Kinetic and mechanistic study on gas phase reactions of ozone with a series of cis-3-hexenyl esters?

RSC Advances Pub Date: 2018-01-23 DOI: 10.1039/C7RA13369C

Abstract

As an important group of green leaf volatiles (GLVs), C6 hexenyl esters, are found to be widely emitted into the atmosphere by plants and vegetation, especially when they suffer mechanical damage. It is indispensable to understand their atmospheric fate for environmental assessment and model simulation. In this paper, the rate constants for reactions of O3 with four cis-3-hexenyl esters have been measured using an absolute method in a flow tube reactor at 298 K and atmospheric pressure. The measured rate constants (in 10?17 cm3 per molecule per s) were 4.06 ± 0.66 for cis-3-hexenyl formate, 5.77 ± 0.70 for cis-3-hexenyl acetate, 7.62 ± 0.88 for cis-3-hexenyl propionate, and 12.34 ± 1.59 for cis-3-hexenyl butyrate, respectively. Theoretical calculations were also carried out for the title reactions to better understand their kinetics and mechanism using density functional theory (DFT) and transition state theory (TST). Geometry optimizations, energy and harmonic vibrational frequency calculations were performed for all of the stationary points at the BHandHLYP/6-311+G(d,p) level of theory. The calculated rate constants were in good agreement with the experimental values. The results showed that the reactivity of the studied compounds towards O3 was obviously dependent on their chemical structure, such as the nature of the substituent, and the relative positions of the double bond and the substituent. The results were also discussed in terms of their atmospheric importance in the degradation of these unsaturated esters by comparing their lifetimes with respect to their reactions with O3 and other main atmospheric oxidants.

Graphical abstract: Kinetic and mechanistic study on gas phase reactions of ozone with a series of cis-3-hexenyl esters
Recommended Literature