Sequential two (blue) photon absorption by NO2 in the presence of H2 as a source of OH in pulsed photolysis kinetic studies:: Rate constants for reaction of OH with CH3NH2, (CH3)2NH, (CH3)3N, and C2H5NH2 at 295 K

被引:64
作者
Carl, SA [1 ]
Crowley, JN [1 ]
机构
[1] Max Planck Inst Chem, Div Atmospher Chem, D-55020 Mainz, Germany
关键词
D O I
10.1021/jp9821937
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The use of the sequential two-photon dissociation of NO2 (420-450 nm) in the presence of H-2 as a novel source of OH in kinetic studies has been assessed. Two-photon absorption by NO2 at these wavelengths leads to both O(D-1) and O(P-3) production ((40% and 60%, respectively); the O(D-1) is rapidly converted to OH in the presence of approximate to 1 x 10(16) cm(-3) H-2 [O(D-1) + H-2 --> OH + H] The H atom reacts with NO2 to generate a further OH radical (H + NO2 --> OH + NO). Laser fluences of approximate to 20-40 mJ cm(-2) were used to generate between 2 x 10(11) and 1 x 10(12) cm(-3) OH from an initial NO2 concentration of (5-13) x 10(14) cm(-3). OH [and O(P-3)] were detected by resonance fluorescence. Rate constants for the reactions of some aliphatic amines with the OH radical have been obtained at 295 K. The results obtained (in cm(3) s(-1)) are k(OH + CH3NH2) = (1.73 +/- 0.11) x 10(-11), k(OH + (CH3)(2)NH) = (6.49 +/- 0.64) x 10(-11), k[OH + (CH3)(3)N] = (3.58 +/- 0.22) x 10(-11), and k(OH + C2H5NH2) = (2.38(-0.15)(+0.5)) x 10(-11). Data for (CH3)(2)NH were also obtained using the 193 nm photolysis of N2O/CH4 as the O(D-1) source; the rate constant above is the average value obtained using both methods. The error limits include both statistical (2 sigma) and systematic errors.
引用
收藏
页码:8131 / 8141
页数:11
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