Kinetics of OH- and Cl-initiated oxidation of CH2=CHC(O)O(CH2)2CH3 and CH2=CHCH2C(O)O(CH2)2CH3 and fate of the alkoxy radicals formed

Abstract

Rate coefficients of the reactions of OH and Cl radicals with vinyl and allyl butyrate were determined for the first time at 298 K and 1 atm using the relative method to be (in cm3 molecule-1 s-1): k1(OH + CH2=CHC(O)O(CH2)2CH3) = (2.61 +/- 0.31) × 10-11, k2(Cl + CH2=CHC(O)O(CH2)2CH3) = (2.48 +/- 0.89) × 10-10, k3(OH + CH2=CHCH2C(O)O(CH2)2CH3) = (2.89 +/- 0.31) × 10-11, and k4(Cl + CH2=CHCH2C(O)O(CH2)2CH3) = (2.25 +/- 0.96) × 10-10. Reactivity trends and atmospheric lifetimes of esters are presented. Additionally, a product study shown butyric acid and polifunctional products for the reactions of vinyl and allyl butyrate, respectively and general mechanism is proposed.