KINETICS OF THE GAS-PHASE REACTIONS OF NO3 RADICALS WITH A SERIES OF ALCOHOLS, GLYCOL ETHERS, ETHERS AND CHLOROALKENES

Using a relative rate method, rate constants have been measured for th e gas-phase reactions of the NO3 radical with methacrolein, a series o f ethers, glycol ethers, alcohols and chloroalkenes at 298 +/- 2 K and atmospheric pressure of air. The rate constants determined tin units of 10(-16) cm(3) molecule(-1) s(-1)) were: methacrolein, 33 +/- 10; di ethyl ether, 31 +/- 10; di-n-propyl ether, 49 +/- 16; diisopropyl ethe r, 40 +/- 13; ethyl tert-butyl ether, 45 +/- 14; 1-methoxypropan-2-ol, less than or equal to 15 +/- 5; 2-butoxyethanol, less than or equal t o 31 +/- 11; propan-1-ol, less than or equal to 21 +/- 8; propan-2-ol, less than or equal to 17 +/- 6; butan-1-ol, less than or equal to 27 +/- 10; butan-2-ol, less than or equal to 25 +/- 8; heptan-4-ol, less than or equal to 60 +/- 20; cis-1,2-dichloroethene, 1.3 +/- 1.3; 1,1-d ichloroethene, 18(-6)(+9); trichloroethene, 3.6(-1.5)(+2.0); tetrachlo roethene, <1.8; and 3-chloropropene, 5.8(-2.0)(+3.0). Carbonyl product s of the alcohol reactions arising after H-atom abstraction at the car bon atom to which the -OH group is attached were observed, and rate co nstants for this reaction pathway obtained. Significant discrepancies with the literature concern propan-2-ol, ethyl tert-butyl ether and 3- chloropropene, with our relative rate constants for these compounds be ing factors of ca. 2, ca. 2, and ca. 8 lower, respectively, than previ ously reported absolute rate constant determinations.