RATE CONSTANTS FOR THE GAS-PHASE REACTION OF OZONE WITH UNSATURATED OXYGENATES

The gas-phase reaction of ozone with a series of unsaturated oxygenate s and with l-pentene has been studied at ambient T (287-296 K) and p = 1 atm. of air. Reaction rate constants, in units of 10(-18) cm(3) mol ecule(-1) s(-1), are 0.22 +/- 0.05 for 2 (5H)-furanone, 1.08 +/-: 0.20 for methacrolein, 1.74 +/- 0.20 for crotonaldehyde. 5.84 +/- 0.39 for methylvinyl ketone,d 1.05 +/- 0.15 for methyl acrylate, 3.20 +/- 0.47 for vinyl acetate, 59.0 +/- 8.7 for cis-3-hexenyl acetate, 154 +/- 30 for ethylvinyl ether, greater than or equal to(315 +/- 23) for linalo ol, and 10.9 +/- 1.4 for l-pentene. The results are compared to litera ture data for the compounds studied and for other unsaturated oxygenat es, and are discussed in terms of reactivity toward ozone as a functio n of the nature, number, and position of the oxygen-containing substit uents -CHO, -C(O)R, -C(O)on, and -OC(O)R. Atmospheric implications are briefly examined. (C) 1998 John Wiley & Sons, Inc.