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@ARTICLE{Iannone:43163,
author = {Iannone, R. and Anderson, R. S. and Vogel, A. and Rudolph,
J. and Eby, P. and Whiticar, M. J.},
title = {{L}aboratory studies of the hydrogen kinetic isotope
effects ({KIE}s) for the reaction of non-methane
hydrocarbons with the {OH} radical in the gas phase},
journal = {Journal of atmospheric chemistry},
volume = {47},
issn = {0167-7764},
address = {Dordrecht [u.a.]},
publisher = {Springer Science + Business Media B.V},
reportid = {PreJuSER-43163},
pages = {191 - 208},
year = {2004},
note = {Record converted from VDB: 12.11.2012},
abstract = {The hydrogen kinetic isotope effects (KIEs) of the
reactions of 15 non-methane hydrocarbons (NMHCs) with the OH
radical were measured at 298 +/- 2 K. The measurements were
made using NMHCs without artificial isotopic labeling or
enrichment. The following average hydrogen KIE values, in
per mil (parts per thousand), were obtained: 29.8 +/- 2.1
(toluene), 51.6 +/- 2.1 (n-butane), 97.3 +/- 12.5
(i-butane), 63.2 +/- 5.9 (cyclopentane), 10.5 (p-xylene),
26.8 +/- 3.5 (ethylbenzene), 65.9 +/- 7.0 (n-pentane), 79.5
+/- 9.6 (cyclohexane), 52.8 +/- 5.0 (n-hexane), 38.9 +/- 7.8
(n-heptane), 33.4 +/- 3.1 (n-octane), 29.6 +/- 1.6
(n-nonane), and 29.0 +/- 5.3 (n-decane). The KIEs for
reactions of two alkenes ( cyclohexene and 1-heptene) could
not be determined accurately due to interference from
reaction with ozone, but nevertheless the results clearly
show that the KIEs for reaction of alkenes with OH are
significantly lower than those for saturated hydrocarbons.
The KIEs for reaction of alkanes are smaller than isotope
effects reported in literature for the reactions of NMHCs
artificially labeled with deuterium. The main reason for
this difference is the reduced probability for reaction at a
labeled site for compounds with close to natural deuterium
abundance, although some impact of secondary isotope effects
cannot be ruled out. Still, the KIEs for NMHCs with natural
or close to natural abundance of deuterium are of sufficient
magnitude to allow determination of the extent of chemical
processing of hydrocarbons in the atmosphere using methods
analogous to stable carbon KIE studies. Furthermore, it is
shown that combining stable hydrogen and stable carbon
isotope ratio data has the potential to also provide
valuable information regarding the stable isotope ratios of
emissions, and specifically to test one of the key
assumptions of the stable isotope hydrocarbon clock, the
absence of significant variations of the stable isotope
ratio for the emitted NMHCs.},
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:000220397700005},
doi = {10.1023/B:JOCH.0000021035.49613.f7},
url = {https://juser.fz-juelich.de/record/43163},
}