Chemical Kinetic Data Base for Combustion Chemistry Part V. Propene

Abstract

This publication contains evaluated and estimated data on the kinetics of reactions involving propene and allyl radical and various small inorganic and organic species which are of importance for the proper understanding of the early stages of propene and the intermediate stages of propane and isobutane combustion and pyrolysis. It is meant to be used in conjunction with the kinetic data given in earlier publications, which is of direct pertinence to the understanding of methane, ethane, methanol, propane and isobutane pyrolysis and combustion, but which also contains a large volume of data that are applicable to the propene system. The temperature range covered is 300–2500 K and the density range 1×1016 to 1×1021 molecules cm−3.

Mechanism of the Aerobic Oxidation of α‐Pinene

“…For the addition of tert-butylperoxyl radicals, a barrier of 13.4 kcal mol À1 was computed (B3LYP/6-311++G(df,pd)//B3LYP/6-31G(d,p) level of theory), independent of from which side the olefin is approached (cis or trans to the dimethyl bridge). Combining this barrier with the reported prefactor for the addition of CH 3 OO · to propylene, [29] (A 9 = 4.0 10 8 m À1 s À1 ), results in k 9 (363 K) of approximately 7 m À1 s À1 , taking into account a reaction path degeneracy of 2 (addition can occur cis or trans to the dimethyl bridge). The barrier to the second step in the epoxidation mechanism, is computed to be 5.5 kcal mol À1 , leading to a transition state theory (TST) calculated rate constant of k 10 (363 K) = 2 10 9 m À1 s À1 .…”

A kinetic modeling study on the oxidation of primary reference fuel–toluene mixtures including cross reactions between aromatics and aliphatics

“…Rate constants of these reactions were taken from the estimates of Tsang [29]. For the benzyl radicals, corresponding reactions are endothermic, and therefore not considered in the present model.…”

Detailed chemical kinetic mechanisms for combustion of oxygenated fuels

“…(3) A new approach for OH and O addition to olefinic species was based on propene literature. [21][22][23]. (4) For radical attack on cyclic compounds, Evans-Polyani relations were used for activation energy estimates, representing each C-H bond 94 kcal/mole or weaker with its own set of abstraction reactions.…”