Theoretical and experimental study of the OH radical with 3-bromopropene gas phase reaction rate coefficients temperature dependence

GONZÁLEZ VERA, MAURO; COMETTO, PABLO MARCELO; CASAÑAS, JUAN MANUEL; BAUERFELDT, GLAUCO F.; MELLOUKI, ABDELWAHID

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

JOHN WILEY & SONS LTD

Año: 2023 vol. 36

0894-3230

In this work, the rate-determining steps of the OH radical + 3-bromopropene gas phase reaction were studied, which could explain for the possible negative activation energy observed in experiments. To obtain new kinetic parameters and data for critical revisions, a reinvestigation of the rate coefficient (k) and its temperature dependence was carried out using the PLP-LIF technique, in the 254- to 371-K range. Moreover, quantum-mechanical and canonical variational transition state theory calculations were performed, taking into consideration four OH addition and two β-hydrogen atom abstraction reaction channels. The proposed kinetic model fits to the observed experimental Arrhenius behavior, and three not negligible reaction pathways are described for the first time.