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Article Dans Une Revue Journal of Physical Chemistry A Année : 2012

Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical

Résumé

The thermal decomposition of the 5-methyl-2furanylmethyl radical (R,), the most important primary radical formed during the combustion and thermal decomposition of 2,5-dimethylfuran (a promising next-generation biofuel), was studied using CBS-QB3 calculations and master equation (ME)/RRKM modeling. Because very little information is available in the literature, the detailed potential energy surface (PES) was investigated thoroughly. Only the main pathways, having a kinetic influence on the decomposition of R-1, were retained in the final ME/RRKIvl model. Among all the channels studied, the ring-opening of the 5-methyl-2-furanylmethyl radical, followed by ring enlargement to form c-yclohexadienone molecules is predicted to be the easiest decomposition channel of R-1. The C-6 cyclic species formed can undergo unimolecular reactions to yield phenol and to a lesser extent cyclopentadiene and CO. Our calculations predict that these species are important products formed during the pyrolysis of 2,5-dimethylfuran (DMF). Other channels involved in the decomposition of R-1 lead directly to the formation of linear and cyclic unsaturated Cs species and constitute an additional source of cyclopentadiene and CO. High-pressure limit rate constants were computed as well as thermochemical properties for important species. ME/RRKM analysis was performed to probe the influence of pressure on the rate coefficients and pressure dependent rate coefficients were proposed for pressures and temperatures ranging, respectively, from 10(-2) bar to 10 bar and 1000 to 2000 K.
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Dates et versions

hal-00777859 , version 1 (18-01-2013)

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René Fournet, Baptiste Sirjean. Theoretical Study of the Thermal Decomposition of the 5-Methyl-2-furanylmethyl Radical. Journal of Physical Chemistry A, 2012, 116 (25), pp.6675-6684. ⟨10.1021/jp303680h⟩. ⟨hal-00777859⟩
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