Atmospheric Autoxidation of Amines
Kristian H Møller1, Torsten Berndt2, Henrik G Kjaergaard1
1Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark.
Environmental Science & Technology
|August 14, 2020
Summary
Atmospheric amines undergo autoxidation, forming hydroperoxy amides. This pathway is crucial for understanding secondary organic aerosols and atmospheric chemistry.
Area of Science:
- Atmospheric Chemistry
- Chemical Kinetics
- Theoretical Chemistry
Background:
- Autoxidation is a key oxidation process for atmospheric volatile organic compounds.
- Amines are significant atmospheric nitrogen-containing compounds.
- Previous studies have not fully explored amine autoxidation pathways.
Purpose of the Study:
- To investigate the atmospheric autoxidation mechanism of amines using theoretical methods.
- To determine the significance of autoxidation as an atmospheric pathway for amines.
- To identify the products of amine autoxidation and their atmospheric implications.
Main Methods:
- High-level theoretical multiconformer transition-state theory calculations.
- Study of trimethylamine (TMA), dimethylamine, and diethylamine.
- Experimental confirmation for TMA autoxidation products.
Main Results:
- Initial hydrogen shift reactions in amines exhibit rate coefficients > 0.1 s-1.
- Autoxidation is confirmed as an important atmospheric pathway for amines.
- Hydroperoxy amides, a novel class of nitrogen-containing compounds, are formed.
Conclusions:
- Amine autoxidation efficiently produces hydroperoxy amides.
- This process has significant implications for secondary organic aerosol formation and growth.
- Amine autoxidation may influence atmospheric hydroxyl radical (OH) recycling.
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