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@ARTICLE{vonHobe:44495,
author = {von Hobe, M. and Grooß, J.-U. and Müller, R. and
Hrechanyy, H. P. and Winkler, U. and Stroh, F.},
title = {{A} re-evaluation of the {C}l{O}/{C}l2/{O}2 equilibrium
constant based on stratospheric in-situ observations},
journal = {Atmospheric chemistry and physics},
volume = {5},
issn = {1680-7316},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {PreJuSER-44495},
pages = {693 - 702},
year = {2005},
note = {Record converted from VDB: 12.11.2012},
abstract = {In-situ measurements of ClO and its dimer carried out
during the SOLVE II/VINTERSOL-EUPLEX and ENVISAT Validation
campaigns in the Arctic winter 2003 suggest that the thermal
equilibrium between the dimer formation and dissociation is
shifted significantly towards the monomer compared to the
current JPL 2002 recommendation. Detailed analysis of
observations made in thermal equilibrium allowed to
re-evaluate the magnitude and temperature dependence of the
equilibrium constant. A fit of the JPL format for
equilibrium constants yields K-EQ=3.61 x 10(-27)
exp(8167/T), but to reconcile the observations made at low
temperatures with the existing laboratory studies at room
temperature, a modified equation,
K-EQ=5.47x10(-25)(T/300)(-2.29)exp(6969/T), is required.
This format can be rationalised by a strong temperature
dependence of the reaction enthalpy possibly induced by
Cl2O2 isomerism effects. At stratospheric temperatures, both
equations are practically equivalent. Using the equilibrium
constant reported here rather than the JPL 2002
recommendation in atmospheric models does not have a large
impact on simulated ozone loss. Solely at large zenith
angles after sunrise, a small decrease of the ozone loss
rate due to the ClO dimer cycle and an increase due to the
ClO-BrO cycle ( attributed to the enhanced equilibrium ClO
concentrations) is observed, the net effect being a slightly
stronger ozone loss rate.},
keywords = {J (WoSType)},
cin = {ICG-I},
ddc = {550},
cid = {I:(DE-Juel1)VDB47},
pnm = {Chemie und Dynamik der Geo-Biosphäre},
pid = {G:(DE-Juel1)FUEK257},
shelfmark = {Meteorology $\&$ Atmospheric Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000227344000003},
url = {https://juser.fz-juelich.de/record/44495},
}