3 Quantum Rice-Ramsperger-Kassel theory 133

      2.3.4 Implementation of QRRK theory 134

2.4. Analysis of hydrogen atom abstraction reactions 138

2.5. Updated rate coefficients for the HlN/O system 141

      2.5.1 0 + N2 → N + NO 141

      2.5.2 NO + Ar 2.5.2 NO + Ar → N + 0 + Ar 143

      2.5.3 N20 + Ar → N2 + 0 + Ar 143

      2.5.4 0 + N20 → Products 145

      2.5.5 NH3 + Ar → NH2 + H + Ar 148

      2.5.6 NH3 + H → NH2 + H2 148

      2.5.7 NH3 + OH → NH2 + H20 148

      2.5.8 NH3 + 0 → NH2 + OH 150

2.6. QRRK treatments 152

      2.6.1 H + NH2 → NH + H2 152

      2.6.2 H02 + NO → N02 + OH 155

      2.6.3 H + N20 → Products 158

      2.6.4 H + N20 → N2 + OH and H + N20 → HNNO 163

      2.6.5 H + N20 → NH + NO 165

      2.6.6 H + N20 → NNH + 0 166

      2.6.7 NH + NO → Products 166

      2.6.8 NH + 02 → Products 168

      2.6.9 NH2 + 02 → Products 174

      2.6.10 NH2 + H02 → Products 177

      2.6.11 NH2 + 0 → Products 179

      2.6.12 NH2 + OH → Products 181

      2.6.l3 NH2 + NH2 → Products 185

      2.6.14 NH2 + NO → Products 188

      2.6.15 CH3 + NO → Products 193

      2.6.16 CH3 + N → Products 201

      2.6.17 CH3 + NH2 → Products 206

      2.6.18 CH2 + N2 → Products 210

      2.6.19 3CH2 + NO → Products 213

      2.6.20 CH + N2 → Products 219

      2.6.21 CH + NO → Products 225

2.7. Other reactions of interest 230

      2.7.1 Reactions of N atoms 230

      2.7.2 Reactions ofNH 232

      2.7.3 Reactions of NNH 234

      2.7.4 Reactions of N2H2 240

      2.7.5 Reactions of H2NN 242

      2.7.6 Reactions of N2H3 245

      2.7.7 Reactions of N2H4 247

      2.7.8 Reactions of NO 248

      2.7.9 Reactions of N02 250

      2.7.10 Reactions of N20 251

      2.7.11 Reactions of HNO 252

      2.7.12 Reactions of NH20 256

      2.7.l3 Reactions of HNOH 258

      2.7.14 Reactions of IHNOO 260

      2.7.15 Reactions of HONO 261

      2.7.16 Reactions of HN02 261

      2.7.l7 Reactions of HCN 262

      2.7.18 Reactions of HNC 265

      2.7.19 Reactions of CN 265

      2.7.20 Reactions of H2CN 269

      2.7.21 Reactions of HCNH 271

      2.7.22 Reactions of HCNN 272

      2.7.23 Reactions of H2CNH 273

      2.7.24 Reactions of CH3NH 273

      2.7.25 Reactions of CH2NH2 274

      2.7.26 Reactions of CH3NH2 276

      2.7.27 Reactions of NCCN 276

      2.7.28 Reactions of NCO 277

      2.7.29 Reactions of HCNO 280

      2.7.30 Reactions of HOCN 281

      2.7.31 Reactions of HNCO 281

      2.7.32 Reactions of CH2NO 283

      2.7.33 Reactions of CH3NO 285

      2.7.34 Reactions of HON 286

      2.7.35 Reactions of HCOH 286

      2.7.36 Reactions of NH20H 287

      2.7.37 Reactions of NH2NO 287

      2.7.38 Reactions of H2NNHO 287

      2.7.39 Reactions of CINO 288

2.8. Illustrative modeling results 290

      2.8.1 Ammonia oxidation 291

      2.8.2 Kinetics of selective noncatalytic reduction of NO 298

      2.8.3 Fuel-rich ammonia flames 300

      2.8.4 Implications of the 0 + NNH reaction 305

      2.8.5 Nitrogen chemistry in hydrocarbon-air flames 310

      2.8.6 General conclusions from modeling tests 313

2.9. Summary 315

2.10. Acknowledgments 315

2.11. References 316

Chapter 3. Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds 343

Anthony J. Hynes and Paul H. Wine

3.1. Introduction 343

3.2. Sulfur emissions 344

3.3. Elementary reactions 344

      3.3.1 Reactions of atoms and radicals with sulfur-containing molecules 349

      3.3.2 Sulfur radical reactions 356

      3.3.3 Sulfuric acid formation 358

3.4. Basic chemistry of sulfur in combustion environments 359

      3.4.1 Hydrogen-oxygen flames 359

      3.4.2 Hydrocarbon flames 367

      3.4.3 Sulfur-nitrogen interactions 369

      3.4.4 Sodium-sulfur interactions 373

      3.4.5 Sulfur reaction studies in shock tubes 373

3.5. Thermochemistry of sulfur-containing compounds 375

3.6. Observations and conclusions 378

      3.6.1 Elementary reactions 378

      3.6.2 High-temperature studies 378

3.7. Acknowledgments 382

3.8. References 382

Chapter 4. Survey of Rate Coefficients in the C-H-CI-O System 389

Selim M. Senkan

4.1. Introduction 389

4.2. Electronic structure and thermochemistry 391

4.3. Characteristic features of elementary reactions of chlorine 394

4.4. Reaction mechanisms 397

4.5. Survey of elementary reactions 400

      4.5.1 Reactions ofH atoms 400

      4.5.2 Reactions of 0 atoms 408

      4.5.3 OH radical reactions 411

      4.5.4 Reactions of CI atoms 426

      4.5.5 Reactions ofCh 451

      4.5.6 Unimolecular and pressure-dependent bimolecular reactions 466

      4.5.7 Reactions of large molecules and radicals 467

4.6. Data gaps and suggestions for future work 467

4.7. Acknowledgments 477

4.8. References 477

Chapter 5. Ideal Gas Thermochemical Data for Combustion and Air Pollution Use 489

Alexander Burcat and William C. Gardiner, Jr.

5.1. Introduction 489

5.2. Thermochemical database 491

5.3. Sources of thermochemical data 491

5.4. Thermochemical polynomials 493

5.5. Calculation procedures 494

5.6. Accuracy of the database 495

5.7. Accuracy of standard enthalpies of formation 496

5.8. Other sources of thermochemical data 500

5.9. Format of the database 501

5.10. Conversion factors 504

5.11. Internet transfer of the database 504

5.12. References 505

5.13. Table of standard enthalpies of formation 510

Index 539

Contributors

Joseph W. Bozzelli, Department of Chemical Engineering and Chemistry, New Jersey Institute of Technology, Newark, New Jersey 07102, U.S.A.

Alexander Burcat, Department of Aeronautical Engineering, Technion-Israel Institute of Technology, Haifa 31000, Israel

Anthony M. Dean, Corporate Research Laboratory, Exxon Research and Engineering Company, Annandale, New Jersey 08801, U.S.A.

William C. Gardiner, Jr., Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, U.S.A.

Anthony J. Hynes, Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Sciences, University of Miami, Miami, Horida 33149, U.S.A.

Vitali V. Lissianski, GE Energy and Environmental Research Corporation, 18

Mason, Irvine, California 92618, U.S.A.

Selim M. Senkan, Department of Chemical Engineering, University of California, Los Angeles, California 90024, U.S.A.

Paul H. Wine, School of Chemistry and Biochemistry, School of Earth and Atmospheric Sciences, and Georgia Tech Research Institute, Georgia Institute of Technology, Atlanta, Georgia 30332, U.S.A.

Vladimir M. Zamansky, GE Energy and Environmental Research Corporation, 18

Mason, Irvine, California 92618, U.S.A.

W. C. GardinerJr.: Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, USA

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