Kinetics and Degradation Mechanism of Atmospheric Isoprene (2-methyl-1,
3-butadiene (C5H8)) with Chlorine Radical and Its Derivatives – A DFT
Study
Abstract
Isoprene (2-methyl-1, 3-butadiene (C5H8)) is one of the most prominent
and abundant non-methane hydrocarbon existing in the lower level of the
troposphere. In this work, possible reaction mechanism of chlorine (Cl)
radical initiated isoprene and its subsequent reactions are investigated
using quantum chemical methods. The calculated thermodynamic result
shows that the reaction of isoprene with the Cl radical at the terminal
C=C bond position plays an important role to predict the end products.
The calculated rate coefficient for the reaction between isoprene and Cl
radicals (Cl addition at C1, C3, C4 and C5 positions) is found to be
4.89⨯10-11, 6.91⨯10-10, 1.63⨯10-10 and 8.12⨯10-10 cm3/molecule/sec at
298K. The branching ratio and atmospheric lifetime have been calculated
from the reaction rate coefficient values of isoprene+Cl. The reaction
force analysis predicts Cl radical addition at the terminal C=C bond
position plays a dominant role by structural rearrangement. The kinetic
and thermodynamic results reveal that the electrophilic addition of Cl
radical to the terminal carbon atom plays the dominant role in the
marine boundary. Further, the subsequent reaction of Cl-isoprene adduct
radical helps for the development of ozone layer during daytime.