Journal of Physical Chemistry A, Vol.104, No.17, 3964-3973, 2000
Temperature dependent kinetics of the OH/HO2/O-3 chain reaction by time-resolved IR laser absorption spectroscopy
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.