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@ARTICLE{Iannone:44370,
author = {Iannone, R. and Anderson, R. S. and Vogel, A. and Eby, P.
S. and Whiticar, M. J. and Rudolph, J.},
title = {{T}he hydrogen kinetic isotope effects of the reactions of
n-alkanes with chlorine atoms in the gas phase},
journal = {Journal of atmospheric chemistry},
volume = {50},
issn = {0167-7764},
address = {Dordrecht [u.a.]},
publisher = {Springer Science + Business Media B.V},
reportid = {PreJuSER-44370},
pages = {121 - 138},
year = {2005},
note = {Record converted from VDB: 12.11.2012},
abstract = {The stable-hydrogen kinetic isotope effects (KIEs) for a
series of n-alkanes in reaction with chlorine atoms in the
gas phase were studied in a 25-L PTFE reaction chamber at
298 K. The time dependence of both the stable hydrogen
isotope ratios and the concentrations was determined using a
gas chromatography pyrolysis isotope ratio mass spectrometry
(GC-P-IRMS) system. The following KIE values, in per mil
(parts per thousand), were obtained: 39.6 +/- 2.7
(n-butane), 28.2 +/- 0.9 (n-pentane), 24.6 +/- 1.0
(n-hexane), 24.0 +/- 1.2 (n-heptane), 17.9 +/- 3.3
(n-octane), 15.1 +/- 0.7 (n-nonane), and 14.9 +/- 1.8
(n-decane). The errors given are the +/- 1 sigma standard
errors. These measured values were used to derive
structure-reactivity relationship (SRRs), which allow for
the calculation of the KIEs for the reaction of n-alkanes
with Cl atoms. The results of the calculations agree with
the measurements within few per mil or better. The site
specific stable hydrogen isotope fractionation effects for
methyl groups are approximately a factor of 3 larger than
those for methylene group, a finding which is qualitatively
similar to site-specific stable hydrogen isotope effects
reported in literature for reactions of alkanes with the OH
radical. Because n-alkanes with close to natural isotope
ratios (i.e. neither artificially labeled, nor enriched or
depleted) were used, the KIE data are directly applicable to
atmospheric studies. Based on these KIE values, the impact
of Cl-atom reactions of the stable hydrogen isotope ratio on
alkanes are estimated for different levels of Cl-atom
concentrations. On average in the troposphere, the impact of
Cl-atom reactions of the stable hydrogen isotope ratio of
n-alkanes will be small. However, in regions of the
troposphere with high concentrations of Cl atoms, such as
the tropospheric ozone depletion episodes during polar
sunrise, the impact of Cl-atom reactions is substantial.},
keywords = {J (WoSType)},
cin = {ICG-II},
ddc = {540},
cid = {I:(DE-Juel1)VDB48},
pnm = {Chemie und Dynamik der Geo-Biosphäre},
pid = {G:(DE-Juel1)FUEK257},
shelfmark = {Environmental Sciences / Meteorology $\&$ Atmospheric
Sciences},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000229220400002},
doi = {10.1007/s10874-005-2365-1},
url = {https://juser.fz-juelich.de/record/44370},
}