Mechanism and kinetics of the reaction of methyl acetate with Cl atom – A theoretical study

Publication date: 1 May 2018 Source:Computational and Theoretical Chemistry, Volume 1131 Author(s): M. Gnanaprakasam, L. Sandhiya, K. Senthilkumar A mechanistic study on the H-atom abstraction and CO bond breaking reaction of methyl acetate with Cl atom is investigated by using electronic structure calculations. Three reaction pathways for the initial reactions were identified. Two pathways corresponding to H-atom abstraction from acetyl site (CH3CO) and methoxy site (OCH3), leading to the formation of alkyl radical intermediate along with HCl. In the third pathway, acetyl chloride and CH3O radical is formed through the breaking of CO bond and addition of Cl atom at acetyl site of methyl acetate. Further, the reaction between alkyl radical intermediate and O2 is studied. The fate of the so formed alkyl peroxy radical is determined by reaction with other atmospheric oxidants, such as HO2, NO and NO2 radicals is studied. We have calculated the rate constant for the initial reactions using CVT with SCT corrections over the temperature range of 278–2000 K. Graphical abstract

Source: Computational and Theoretical Chemistry - April 4, 2018 Category: Chemistry Source Type: research