Low-temperature Combustion and Autoignition

Chapter and main section headings: Introduction. Basic Chemistry of Combustion. Historical perspective. Characteristics of low-temperature combustion. Computer modelling and associated problems. Overview of alkane oxidation. Review of experimental methods for establishing mechanisms and determining rate constants. Primary initiation reactions. Propagation reaction X + RH → XH + R (2). Homolysis of alkyl radicals. The reaction of alkyl radicals with O2. Reactions of RO2 radicals. Reactions of QOOH and QOOHO2 radicals. Oxidation chemistry of CH3 radicals. Reactions of alkoxy radicals. Branching reactions. Oxidation of cyclic alkanes. Oxidation of alkenes. Atom and radical addition to alkenes. Oxidation of oxygenated compounds. Oxidation of aromatic compounds. Summarizing remarks. References. Elementary Reactions. Introduction. Reaction initiation. Abstraction reactions. Radical decomposition reactions. Radical recombination and association reactions. R +O2 &rlarr2; RO2. Peroxy radical isomerization. Theoretical and dynamical studies of the hydrogen/oxygen system. References. Kinetics Databases. Data for combustion modelling. Primary sources of kinetic data: the need for evaluation. Evaluation of kinetic data. Interpolation, extrapolation and estimation procedures. Data sources for modelling. References. Mathematical Tools for the Construction, Investigation and Reduction of Combustion Mechanisms. Introduction. Notation. The construction of combustion mechanisms. Numerical investigation of complex models. Sensitivity and uncertainty analysis. Mechanism reduction without time-scale analysis. Formal lumping procedures. Reduction based on the investigation of time-scales. Approximate lumping in systems with time-scale separation. Fitted kinetic models. Conclusions and future directions. Global Behaviour in the Oxidation of Hydrogen, Carbon Monoxide and Simple Hydrocarbons. Introduction. Notation. Non-linearity and feedback in chemical kinetics: stoichiometry and elementary steps. Chemical feedback: branched-chain ignition. Thermal feedback: ignition, extinction and singularity theory. Thermokinetic feedback: oscillations and local stability analysis. The H2 + O2 reaction: p-Ta ignition limits in closed vessels. Flow reactor studies of the H2 + O2 reaction. Complexity in the oscillatory ignition region. Mechanistic modelling of complexity in the H2 + O2 reaction. The CO + O2 reaction. Hydrocarbon oxidation. Conclusions and future directions. References. Experimental and Numerical Studies of Oxidation Chemistry and Spontaneous Ignition Phenomena. Introduction. Measurements of reaction rate and its dependence on experimental conditions. Experimental methods. Global combustion phenomena associated with hydrocarbon oxidation. Product distributions during hydrocarbon oxidation and its kinetic interpretation. Detailed numerical modelling of alkane oxidation and spontaneous ignition. Conclusions. References. Appendix. Autoignition in Spark-ignition Engines. Introduction. Fuels for spark-ignition engines. Chemical modelling of autoignition. Combustion in engines. Autoignition in engines: modelling and experiments. Development of pressure pulses and knock. Conclusions. References. Author Index. Subject Index.