Mechanism and kinetic study of 3-fluoropropene with hydroxyl radical reaction.

Potential energy surface for the reaction of hydroxyl radical (OH) with 3-fluoropropene (CH₂CHCH₂F) has been studied to evaluate the reaction mechanisms, possible products and rate constants. It has been shown that the CH₂CHCH₂F with OH reaction takes place via a barrierless addition/elimination and hydrogen abstraction mechanism. It is revealed for the first time that the initial step for the barrierless additional process involves a pre-reactive loosely bound complex (CR1) that is 1.60 kcal/mol below the energy of the reactants. Subsequently, the reaction bifurcates into two different pathways to form IM1 (CH₂CHOHCH₂F) and IM2 (CH₂OHCHCH₂F), which can decompose or isomerize to various products via complicated mechanisms. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants and branching ratios. At atmospheric pressure with He as bath gas, IM1 formed by collisional stabilization is dominated at T≤600 K; whereas the direct hydrogen abstraction leading to CH₂CHCHF and H₂O are the major products at temperatures between 600 and 3000 K, with estimated contribution of 72.9% at 1000 K. Furthermore, the predicted rate constants are in good agreement with the available experimental values.