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Title: Temperature dependent kinetics of the OH/HO{sub 2}/O{sub 3} chain reaction by time-resolved IR laser absorption spectroscopy

Abstract

This paper presents an extensive temperature dependent kinetic study of the catalytic HO{sub x} ozone cycle, (1) OH + O{sub 3} {r_arrow} HO{sub 2} + O{sub 2} and (2) HO{sub 2} + O{sub 3} {r_arrow} OH + 2 O{sub 2}, based on time-resolved, Doppler limited direct absorption spectroscopy of OH with a single mode ({Delta}{nu} = 0.0001 cm{sup {minus}1}) high-resolution infrared laser. The sum of the two chain rate constants, k{sub 1} + k{sub 2}, is measured over the 190--315 K temperature range and can be accurately described by an Arrhenius-type expression: k{sub 1} + k{sub 2} (cm{sup 3}/s) = 2.26(40) x 10{sup {minus}12} exp[{minus}976(50)/T]. These results are in excellent agreement with studies by Ravishankara et al. and Smith et al. 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 ozone chain loss in the lower stratosphere.

Authors:
; ; ;
Publication Date:
Research Org.:
National Inst. of Standards and Technology, Boulder, CO (US); Univ. of Colorado, Boulder, CO (US)
OSTI Identifier:
20034417
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 104; Journal Issue: 17; Other Information: PBD: 4 May 2000; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; ATMOSPHERIC CHEMISTRY; OZONE; CHEMICAL REACTION KINETICS; HYDROXYL RADICALS; TEMPERATURE DEPENDENCE; INFRARED SPECTRA

Citation Formats

Nizkorodov, S.A., Harper, W.W., Blackmon, B.W., and Nesbitt, D.J. Temperature dependent kinetics of the OH/HO{sub 2}/O{sub 3} chain reaction by time-resolved IR laser absorption spectroscopy. United States: N. p., 2000. Web. doi:10.1021/jp9934984.
Nizkorodov, S.A., Harper, W.W., Blackmon, B.W., & Nesbitt, D.J. Temperature dependent kinetics of the OH/HO{sub 2}/O{sub 3} chain reaction by time-resolved IR laser absorption spectroscopy. United States. doi:10.1021/jp9934984.
Nizkorodov, S.A., Harper, W.W., Blackmon, B.W., and Nesbitt, D.J. Thu . "Temperature dependent kinetics of the OH/HO{sub 2}/O{sub 3} chain reaction by time-resolved IR laser absorption spectroscopy". United States. doi:10.1021/jp9934984.
@article{osti_20034417,
title = {Temperature dependent kinetics of the OH/HO{sub 2}/O{sub 3} chain reaction by time-resolved IR laser absorption spectroscopy},
author = {Nizkorodov, S.A. and Harper, W.W. and Blackmon, B.W. and Nesbitt, D.J.},
abstractNote = {This paper presents an extensive temperature dependent kinetic study of the catalytic HO{sub x} ozone cycle, (1) OH + O{sub 3} {r_arrow} HO{sub 2} + O{sub 2} and (2) HO{sub 2} + O{sub 3} {r_arrow} OH + 2 O{sub 2}, based on time-resolved, Doppler limited direct absorption spectroscopy of OH with a single mode ({Delta}{nu} = 0.0001 cm{sup {minus}1}) high-resolution infrared laser. The sum of the two chain rate constants, k{sub 1} + k{sub 2}, is measured over the 190--315 K temperature range and can be accurately described by an Arrhenius-type expression: k{sub 1} + k{sub 2} (cm{sup 3}/s) = 2.26(40) x 10{sup {minus}12} exp[{minus}976(50)/T]. These results are in excellent agreement with studies by Ravishankara et al. and Smith et al. 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 ozone chain loss in the lower stratosphere.},
doi = {10.1021/jp9934984},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 17,
volume = 104,
place = {United States},
year = {2000},
month = {5}
}