Journal cover Journal topic
Atmospheric Chemistry and Physics An interactive open-access journal of the European Geosciences Union
Atmos. Chem. Phys., 16, 15425-15432, 2016
https://doi.org/10.5194/acp-16-15425-2016
© Author(s) 2016. This work is distributed under
the Creative Commons Attribution 3.0 License.
Research article
13 Dec 2016
The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact
Joel D. Rindelaub, Carlos H. Borca, Matthew A. Hostetler, Jonathan H. Slade, Mark A. Lipton, Lyudmila V. Slipchenko, and Paul B. Shepson Department of Chemistry, Purdue University, West Lafayette, IN 47907, USA
Abstract. The production of atmospheric organic nitrates (RONO2) has a large impact on air quality and climate due to their contribution to secondary organic aerosol and influence on tropospheric ozone concentrations. Since organic nitrates control the fate of gas phase NOx (NO + NO2), a byproduct of anthropogenic combustion processes, their atmospheric production and reactivity is of great interest. While the atmospheric reactivity of many relevant organic nitrates is still uncertain, one significant reactive pathway, condensed phase hydrolysis, has recently been identified as a potential sink for organic nitrate species. The partitioning of gas phase organic nitrates to aerosol particles and subsequent hydrolysis likely removes the oxidized nitrogen from further atmospheric processing, due to large organic nitrate uptake to aerosols and proposed hydrolysis lifetimes, which may impact long-range transport of NOx, a tropospheric ozone precursor. Despite the atmospheric importance, the hydrolysis rates and reaction mechanisms for atmospherically derived organic nitrates are almost completely unknown, including those derived from α-pinene, a biogenic volatile organic compound (BVOC) that is one of the most significant precursors to biogenic secondary organic aerosol (BSOA). To better understand the chemistry that governs the fate of particle phase organic nitrates, the hydrolysis mechanism and rate constants were elucidated for several organic nitrates, including an α-pinene-derived organic nitrate (APN). A positive trend in hydrolysis rate constants was observed with increasing solution acidity for all organic nitrates studied, with the tertiary APN lifetime ranging from 8.3 min at acidic pH (0.25) to 8.8 h at neutral pH (6.9). Since ambient fine aerosol pH values are observed to be acidic, the reported lifetimes, which are much shorter than that of atmospheric fine aerosol, provide important insight into the fate of particle phase organic nitrates. Along with rate constant data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.

Citation: Rindelaub, J. D., Borca, C. H., Hostetler, M. A., Slade, J. H., Lipton, M. A., Slipchenko, L. V., and Shepson, P. B.: The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact, Atmos. Chem. Phys., 16, 15425-15432, https://doi.org/10.5194/acp-16-15425-2016, 2016.
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This study provides new insight into the hydrolysis reaction mechanism, which was elucidated for atmospherically relevant organic nitrates using kinetic measurements, product identification, and theoretical calculations. The results help broaden our knowledge of the organic chemistry that impacts the fate of NOx, ozone production, aerosol phase processing, and aerosol composition.
This study provides new insight into the hydrolysis reaction mechanism, which was elucidated for...
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