Kinetics of the Gas-Phase Reactions of OH and NO₃ Radicals and O₃ with Allyl Alcohol and Allyl Isocyanate

Abstract

Rate constants for the gas-phase reactions of OH radical, NO 3 radical, and ozone with allyl alcohol (AAL) and allyl isocyanate (AIC) have been measured using relative rate methods at atmospheric pressure in purified air. The experimental Arrhenius expression obtained for the reaction of the OH radical with AAL is (1.68 ( 0.89) × 10 -12 × exp(1100/T) cm 3 molecule -1 s -1 , for T ) 282-315 K; the Arrhenius expression for the reaction of OH radical with AIC is (1.94 ( 1.04) × 10 -14 × exp(2207/T) cm 3 molecule -1 s -1 , for T ) 282-317 K, where the indicated errors are one least-squares standard deviation. All OH radical reaction rate constants have been measured relative to k(OH + R-pinene) and k(OH + 1,3,5-trimethylbenzene). The rate constant for the gas-phase reaction of OH radical with allyl alcohol-d 6 isotopomer (AAL-d 6 ) has been measured at T ) 298 K, and the value is 5.10 × 10 -11 cm 3 molecule -1 s -1 . The kinetic isotope effect is small, with k(AAL)/k(AAL-d 6 ) ) 1.32. Rate constants for the gas-phase reactions of NO 3 radical with AAL [relative to k(NO 3 +methacrolein)] and O 3 [relative to k(O 3 + β-pinene)] have been measured, and the values are 7.7 × 10 -15 cm 3 molecule -1 s -1 at T ) 298 K and 1.6 × 10 -17 cm 3 molecule -1 s -1 at T ) 296 K, respectively. Rate constants for the gas-phase reactions of NO 3 radical and O 3 with AIC have been measured, and the values are 9.4 × 10 -16 cm 3 molecule -1 s -1 at T ) 299 K and 5.54 × 10 -18 cm 3 molecule -1 s -1 at T ) 299 K, respectively. Multireference ab initio calculations at the MRMP2/6-311G(d,p) level have been carried out for reactions of OH radical with AAL and AIC. Results indicate that prereactive hydrogen bonded complexes form in the entrance channels for these reactions.

Kinetics and mechanisms of OH‐initiated oxidation of small unsaturated alcohols

“…Our rate coefÞcients are consistent with the relative and absolute rate results from Le Person et al [11] and Parker and Espada-Jallad [12]. The pulsed laser photolysis-laser-induced ßuo-rescence (PLP-LIF) measurements by Upadhyaya et al [9] in 10-20 Torr argon give a rate coefÞcient that is approximately 25% lower than our measurement in 700 Torr air.…”

“…There have been six studies of reaction (1) (Papagni et al [7], Orlando et al [8], Upadhyaya et al [9], Holloway et al [10], Le Person et al [11], and Parker and Espada-Jallad [12]), and values of k 1 in the range (3.7-6.8) × 10 −11 cm 3 molecule −1 s −1 have been reported at room temperature. There has been one study of reaction (2); Papagni et al [7] measured k 2 = 5.9 × 10 −11 cm 3 molecule −1 s −1 at 296 K. Nine experimental studies of the kinetics of reaction of OH radicals with 2-methyl-3-buten-2-ol have been conducted (Papagni et al [7], Rudich et al [13], Fantechi et al [14], Ferronato et al [15], Alvarado et al [16], Reisen et al [17], Imamura et al [18], Baasandorj and Stevens [19], and Carrasco et al [20]).…”

Theoretical study on the reaction mechanism of the OH-initiated oxidation of CH2=C(CH3)CH2CH2OH

“…While many kinetics and products studies have been carried out for the unsaturated alcohols such as allyl alcohol [8][9][10][11][12][13][14] and MBO232 [11,[15][16][17][18][19][20] with OH radical, as far as we know, only two kinetic studies have been done for the reaction of MBO331 ? OH [20,21].…”

Theoretical study on the gas phase reaction of propargyl alcohol with hydroxyl radical

“…It is very important to compare the mechanism and kinetics feature of the CHCCH 2 OH + OH reaction with that of analogous reaction CH 2 CHCH 2 OH + OH, and the two reactions were studied experimentally and theoretically already . The comparisons will give some interesting similarities and differences.…”