This chapter is a critical survey of reaction rate coefficient data important in describing high-temperature combustion of H2, CO, and small hydrocarbons up to C4. A recommended reaction mechanism and rate coefficient set is presented. The approximate temperature range for this mechanism is from 1200 to 2500 K, which therefore excludes detailed consideration of cool flames, low-temperature ignition, or reactions of organic peroxides or peroxy radicals. Low-temperature rate-coefficient data are presented, however, when they contribute to defining or understanding high-temperature rate coefficients. Because our current knowledge of reaction kinetics is incomplete, this mechanism is inadequate for very fuel-rich conditions (see Warnatz et al., 1982). For the most part, reactions are considered only when their rates may be important for modeling combustion processes. This criterion eliminates considering many reactions among minor species present at concentrations so low that reactions of these species cannot play an essential part in combustion processes. The philosophy in evaluating the rate-coefficient data was to be selective rather than exhaustive: Recent results obtained with experimental methods capable of measuring isolated elementary reaction rate parameters directly were preferred, while results obtained using computer simulations of complex reacting systems were considered only when sensitivity to a particular elementary reaction was demonstrated or when direct measurements are not available. Theoretical results were not considered.

Rate Coefficients in the C/H/O System

Optimization and analysis of large chemical kinetic mechanisms using the solution mapping method—combustion of methane

Consideration of reaction mechanisms leading to pyrolytic carbon of different textures

Ensembles of classical trajectories are used to study collisional energy transfer in highly vibrationally excited CH4 for eight bath gases. Several simplifying assumptions for the CH4 + M interaction potential energy surface are tested against full dimensional direct dynamics trajectory calculations for M = He, Ne, and H2. The calculated energy transfer averages are confirmed to be sensitive to the shape of the repulsive wall of the intermolecular potential, with an exponential repulsive wall required for quantitative predictions. For the diatomic baths, the usual “separable pairwise” approximation for the interaction potential is unable to describe the orientation dependence of the interaction potential accurately, and the ambiguity in the resulting parametrizations contributes an additional uncertainty to the predicted energy transfer averages of 20–40%. On the other hand, the energy transfer averages are shown to be insensitive to the level of theory used to describe the intramolecular CH4 potential, w...

Theoretical Unimolecular Kinetics for CH4 + M ⇄ CH3 + H + M in Eight Baths, M = He, Ne, Ar, Kr, H2, N2, CO, and CH4

https://publikationen.bibliothek.kit.edu/1000056467/3940752

Hydrogen production via methane pyrolysis in a liquid metal bubble column reactor with a packed bed

The pyrolysis of methane has been studied in a static system at temperatures of 995, 1038, 1068, and 1103 K and pressures from 25 to 700 Torr. It was concluded that the initial stages of the reacti...

The Thermal Decomposition of Methane. I. Kinetics of the Primary Decompositionto C2H6 + H2; Rate Constant for the Homogeneous Unimolecular Dissociation of Methane and its Pressure Dependence

M. H. Back

Papers

The Thermal Decomposition of Methane. I. Kinetics of the Primary Decompositionto C2H6 + H2; Rate Constant for the Homogeneous Unimolecular Dissociation of Methane and its Pressure Dependence