Atmospheric Oxidation of Hydroperoxy Amides
Eva R Kjærgaard1, Kristian H Møller1, Henrik G Kjaergaard1
1Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark.
Hydroperoxy amides, formed from tertiary amine oxidation, transform into imides or more oxidized forms. Their atmospheric fate is clarified, revealing slow unimolecular reactions due to their planar structure.
Area of Science:
- Atmospheric Chemistry
- Chemical Kinetics
- Computational Chemistry
Background:
- Hydroperoxy amides are significant products of tertiary amine autoxidation in the atmosphere.
- Their formation mechanism is faster than analogous reactions in ethers and sulfides.
- The atmospheric degradation pathways of hydroperoxy amides were previously unknown.
Purpose of the Study:
- To investigate the atmospheric fate of hydroperoxy and dihydroperoxy amides.
- To elucidate the OH-initiated oxidation pathways of these compounds derived from trimethylamine.
Main Methods:
- Utilized high-level theoretical calculations.
- Studied the hydroxyl radical (OH)-initiated oxidation mechanisms.
- Analyzed pathways under both nitrogen oxide (NO)- and hydroperoxyl radical (HO2)-dominated conditions.
Main Results:
- OH-initiated oxidation predominantly yields imides under NO-rich conditions.
- More highly oxidized hydroperoxy amides are formed under HO2-rich conditions.
- Unimolecular reactions of these amides are unexpectedly slow, attributed to their planar structure.
Conclusions:
- The study clarifies the atmospheric transformation of hydroperoxy amides.
- Product distribution is dependent on atmospheric radical concentrations (NO vs. HO2).
- The inherent structural properties of hydroperoxy amides influence their reactivity.
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