Rate constants for the gas‐phase reactions of Ozone with unsaturated Aliphatic Alcohols

Abstract

The gas-phase reaction of ozone with unsaturated alcohols in air has been investigated a t atmospheric pressure and ambient temperature (288-291 K). Cyclohexane was added to scavenge the hydroxyl radical which forms as a product of the ozone-unsaturated alcohol reaction. The reaction rate constants, in units of cm3 molecule-' s-l, are 16.2 +-0.7 for (2) 3-buten-2-01, 17.9 2 1.8 for 1-penten-3-01, 10.0 +-0.3 for 2-methyl-3-buten-2-01, 169 t 25 for cis-2 penten-1-01, and 251 2 41 for 2-buten-1-01 (mixture of isomers). Substituent effects on reactivity are discussed. The reactivity of unsaturated alcohols towards ozone is similar to that of their alkene structural homologues. Implications of these results with respect to the atmospheric persistence of unsaturated alcohols are briefly discussed.

Gas-phase reaction of ozone withtrans-2-hexenal,trans-2-hexenyl acetate, ethylvinyl ketone, and 6-methyl-5-hepten-2-one

“…This value is consistent with those obtained in earlier measurements made in this laboratory [ 19,201 ( R = 0.941) and (1.64 2 0.04) X lop6 s-' ( R = 0.997) were essentially the same as that measured for loss of ozone alone in pure air. These results show that the ozone-cyclohexane reaction is negligibly slow at the ozone and cyclohexane concentrations employed in this study.…”

“…As more information becomes available concerning the nature and abundance of these compounds, it is necessary to obtain the kinetic and product data that are needed to assess their persistence and fate in the atmosphere. Kinetic data have recently been reported for the reaction of ozone with unsaturated alcohols and with other unsaturated oxygenates [19][20][21]. Carbonyl products of the ozone-unsaturated alcohol reaction have been identified 1221 and carbonyl and peroxyacyl nitrate (RC(0)OONOz) products have been characterized in sunlight-irradiated mixtures of unsaturated alcohols and oxides of nitrogen [23,24].…”

2-methyl-3-buten-2-ol: A Pheromone Component of Conifer Bark Beetles Found in the Bark of Nonhost Deciduous Trees

“…Following the observation of MB emission in pine forest by Goldan et al (1993) [25], several studies on the atmospheric chemistry of this BVOC alcohol have been actively carried out [29][30][31][32][33][34][35]. Harley et al…”

“…(1998) claimed that the major photochemical sink for MB [32] or with NO 3 [33,34] imply significantly longer MB lifetimes with respect to these destruction processes. Further reaction chamber experiments [29,30] indicate that the MB-OH reaction leads to the production of acetone, glycol aldehyde, formaldehyde, and presumably 2-hydroxy-2-methylpropanal.…”

“…Further reaction chamber experiments [29,30] indicate that the MB-OH reaction leads to the production of acetone, glycol aldehyde, formaldehyde, and presumably 2-hydroxy-2-methylpropanal. The reaction with O 3 appears to yield the same major products, though in different proportions [29,32]. Recently, Chan et al (2009) suggested that photooxidation of MB might be a potential but minor source of secondary organic aerosol (SOA) [35].…”