Temperature dependent kinetics of the OH/HO2/O3 chain reaction by time-resolved IR laser absorption spectroscopy

被引:39
作者
Nizkorodov, SA
Harper, WW
Blackmon, BW
Nesbitt, DJ [1 ]
机构
[1] Natl Inst Stand & Technol, Joint Inst Lab Astrophys, Boulder, CO 80309 USA
[2] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
关键词
D O I
10.1021/jp9934984
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
This paper presents an extensive temperature dependent kinetic study of the catalytic HOx ozone cycle, (1) OH + O-3 --> HO2 + O-2 and (2) HO2 + O-3 --> OH + 2 O-2, based on time-resolved, Doppler limited direct absorption spectroscopy of OH with a single mode (Delta nu = 0.0001 cm(-1)) high-resolution infrared laser. The sum of the two chain rate constants, k(1) + k(2), is measured over the 190-315 K temperature range and can be accurately described by an Arrhenius-type expression: k(1) + k(2) (cm(3)/s) = 2.26(40) x 10(-12) exp[-976(50)/T]. These results are in excellent agreement with studies by Ravishankara et al. [J. Chem. Phys. 1979, 70, 984] and Smith et al. [Int. J. Chem. Kinet. 1984, 16, 41] but are significantly higher than the values currently accepted for atmospheric modeling. In addition, these studies also reflect the first such rate measurements to access the 190-230 K temperature range relevant to kinetic modeling of stone chain loss in the lower stratosphere.
引用
收藏
页码:3964 / 3973
页数:10
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