Gas-Phase Combustion Chemistry (2^nd Ed., 2nd ed. 2000. Softcover reprint of the original 2nd ed. 2000)

Superseding Gardiner's "Combustion Chemistry", this is an updated, comprehensive coverage of those aspects of combustion chemistry relevant to gas-phase combustion of hydrocarbons. The book includes an extended discussion of air pollutant chemistry and aspects of combustion, and reviews elementary reactions of nitrogen, sulfur and chlorine compounds that are relevant to combustion. Methods of combustion modeling and rate coefficient estimation are presented, as well as access to databases for combustion thermochemistry and modeling.

1. Combustion Chemistry Modeling.- 1.1. Introduction.- 1.1.1 Terms used in dynamic modeling of chemical reaction.- 1.1.2 Chain reactions.- 1.1.3 Reaction rates, rate laws, and rate coefficients.- 1.1.4 Model constraints.- 1.1.5 Differential equations of chemical reaction without transport.- 1.1.6 Methods of numerical integration.- 1.1.7 Sensitivity and flux analysis of reaction profiles.- 1.2. Oxidation of hydrogen and carbon monoxide.- 1.2.1 Hydrogen oxidation at high temperatures.- 1.2.2 Role of peroxides at low temperatures.- 1.2.3 Carbon monoxide oxidation.- 1.2.4 Rate coefficients of the rate-limiting steps of H2and CO oxidation.- 1.3. Hydrocarbon combustion chemistry.- 1.3.1 General features of hydrocarbon oxidation.- 1.3.2 Low-and intermediate-temperature oxidation.- 1.3.3 High-temperature oxidation.- 1.3.4 Combustion of higher hydrocarbons.- 1.4. Nitrogen, sulfur, and halogens in flames.- 1.4.1 Oxidation of ammonia and hydrogen cyanide.- 1.4.2 Formation and destruction of nitrogen oxides in flames.- 1.4.3 Chemistry of NOxcontrol methods.- 1.4.4 Sulfur.- 1.4.5 Halogens.- 1.5. Combustion of alternative fuels.- 1.5.1 Methanol.- 1.5.2 Ethanol.- 1.5.3 Higher alcohols and MTBE.- 1.6. Combustion inhibitors.- 1.7. Combustion promoters.- 1.8. Reduced chemistry models of combustion.- 1.8.1 One-step chemistry.- 1.8.2 The steady-state approximation and global reaction models.- 1.8.3 Empirically derived global mechanisms.- 1.8.4 Automated mechanism reduction by sensitivity analysis.- 1.8.5 Generalized mechanisms: Combustion chemistry in outline form.- 1.8.6 Local linearization and eigenvalue analysis.- 1.8.7 Algebraic representation of databases generated from detailed models: Repro-models.- 1.8.8 Chemical lumping methods.- 1.9. Resources for combustion chemistry modeling.- 1.9.1 Elementary reaction rate coefficient data.- 1.9.2 Validated reaction mechanisms.- 1.9.3 Combustion modeling software.- 1.9.4 Notes on the mechanism used in this chapter.- 1.10. References.- 2. Combustion Chemistry of Nitrogen.- 2.1. Introduction.- 2.2. Overview of nitrogen chemistry.- 2.2.1 Thermal, or Zeldovich, NO.- 2.2.2 Prompt, or Fenimore, NO.- 2.2.3 The N2O pathway.- 2.2.4 Fuel nitrogen.- 2.2.5 The NNH mechanism.- 2.2.6 Effects of temperature and pressure.- 2.2.7 NO reduction.- 2.3. Unimolecular and chemically activated bimolecular reactions.- 2.3.1 Unimolecular reactions.- 2.3.2 Pressure-dependent bimolecular reactions.- 2.3.3 Quantum Rice—Ramsperger—Kassel theory.- 2.3.4 Implementation of QRRK theory.- 2.4. Analysis of hydrogen atom abstraction reactions.- 2.5. Updated rate coefficients for the H/N/O system.- 2.5.1 O + N2? N + NO.- 2.5.2 NO + Ar ? N + O + Ar.- 2.5.3 N2O + Ar ? N2+ O + Ar.- 2.5.4 O + N2O ? Products.- 2.5.5 NH3+ Ar ? NH2+ H + Ar.- 2.5.6 NH3+ H ? NH2+ H2.- 2.5.7 NH3+ OH ? NH2+ H2O.- 2.5.8 NH3+ O ? NH2+ OH.- 2.6. QRRK treatments.- 2.6.1 H + NH2? NH + H2.- 2.6.2 HO2+ NO ? NO2+ OH.- 2.6.3 H + N2O ? Products.- 2.6.4 H + N2O ? N2+ OH and H + N2O ? HNNO.- 2.6.5 H + N2O ? NH + NO.- 2.6.6 H + N2O ? NNH + O.- 2.6.7 NH + NO ? Products.- 2.6.8 NH + O2? Products.- 2.6.9 NH2+ O2? Products.- 2.6.10 NH2+ HO2? Products.- 2.6.11 NH2+ O ? Products.- 2.6.12 NH2+ OH ? Products.- 2.6.13 NH2+ NH2? Products.- 2.6.14 NH2+ NO ? Products.- 2.6.15 CH3+ NO ? Products.- 2.6.16 CH3+ N ? Products.- 2.6.17 CH3+ NH2? Products.- 2.6.18 CH2+ N2? Products.- 2.6.193CH2+ NO ? Products.- 2.6.20 CH + N2? Products.- 2.6.21 CH + NO ? Products.- 2.7. Other reactions of interest.- 2.7.1 Reactions of N atoms.- 2.7.2 Reactions of NH.- 2.7.3 Reactions of NNH.- 2.7.4 Reactions of N2H2.- 2.7.5 Reactions of H2NN.- 2.7.6 Reactions of N2H3.- 2.7.7 Reactions of N2H4.- 2.7.8 Reactions of NO.- 2.7.9 Reactions of NO2.- 2.7.10 Reactions of N2O.- 2.7.11 Reactions of HNO.- 2.7.12 Reactions of NH2O.- 2.7.13 Reactions of HNOH.- 2.7.14 Reactions of1HNOO.- 2.7.15 Reactions of HONO.- 2.7.16 Reactions of HNO2.- 2.7.17 Reactions of HCN.- 2.7.18 Reactions of HNC.- 2.7.19 Reactions of CN.- 2.7.20 Reactions of H2CN.- 2.7.21 Reactions of HCNH.- 2.7.22 Reactions of HCNN.- 2.7.23 Reactions of H2CNH.- 2.7.24 Reactions of CH3NH.- 2.7.25 Reactions of CH2NH2.- 2.7.26 Reactions of CH3NH2.- 2.7.27 Reactions of NCCN.- 2.7.28 Reactions of NCO.- 2.7.29 Reactions of HCNO.- 2.7.30 Reactions of HOCN.- 2.7.31 Reactions of HNCO.- 2.7.32 Reactions of CH2NO.- 2.7.33 Reactions of CH3NO.- 2.7.34 Reactions of HON.- 2.7.35 Reactions of HCOH.- 2.7.36 Reactions of NH2OH.- 2.7.37 Reactions of NH2NO.- 2.7.38 Reactions of H2NNHO.- 2.7.39 Reactions of CINO.- 2.8. Illustrative modeling results.- 2.8.1 Ammonia oxidation.- 2.8.2 Kinetics of selective noncatalytic reduction of NO.- 2.8.3 Fuel-rich ammonia flames.- 2.8.4 Implications of the O + NNH reaction.- 2.8.5 Nitrogen chemistry in hydrocarbon—air flames.- 2.8.6 General conclusions from modeling tests.- 2.9. Summary.- 2.10. Acknowledgments.- 2.11. References.- 3. Kinetics and Mechanisms of the Oxidation of Gaseous Sulfur Compounds.- 3.1. Introduction.- 3.2. Sulfur emissions.- 3.3. Elementary reactions.- 3.3.1 Reactions of atoms and radicals with sulfur-containing molecules.- 3.3.2 Sulfur radical reactions.- 3.3.3 Sulfuric acid formation.- 3.4. Basic chemistry of sulfur in combustion environments.- 3.4.1 Hydrogen—oxygen flames.- 3.4.2 Hydrocarbon flames.- 3.4.3 Sulfur—nitrogen interactions.- 3.4.4 Sodium—sulfur interactions.- 3.4.5 Sulfur reaction studies in shock tubes.- 3.5. Thermochemistry of sulfur-containing compounds.- 3.6. Observations and conclusions.- 3.6.1 Elementary reactions.- 3.6.2 High-temperature studies.- 3.7. Acknowledgments.- 3.8. References.- 4. Survey of Rate Coefficients in the C-H-Cl-O System.- 4.1. Introduction.- 4.2. Electronic structure and thermochemistry.- 4.3. Characteristic features of elementary reactions of chlorine.- 4.4. Reaction mechanisms.- 4.5. Survey of elementary reactions.- 4.5.1 Reactions of H atoms.- 4.5.2 Reactions of O atoms.- 4.5.3 OH radical reactions.- 4.5.4 Reactions of Cl atoms.- 4.5.5 Reactions of Cl2.- 4.5.6 Unimolecular and pressure-dependent bimolecular reactions.- 4.5.7 Reactions of large molecules and radicals.- 4.6. Data gaps and suggestions for future work.- 4.7. Acknowledgments.- 4.8. References.- 5. Ideal Gas Thermochemical Data for Combustion and Air Pollution Use.- 5.1. Introduction.- 5.2. Thermochemical database.- 5.3. Sources of thermochemical data.- 5.4. Thermochemical polynomials.- 5.5. Calculation procedures.- 5.6. Accuracy of the database.- 5.7. Accuracy of standard enthalpies of formation.- 5.8. Other sources of thermochemical data.- 5.9. Format of the database.- 5.10. Conversion factors.- 5.11. Internet transfer of the database.- 5.12. References.- 5.13. Table of standard enthalpies of formation.