Rate Constants for the Reaction of OH with a Series of Unsaturated Alcohols between 263 and 371 K.

COMETTO, PABLO MARCELO; DALMASSO, PABLO ROBERTO; TACCONE, RAÚL ALBERTO; LANE, SILVIA IRENE; OUSSAR, FÁTIMA; DAËLE, VÉRONIQUE; MELLOUKI, ABDELWAHID; LE BRAS, GEORGES

JOURNAL OF PHYSICAL CHEMISTRY A

Año: 2008 vol. 112 p. 4444 - 4450

1089-5639

  Rate coefficients for the gas-phase reactions of OH radicals with four unsaturated alcohols, 3-methyl-3-buten-1-ol (k1), 2-buten-1-ol (k2), 2-methyl-2-propen-1-ol (k3) and 3-buten-1-ol (k4), were measured using two different techniques, a conventional relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The Arrhenius rate coefficients (in units of cm3molecule-1 s-1) over the temperature range 263-371 K were determined from the kinetic data obtained as k1 ) (5.5 ( 1.0) × 10–12 exp [(836 ( 54)/T]; k2 ) (6.9 ( 0.9) × 10–12 exp [(744 ( 40)/T]; k3 ) (10 ( 1) × 10–12 exp [(652 ( 27)/T]; and k4 ) (4.0 ( 0.4) × 10–12 exp [(783 ( 32)/T]. At 298 K, the rate coefficients obtained by the two methods for each of the alcohols studied were in good agreement. The results are presented and compared with those obtained previously for the same and related reactions of OH radicals. Reactivity factors for substituent groups containing the hydroxyl group are determined. The atmospheric implications for the studied alcohols are considered briefly.k1), 2-buten-1-ol (k2), 2-methyl-2-propen-1-ol (k3) and 3-buten-1-ol (k4), were measured using two different techniques, a conventional relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The Arrhenius rate coefficients (in units of cm3molecule-1 s-1) over the temperature range 263-371 K were determined from the kinetic data obtained as k1 ) (5.5 ( 1.0) × 10–12 exp [(836 ( 54)/T]; k2 ) (6.9 ( 0.9) × 10–12 exp [(744 ( 40)/T]; k3 ) (10 ( 1) × 10–12 exp [(652 ( 27)/T]; and k4 ) (4.0 ( 0.4) × 10–12 exp [(783 ( 32)/T]. At 298 K, the rate coefficients obtained by the two methods for each of the alcohols studied were in good agreement. The results are presented and compared with those obtained previously for the same and related reactions of OH radicals. Reactivity factors for substituent groups containing the hydroxyl group are determined. The atmospheric implications for the studied alcohols are considered briefly.