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Theoretical and kinetic modeling study of chloromethane (CH 3 Cl) pyrolysis and oxidation
Author(s) -
Pelucchi Matteo,
Cavallotti Carlo,
Frassoldati Alessio,
Ranzi Eliseo,
Glarborg Peter,
Faravelli Tiziano
Publication year - 2021
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21452
Subject(s) - chloromethane , chemistry , kinetic energy , reaction rate constant , decomposition , pyrolysis , computational chemistry , kinetics , catalysis , organic chemistry , physics , quantum mechanics
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.