Pulsed laser photolysis kinetics study of the O(3P)+ClO reaction

Article abstract of DOI:10.1063/1.455574

A pulsed laser photolysis technique has been employed to study the kinetics of the important stratospheric reaction O + ClO <*> Cl + O2 in N2 buffer gas over the temperature and pressure ranges 231-367 K and 25-500 Torr. 351 nm pulsed laser photolysis of Cl2/O3/N2 mixtures produced Cl atoms in excess over O3.After a delay sufficient for the reaction Cl + O3-->ClO + O2 to go to completion, a small fraction of the ClO was photolyzed at 266 nm to produce O(³P).The decay of O(³P) in the presence of an excess, known concentration of ClO was then followed by time-resolved resonance fluorescence spectroscopy.We find that k₁ is independent of pressure, but that k₁( T) increases with decreasing temperature.Our results suggest that the Arrhenius expression k₁( T) = ( 1.55 +/- 0.33 )*10^-11exp< (263 +/- 60)/T> cm³ molecule^-1 s^-1 is appropriate for modeling stratospheric chemistry.Errors in the Arrhenius expression are 2δ and represent precison only.The absolute accuracy of k, at any temperature within the range studied is estimated to be + 20percent.Our results agree with other recent measurements of k₁ at 298 K but give significantly faster rate coefflcients at stratospheric temperatures.A few measurements of the rate coefflcient for the reaction ClO + ClO <*> products were also carried out.These measurements were necessary to assess the time dependence of .

Full text of DOI:10.1063/1.455574

Pulsed laser photolysis kinetics study of the O(3 P)+ClO reaction
J. M. Nicovich, P. H. Wine, and A. R. Ravishankara
Citation: The Journal of Chemical Physics 89, 5670 (1988); doi: 10.1063/1.455574
View online: http://dx.doi.org/10.1063/1.455574
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/89/9?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
130.216.129.208 On: Fri, 12 Dec 2014 03:20:53