Temperature‐dependent kinetics for the ozonolysis of selected chlorinated alkenes in the gas phase

Abstract

The ozonolysis of olefinic species is an important tropospheric process impacting on climate and human health. However, few studies have investigated these reactions as a function of temperature and even less information is available upon the effects of alkene heteroatomic substitution on the Arrhenius parameters. The electron-withdrawing capacity of substituents about the olefinic bond strongly influences the rate of alkene ozonolysis. To understand better the effect of these substitutions, the temperature-dependence of a series of ozonechloroalkene reactions is investigated. Experiments were conducted in the EXTreme RAnge (EXTRA) chamber, over the range of 292-409 K and 760 Torr. The experimentally determined rate coefficients were fitted using an Arrhenius-type analysis to yield the following activation energies: 30.80 ± 0.79, 23.18 ± 0.59, 65.2 ± 2.8, 116.9 ± 5.6, 29.5 ± 1.8, and 18.67 ± 0.96 kJ mol −1 and preexponential A-factors 1.22

Atmospheric chemistry of (Z)- and (E)-1,2-dichloroethene: kinetics and mechanisms of the reactions with Cl atoms, OH radicals, and O3

“…Zhang et al 37 reported k 34 = (1.80 ± 0.29) × 10 −19 cm 3 molecule −1 s −1 . Within the error bars, the present work agrees with the reported values by Leather et al 35 with regard to k 33 , but not k 34 . Both the reported values for k 33 and k 34 by Blume et al 36 and the value for k 34 by Zhang et al 37 are all outside the error limits of the present study.…”

“…Two reports exist in the literature on k 33 and three on k 34 , some of which do not agree with each other, see Table 4. Leather et al 35 reported k 33 = (4.9 +4.0 −2.2 ) × 10 −21 , and k 34 = (8 +10 −5.4 ) × 10 −19 cm 3 molecule −1 s −1 , while Blume et al 36 reported k 33 = 3.59 × 10 −20 and k 34 = 2.46 × 10 −19 cm 3 molecule −1 s −1 . Zhang et al 37 reported k 34 = (1.80 ± 0.29) × 10 −19 cm 3 molecule −1 s −1 .…”

“…34 Two reports exist in the literature on k 33 and three on k 34 , some of which do not agree with each other, see Table 4. Leather et al 35 In their reaction with O 3 , (E)-CHClQCHCl and (Z)-CHClQCHCl are less reactive than their non-substituted counterpart (ethene) by a factors of 350 and 15, respectively. 33 The reaction occurs by electrophilic addition to the 4CQCo double bond.…”

Oxidation and Reduction

“…222 The E a and pre-exponential factor A for the temperature dependence of reactions of O 3 with cis-1,2-dichloroethene, trans-1,2-dichloroethene, trichloroethene, tetrachloroethene, 2-chloropropene, and 3-chloro-1-butene have been reported. 223 The Arrhenius expressions for the gas-phase reactions of 1-butene, isobutene, 2-methyl-1-butene, and 3-methyl-1-butene with O 3 were determined, and the reaction rate constant and activation energy agreed with those reported in the literature. 224 The Arrhenius expressions, rate constants, and atmospheric residence times for gas-phase reactions of α- (71) and β-farnesene (72), β-myrcene (73), and β-ocimene (74) with O 3 and • OH radicals using He as the diluent gas were reported.…”

Structure–activity relationship (SAR) for the prediction of gas-phase ozonolysis rate coefficients: an extension towards heteroatomic unsaturated species

“…22 These rate coefficients were also determined using the absolute method, where ozone was monitored using a Monitor Labs Inc. 8810 ozone analyzer. The resulting Arrhenius expressions are published elsewhere, 23 extrapolations of which provide experimental estimates of the room temperature rate coefficients presented in this work.…”