Theoretical Kinetic Study of the Ring Opening of Cyclic Alkanes

Baptiste Sirjean (1) , Pierre-Alexandre Glaude (1) , M.F. Ruiz-Lopez (2) , René Fournet (1)

1 DCPR - Département de Chimie Physique des Réactions
2 SRSMC - Structure et Réactivité des Systèmes Moléculaires Complexes

This work reports a theoretical study of the gas phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data (ΔH°f, S°, C°p) for all the involved species have been obtained by means of isodesmic reactions. Rate constants have been derived for all elementary reactions using transition state theory at 1 atm and temperatures ranging from 600 to 2000 K. These values have been compared with the few data available in the literature and showed a rather good agreement.

Domaines: Chimie-Physique [physics.chem-ph]

Baptiste Sirjean, Pierre-Alexandre Glaude, M.F. Ruiz-Lopez, René Fournet. Theoretical Kinetic Study of the Ring Opening of Cyclic Alkanes. European Combustion Meeting, Apr 2007, Chania, Greece. CD Rom du congrès, 6 p. ⟨hal-00377654⟩