Highly Efficient Autoxidation of Triethylamine.
J Phys Chem A
; 127(41): 8623-8632, 2023 Oct 19.
Article
em En
| MEDLINE
| ID: mdl-37802497
ABSTRACT
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 OC 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 ß-carbon abstraction yield being less than a few percent.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
Dinamarca