Direct measurements of OH and other product yields from the HO<sub>2</sub> + CH<sub>3</sub>C(O)O<sub>2</sub> reaction
The reaction CH<sub>3</sub>C(O)O<sub>2</sub> + HO<sub>2</sub> → CH<sub>3</sub>C(O)OOH + O<sub>2</sub> (Reaction R5a), CH<sub>3</sub>C(O)OH + O<sub>3</sub> (Reaction R5b), CH<sub>3</sub> + CO<sub>...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Copernicus Publications
2016-03-01
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| Series: | Atmospheric Chemistry and Physics |
| Online Access: | https://www.atmos-chem-phys.net/16/4023/2016/acp-16-4023-2016.pdf |
| Summary: | The reaction CH<sub>3</sub>C(O)O<sub>2</sub> + HO<sub>2</sub> →
CH<sub>3</sub>C(O)OOH + O<sub>2</sub> (Reaction R5a), CH<sub>3</sub>C(O)OH + O<sub>3</sub>
(Reaction R5b), CH<sub>3</sub> + CO<sub>2</sub> + OH + O<sub>2</sub> (Reaction R5c)
was studied in a series of experiments conducted at 1000 mbar and
(293 ± 2) K in the HIRAC simulation chamber. For the first time,
products, (CH<sub>3</sub>C(O)OOH, CH<sub>3</sub>C(O)OH, O<sub>3</sub> and OH) from all three
branching pathways of the reaction have been detected directly and
simultaneously. Measurements of radical precursors (CH<sub>3</sub>OH, CH<sub>3</sub>CHO),
HO<sub>2</sub> and some secondary products HCHO and HCOOH further constrained the
system. Fitting a comprehensive model to the experimental data, obtained over
a range of conditions, determined the branching ratios <i>α</i><sub>(R5a)</sub> = 0.37 ± 0.10, <i>α</i><sub>(R5b)</sub> = 0.12 ± 0.04 and
<i>α</i><sub>(R5c)</sub> = 0.51 ± 0.12 (errors at 2<i>σ</i> level).
Improved measurement/model agreement was achieved using <i>k</i><sub>(R5)</sub> =
(2.4 ± 0.4) × 10<sup>−11</sup> cm<sup>3</sup> molecule<sup>−1</sup> s<sup>−1</sup>,
which is within the large uncertainty of the current IUPAC and JPL
recommended rate coefficients for the title reaction. The rate coefficient
and branching ratios are in good agreement with a recent study performed by
Groß et al. (2014b); taken together, these two studies show that the rate of OH
regeneration through Reaction (R5) is more rapid than previously thought.
GEOS-Chem has been used to assess the implications of the revised rate
coefficients and branching ratios; the modelling shows an enhancement of up
to 5 % in OH concentrations in tropical rainforest areas and increases of
up to 10 % at altitudes of 6–8 km above the equator, compared to
calculations based on the IUPAC recommended rate coefficient and yield. The
enhanced rate of acetylperoxy consumption significantly reduces PAN in remote
regions (up to 30 %) with commensurate reductions in background NO<sub><i>x</i></sub>. |
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| ISSN: | 1680-7316 1680-7324 |