Highly Efficient Autoxidation of Triethylamine
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Highly Efficient Autoxidation of Triethylamine. / Kjærgaard, Eva R.; Møller, Kristian H.; Berndt, Torsten; Kjaergaard, Henrik G.
In: The journal of physical chemistry. A, Vol. 127, No. 41, 2023, p. 8623-8632.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Highly Efficient Autoxidation of Triethylamine
AU - Kjærgaard, Eva R.
AU - Møller, Kristian H.
AU - Berndt, Torsten
AU - Kjaergaard, Henrik G.
PY - 2023
Y1 - 2023
N2 - Autoxidation has been acknowledged as a major oxidation pathway in a broad range of atmospherically important compounds including isoprene and monoterpenes. More recently, autoxidation has also been identified as central and even dominant in the atmospheric oxidation of the rather small nonhydrocarbons dimethyl sulfide (DMS) and trimethylamine (TMA). Here, we find even faster autoxidation in the aliphatic amine triethylamine (TEA). The atmospherically dominating autoxidation leads to highly oxygenated and functionalized compounds. Products with as many as three hydroperoxy (OOH) groups and an O:C ratio larger than 1 are formed. We present theoretical multiconformer transition-state theory (MC-TST) calculations of the unimolecular reactions in the autoxidation following the OH + TEA reaction and calculate peroxy radical H-shift rate coefficients >20 s-1 for the first two generations of H-shifts. The efficient autoxidation in TEA is verified by the observation of the proposed highly oxidized products and radicals in flow-tube experiments. We find that the initial OH hydrogen abstraction at the α-carbon is strongly favored, with the β-carbon abstraction yield being less than a few percent.
AB - Autoxidation has been acknowledged as a major oxidation pathway in a broad range of atmospherically important compounds including isoprene and monoterpenes. More recently, autoxidation has also been identified as central and even dominant in the atmospheric oxidation of the rather small nonhydrocarbons dimethyl sulfide (DMS) and trimethylamine (TMA). Here, we find even faster autoxidation in the aliphatic amine triethylamine (TEA). The atmospherically dominating autoxidation leads to highly oxygenated and functionalized compounds. Products with as many as three hydroperoxy (OOH) groups and an O:C ratio larger than 1 are formed. We present theoretical multiconformer transition-state theory (MC-TST) calculations of the unimolecular reactions in the autoxidation following the OH + TEA reaction and calculate peroxy radical H-shift rate coefficients >20 s-1 for the first two generations of H-shifts. The efficient autoxidation in TEA is verified by the observation of the proposed highly oxidized products and radicals in flow-tube experiments. We find that the initial OH hydrogen abstraction at the α-carbon is strongly favored, with the β-carbon abstraction yield being less than a few percent.
U2 - 10.1021/acs.jpca.3c04341
DO - 10.1021/acs.jpca.3c04341
M3 - Journal article
C2 - 37802497
AN - SCOPUS:85174751552
VL - 127
SP - 8623
EP - 8632
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
SN - 1089-5639
IS - 41
ER -
ID: 371612925