Detailed chemical kinetic models for the combustion of hydrocarbon fuels

Formation of polycyclic aromatic hydrocarbons and soot in fuel-rich oxidation of methane in a laminar flow reactor

The chemical kinetics of the pyrolysis of the hydrocarbons ethylene, acetylene, and propylene are modeled in detail under conditions relevant to the chemical vapor deposition of pyrolytic carbon. A mechanism that consisted of 227 species and 827 reactions (most of which are reversible) is developed and computed using a software package designed for computing time-dependent homogeneous reaction systems. Experimental results used for model validation are obtained using a vertical flow reactor at 900 °C, pressures of 2−15 kPa, and residence times of up to 1.6 s. The products are analyzed using on-line and off-line gas chromatography. Computational and experimental results are compared for more than 30 products, including hydrogen, small hydrocarbons (ranging from methane to C4 species), and aromatic hydrocarbons (ranging from benzene to coronene). The resulting reaction model predicts the profiles of the major pyrolysis products (mole fractions of >10-2) of the three hydrocarbons, as a function of both resid...

Detailed Kinetic Modeling of Gas-Phase Reactions in the Chemical Vapor Deposition of Carbon from Light Hydrocarbons

The high-temperature kinetics of 1,3-butadiene oxidation was examined with detailed kinetic modeling. To facilitate model validation, flow reactor experiments were carried out for 1,3-butadiene pyrolysis and oxidation over the temperature range 1035–1185 K and at atmospheric pressure, extending similar experiments found in the literature to a wider range of equivalence ratio and temperature. The kinetic model was compiled on the basis of an extensive review of literature data and thermochemical considerations. The model was critically validated against a range of experimental data. It is shown that the kinetic model compiled in this study is capable of closely predicting a wide range of high-temperature oxidation and combustion responses. Based on this model, three separate pathways were identified for 1,3-butadiene oxidation, with the chemically activated reaction of H· and 1,3-butadiene to produce ethylene and the vinyl radical being the most important channel over all experimental conditions. The remaining uncertainty in the butadiene chemistry is also discussed. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 589–614, 2000

http://ignis.usc.edu/Mechanisms/C4H6/C4H6.pdf

Detailed kinetic modeling of 1,3‐butadiene oxidation at high temperatures

A novel route for PAH growth in HACA based mechanisms

The thermal isomerization and decomposition of 2-C 4 H 6 behind reflected shock wave with 1100<T 5 <1600 K and 1.6×10 -5 <ρ 5 <2.1×10 -5 mol/cm 3 were studied by UV kinetic absorption spectroscopy, IR laser kinetic absorption spectroscopy, and gas-chromatographic analysis of reaction products. The major products of the pyrolysis were 1,2-butadiene, 1,3-butadiene, CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , allene, propyne, C 4 H 2 , vinylacetylene, and benzene

Thermal isomerization and decomposition of 2-butyne in shock waves

Pyrolysis of n-pentane, n-hexane and n-heptane in a single pulse shock tube

The thermal decomposition of vinylacetylene (C4H4) was studied behind reflected shock waves using both a single-pulse method (reaction time between 0.8 and 3.3 ms) and a time-resolved UV-absorption method (230 nm). The studies were done over the temperature range of 1170–1690 K at the total pressure range of 1.3–2.3 atm. The mechanism was used to interpret both the early and late stages of vinylacetylene decomposition at the high temperatures. It was confirmed that C4H4 dissociation proceeded through the following three channels. 






The rate constant expression of reaction (1) was determined as k1 = 6.3 × 1013 exp(−87.1 kcal/RT) s−1. The rate constants of the succeeding reactions (chain reaction, C4H4 + H i-C4H3 + H2 and C4H4 + H C2H2 + C2H3 and decomposition reactions of free radicals, i-C4H3 + M C4H2 + H + M) were confirmed or estimated. © John Wiley & Sons, Inc.

Thermal decomposition of vinylacetylene in shock waves

Species concentration profiles produced from pyrolysis of n-heptane and isooctane diluted in argon were measured behind reflected shock waves at temperatures of 1000–1500 K and pressures of 1.2–2.6 atm. Simulation was performed using a chemical kinetic model based on KUCRS. The model reproduced the concentration profiles of n-heptane and isooctane surprisingly well over experimental conditions, while it did not cover some product species. The model was updated including additional species and reactions to reproduce concentration profiles of products.

Modeling and Experimental Study on Pyrolysis of Isooctane and n-Heptane behind Reflected Shock Waves

1,5-cyclooctadiene or 4-vinylcyclohexene mixture diluted with argon was heated to temperatures in the range 880–1230 K behind reflected shock waves. Profiles of IR-laser absorption were measured at 3.39 μm. From these profiles, rate constants k1 and k2 for the decyclization reactions 1,5-cyclooctadiene biradical and 4-vinylcyclohexene biradical were evaluated as k1 = 5.2 × 1014 exp(−48.3 kcal/RT) s−1 and k2 = 3.5 × 1014 exp(−55.3 kcal/RT) s−1, respectively. © 1993 John Wiley & Sons, Inc.

Hidekazu Oshita

Papers

Thermal isomerization and decomposition of 2-butyne in shock waves

Pyrolysis of n-pentane, n-hexane and n-heptane in a single pulse shock tube

Thermal decomposition of vinylacetylene in shock waves

Modeling and Experimental Study on Pyrolysis of Isooctane and n-Heptane behind Reflected Shock Waves

High temperature pyrolysis of 1,5-cyclooctadiene and 4-vinylcyclohexene in shock waves