Relative Rate Studies of the Reactions of Atomic Chlorine with Acetone and Cyclic Ketones

Abstract

Rate coefficients have been measured for Cl atom reactions under ambient conditions with acetone and four cyclic ketones. Cl was generated by UV photolysis of Cl 2 , and other species were monitored by FT-IR spectroscopy. The measurements yield k(Cl + acetone) = (2.0 ± 0.7) × 10 −12 , k(Cl + cyclobutanone) = (10.1 ± 0.8) × 10 −11 , k(Cl + cycloheptanone) = (24.0 ± 2.3) × 10 −11 , k(Cl + 2-methyl cyclopentanone) = (15.2 ± 1.2) × 10 −11 , and k(Cl + 2-methyl cyclohexanone) = (11.2 ± 1.0) × 10 −11 cm 3 molecule −1 s −1 , where the uncertainties represent 95% confidence limits. These results are discussed in the context of structure-activity relationships. We also present a prediction for Cl + cyclopropanone based on ab initio properties of the transition state.

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

“…Experimental conditions and molecular yields of (E)-4-methylcyclohexanone for the reaction of 4MCHexOH with atmospheric oxidants. Rate coefficient of k= 11.2 × 10 −11 (in cm 3 molecule −1 s −1 ) used to correct the concentration of (E)-4-methylcyclohexanone by loss with the reaction of Cl atoms (data of 2-methylcyclohexanone and Cl atoms Herath et al, 2018). Photolysis rate coefficient estimated for (E)-4-methylcyclohexanone under our experimental conditions, kp = 5 × 10 −5 s −1 .…”

“…This work is the first study of the products of the reaction of 3,3DM1ButOH with atmospheric oxidants; therefore, there is no other study with which to compare the results. Figure 7 shows the reaction mechanism proposed based on existing studies of saturated alcohols' reactions with Cl atoms and the OH radical in the literature (Cavalli et al, 2002;Hurley et al, 2009;McGillen et al, 2013;Welz et al, 2013) and considering the reaction products identified in our work. Table S2 shows a summary of the reaction products, either observed or tentatively identified, proposed in this mechanism of the reaction of 3,3DM1ButOH with the atmospheric oxidants.…”

“…Although some studies into the reactivity of higher alcohols have been carried out over the last few years (Ballesteros et al, 2007;Hurley et al, 2009;Andersen et al, 2010;Calvert et al, 2011;Moreno et al, 2012Moreno et al, , 2014Mellouki et al, 2015), the kinetic and mechanistic database is still scarce. In the case of 3,3-dimethyl-1-butanol and 3,3-dimethyl-2butanol (derivatives of 1-butanol and 2-butanol), there is a lack of information with respect to the diurnal reactivity (Moreno et al, 2014;Mellouki et al, 2015).…”