Kinetics of the reaction of F atoms with CH3ONO and CH3O, and the reaction of CH3O with a number of hydrocarbons
作者:Peter Biggs、Carlos E. Canosa-Mas、Jean-Marc Fracheboud、Dudley E. Shallcross、Richard P. Wayne
DOI:10.1039/a701175j
日期:——
A discharge-flow system equipped with a laser-induced fluorescence cell to detect the methoxyl radical and a quadrupole mass spectrometer to detect products has been used to determine the kinetics of the reactions: CH
3
ONO + F → products (1), CH
3
O + F → products (2), CH
3
O + CH
3
O → products (3), CH
3
O + n-C
4
H
10
→ products (4), CH
3
O + i-C
4
H
10
→ products (5), CH
3
O + C
2
H
4
→ products (6), at T = 295 K and P = 2–3 Torr. The rate constants determined are: k
1
= (8.0 ± 0.5) × 10
−11
cm
3
molecule
−1
s
−1
, k
2
= (1.5 ± 0.5) × 10
−10
cm
3
molecule
−1
s
−1
, k
3
= (1.3 ± 0.4) × 10
−11
cm
3
molecule
−1
s
−1
, and upper limits for the rate constants k
4
⩽ 1.0 × 10
−14
cm
3
molecule
−1
s
−1
, k
5
⩽ 1.7 × 10
−14
cm
3
molecule
−1
s
−1
and k
6
⩽ 1.1 × 10
−15
cm
3
molecule
−1
s
−1
. In addition, a summary of the sources of CH
3
O developed for use in low-pressure flow systems in this and other groups is presented.
放电流系统配备了激光诱导荧光池检测甲氧基自由基,四极质谱仪检测产物,用于确定反应的动力学:在 T = 295 K 和 P = 2-3 Torr 条件下,测定了 CH 3 ONO + F → 产物 (1)、CH 3 O + F → 产物 (2)、CH 3 O + CH 3 O → 产物 (3)、CH 3 O + n-C 4 H 10 → 产物 (4)、CH 3 O + i-C 4 H 10 → 产物 (5)、CH 3 O + C 2 H 4 → 产物 (6)。确定的速率常数为:k 1 = (8.0 ± 0.5) × 10 -11 cm 3 molecule -1 s -1 , k 2 = (1.5 ± 0.5) × 10 -10 cm 3 molecule -1 s -1 , k 3 = (1.3 ± 0.4) × 10 -11 cm 3 molecule -1 s -1 ,以及速率常数 k 4 ⩽ 1.0 × 10 -14 cm 3 molecule -1 s -1 、k 5 ⩽ 1.7 × 10 -14 cm 3 molecule -1 s -1 和 k 6 ⩽ 1.1 × 10 -15 cm 3 molecule -1 s -1 的上限。此外,还概述了本研究组和其他研究组开发的用于低压流动系统的 CH 3 O 源。