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@ARTICLE{Alarcn:902288,
author = {Alarcón, Paulo and Bohn, Birger and Berkemeier, Thomas and
Lammel, Gerhard and Pöschl, Ulrich and Zetzsch, Cornelius},
title = {{G}as-{P}hase {R}eaction {K}inetics of the {O}rtho and
{I}pso {A}dducts 1,2,4,5-{T}etramethylbenzene–{OH} with
{O} 2},
journal = {ACS earth and space chemistry},
volume = {5},
number = {9},
issn = {2472-3452},
address = {Washington, DC},
publisher = {ACS Publications},
reportid = {FZJ-2021-04151},
pages = {2243 - 2251},
year = {2021},
abstract = {The reversible reaction of OH radicals with
1,2,4,5-tetramethylbenzene (1245-TeMB, durene) leads to
adducts at the substituted (ipso) and unsubstituted (ortho)
positions of the ring. By the use of flash photolysis for
production and resonance fluorescence for detection of OH,
the gas-phase reactions of O2 with these adducts were
investigated over the temperature range of 300–340 K in He
at 200 mbar. The decay of OH, generated by pulsed vacuum-UV
photolysis of H2O, was monitored under slow-flow conditions
in the presence of 1245-TeMB and O2 at concentrations of up
to 19 × 1012 cm–3 and 2 × 1016 cm–3, respectively.
Triexponential OH decays resulted from the unimolecular
decomposition of the two adducts, representing OH reservoirs
with different stabilities. In the presence of O2,
additional adduct loss pathways exist, leading to faster OH
consumption. Triexponential functions fitted to these decays
were analyzed to obtain rate constants for the reactions of
O2 with both adducts. Rate constants in the range of
(4–13) × 10–15 and (0.3–3) × 10–15 cm3 s–1 were
obtained for the ortho and the ipso adducts, respectively,
depending on temperature and assumptions regarding details
of the underlying mechanism of adduct isomer formation and
isomerization. At O2 concentrations exceeding about 1 ×
1016 cm–3, deviations from a linear dependence of the
adduct loss rates on the O2 concentration indicate an even
more complex mechanism. The validity of the rate constants
is therefore confined to O2 concentrations below 1 × 1016
cm–3. The adduct + O2 rate constants for 1245-TeMB are
greater than the corresponding previously obtained rate
constants for benzene, toluene, and p- and m-xylene but
smaller than those for hexamethylbenzene. The results are
discussed in terms of the current knowledge about the
mechanism of OH-induced degradation of aromatic compounds in
the presence of O2.},
cin = {IEK-8},
ddc = {550},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000697335600006},
doi = {10.1021/acsearthspacechem.1c00230},
url = {https://juser.fz-juelich.de/record/902288},
}