Add time:07/21/2019         Source:sciencedirect.com

Ignition delay times of cyclohexane–oxygen–argon and cyclopentane–oxygen–argon mixtures have been measured in a shock tube, the onset of ignition being detected by OH radical emission. Mixtures contained 0.5 or 1% of hydrocarbon for values of the equivalence ratio ranging from 0.5 to 2. Reflected shock waves allowed temperatures from 1230 to 1840 K and pressures from 7.3 to 9.5 atm to be obtained. These measurements have shown that cyclopentane is much less reactive than cyclohexane, as for a given temperature the observed autoignition delay times were about 10 times higher for the C5 compound than for the C6. Detailed mechanisms for the combustion of cyclohexane and cyclopentane have been proposed to reproduce these results. The elementary steps included in the kinetic models of the oxidation of cyclanes are close to those proposed to describe the oxidation of non cyclic alkanes and alkenes. Consequently, it has been possible to obtain these models by using an improved version of the EXGAS software, a computer package for the automatic generation of detailed kinetic models for the gas-phase combustion of alkanes and alkenes. Nevertheless, the modeling of the oxidation of cyclanes requires new types of generic reactions to be considered, and especially to define new correlations for the estimation of the rate constants. Quantum chemical calculations have been used to improve the estimation of some sensitive rate constants in the case of cyclopentane. The main reaction pathways have been derived from flow rate and sensitivity analysis.

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