This title appears in the Scientific Report :
2019
Please use the identifier:
http://dx.doi.org/10.1142/9789813271838_0006 in citations.
Reaction Mechanisms for the Atmospheric Oxidation of Monocyclic Aromatic Compounds
Reaction Mechanisms for the Atmospheric Oxidation of Monocyclic Aromatic Compounds
The atmospheric oxidation of aromatic compounds leads to highly oxidized intermediates with oxygenation ratios O:C nearing or exceeding unity, and contributes efficiently to the formation of secondary organic aerosols and ozone. The intermediates in the mechanism differ strongly from those in alipha...
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Personal Name(s): | Vereecken, Luc (Corresponding author) |
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Contributing Institute: |
Troposphäre; IEK-8 |
Published in: |
Advances in Atmospheric Chemistry / Barker, J R ; : WORLD SCIENTIFIC, 2019, ; ISBN: 978-981-327-182-1 ; doi:10.1142/11031 |
Imprint: |
Singapore
WORLD SCIENTIFIC
2019
|
Physical Description: |
377-527 |
DOI: |
10.1142/9789813271838_0006 |
Document Type: |
Contribution to a book |
Research Program: |
Tropospheric trace substances and their transformation processes |
Publikationsportal JuSER |
The atmospheric oxidation of aromatic compounds leads to highly oxidized intermediates with oxygenation ratios O:C nearing or exceeding unity, and contributes efficiently to the formation of secondary organic aerosols and ozone. The intermediates in the mechanism differ strongly from those in aliphatic or unsaturated compounds oxidation, with multifunctionalization showing cyclic peroxides, epoxides, hydroperoxides, resonance-stabilized alkyl radicals, peroxy- and alkoxy radicals, and other functionalities. The multistep oxidation sequence is complex, with a highly branched mechanism where the relative importance of the competing reactions is highly site- and stereo-specific. Several of the critical steps are reversible, leading to kinetics, and product yields that depend on the reaction conditions. In this chapter, the literature data on the elementary reaction steps in this mechanism are summarized and tabulated, based mostly on the available theoretical work, with support from experimental studies. The influence of substitution on the oxidation mechanism is discussed. Significant progress was made in recent years to understand the chemistry, with several novel reaction steps shown to be of importance. At the same time, the quantification of the reaction kinetics remains limited to information on a subset of compounds, with no available structure–activity relationships predicting substitution-, site-, and stereo-specific rate coefficients. |