This work studies the mechanism steps of the OH radical + 3-chloropropene gas phase reaction that could explain the apparent negative activation energy experimentally observed. A reinvestigation of the rate coefficients (k) temperature dependence, using a PLP-LIF technique, between 253 and 371 K, was performed to provide new data for kinetic parameters critical revisions. A canonical Variational Transition State Theory study was performed to obtain the k temperature dependence considering four additions and one H atom abstraction pathways. The theoretical results can explain the experimental Arrhenius behavior, being an OH addition channel not described in previous literature the main reaction pathway.

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.