Theoretical and kinetic modeling study of chloromethane (CH<sub>3</sub>Cl) pyrolysis and oxidation
Matteo Pelucchi, Carlo Cavallotti, Alessio Frassoldati, E. Ranzi, Peter Glarborg, Tiziano Faravelli
Abstract
Abstract This work presents a comprehensive kinetic modeling study of the pyrolysis and oxidation of chloromethane. Theoretical calculations were performed for the decomposition reaction CH 3 Cl + M = CH 3 + Cl + M and for a set of relevant H‐abstraction reactions (CH 3 Cl + R, R = Cl, Ḣ, ȮH, HȮ 2 , O 2 , Ö, ĊH 3 , Ċ 2 H 3 , Ċ 2 H 5 ; CH 4 + Cl, C 2 H 6 + Cl, C 2 H 4 + Cl, C 2 H 2 + Cl). Comparison with previous experimental or theoretical determinations, when available, proved the appropriateness of the adopted protocols and the accuracy of the calculated rate constants. Previously developed subsets for CH 3 Cl and HCl/Cl 2 were updated with the theoretical rate constants and combined with the CRECK C 1 –C 3 mechanism, yielding a kinetic mechanism consisting of 143 species and 2347 reactions. The validation was performed through comparison with all the pyrolysis and oxidation measurements available for pure CH 3 Cl and its mixtures with CH 4 , H 2 , and CO/H 2 O. The kinetic discussion highlights the role of key reaction steps that have been theoretically investigated in this work and in previous efforts and sheds light on additional reaction pathways needing better assessments.