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Understanding the Kinetics of the Clo Dimer Cycle : Volume 6, Issue 4 (14/08/2006)

By Von Hobe, M.

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Book Id: WPLBN0003990358
Format Type: PDF Article :
File Size: Pages 40
Reproduction Date: 2015

Title: Understanding the Kinetics of the Clo Dimer Cycle : Volume 6, Issue 4 (14/08/2006)  
Author: Von Hobe, M.
Volume: Vol. 6, Issue 4
Language: English
Subject: Science, Atmospheric, Chemistry
Collections: Periodicals: Journal and Magazine Collection (Contemporary), Copernicus GmbH
Publication Date:
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications


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Canty, T., Grooß, J., Keller-Rudek, H., Moortgat, G. K., Müller, R., Salawitch, R. J.,...Stroh, F. (2006). Understanding the Kinetics of the Clo Dimer Cycle : Volume 6, Issue 4 (14/08/2006). Retrieved from

Description: Forschungszentrum Jülich GmbH, Institute for Chemistry and Dynamics of the Geosphere (ICG-I), Jülich, Germany. Among the major factors controlling ozone loss in the polar winter is the kinetics of the ClO dimer catalytic cycle. The most important issues are the thermal equilibrium between ClO and Cl2O2, the rate of Cl2O2 formation, and the Cl2O2 photolysis rate. All these issues have been addressed in a large number of laboratory, field and theoretical studies, but large discrepancies between individual results exist and a self-consistent set of parameters compatible with field observations of ClO and Cl2O2 has not been identified. Here, we use thermodynamic calculations and unimolecular rate theory to constrain the ClO/Cl2O2 equilibrium constant and the rate constants for Cl2O2 formation and dissociation. This information is used together with available atmospheric data to examine Cl2O2 photolysis rates based on different Cl2O2 absorption cross sections. Good overall consistency is achieved using a ClO/Cl2O2 equilibrium constant recently suggested by Plenge et al. (2005), the Cl2O2 recombination rate constant reported by Nickolaisen et al. (1994) and Cl2O2 photolysis rates based on averaged absorption cross sections that are roughly intermediate between the JPL 2002 assessment and a laboratory study by Burkholder et al. (1990).

Understanding the kinetics of the ClO dimer cycle


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