Theoretical studies of the hydration reactions of stabilized Criegee intermediates from the ozonolysis of β-pinene

RSC Advances ◽  
2014 ◽  
Vol 4 (54) ◽  
pp. 28490 ◽  
Author(s):  
Xiao-Xiao Lin ◽  
Yi-Rong Liu ◽  
Teng Huang ◽  
Kang-Ming Xu ◽  
Yang Zhang ◽  
...  
Keyword(s):  
Theoretical Studies ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

scholarly journals Measurement-model comparison of stabilized Criegee Intermediate and Highly Oxygenated Molecule production in the CLOUD chamber

2017 ◽  
Author(s):  
Nina Sarnela ◽  
Tuija Jokinen ◽  
Jonathan Duplissy ◽  
Chao Yan ◽  
Tuomo Nieminen ◽  
...  
Keyword(s):  
Sulphuric Acid ◽  
Model Comparison ◽  
Cloud Condensation Nuclei ◽  
Measurement Model ◽  
Cloud Chamber ◽  
Oxidation Products ◽  
Atmospheric Oxidation ◽  
European Organization ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Atmospheric oxidation is an important phenomenon, which produces large quantities of low-volatile compounds such as sulphuric acid and oxidised organic compounds. Such species may be involved in nucleation of particles and enhance their subsequent growth to reach the size of cloud condensation nuclei (CCN). In this study, we investigate α-pinene, the most abundant monoterpene globally, and its oxidation products formed through the ozonolysis in the Cosmic Leaving OUtdoors Droplets (CLOUD) chamber at CERN (the European Organization for Nuclear Research). By scavenging hydroxyl radicals (OH) with hydrogen (H2), we were able to investigate the formation of Highly Oxygenated Molecules (HOM) purely driven by ozonolysis, and study the oxidation of sulphur dioxide (SO2) driven by stabilized Criegee Intermediates (sCI). We measured the concentrations of HOM and sulphuric acid with a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer and compared the measured concentrations with simulated concentrations calculated with a dynamic model. We found molar yields in the range of 3.5–6.5 % for the HOM formation and 22–32 % for the formation of stabilized Criegee Intermediates by fitting our model to the measured concentrations. The simulated time evolution of the ozonolysis products was in good agreement with measured concentrations except that in some of the experiments sulphuric acid formation was faster than simulated. The results shown here are consistent with the recently published yields for HOM formation from different laboratory experiments. Together with the sCI yields, these results help to understand atmospheric oxidation processes better and make the reaction parameters more comprehensive for broader use.

Computational Study of the Reaction between Biogenic Stabilized Criegee Intermediates and Sulfuric Acid

2007 ◽  
Vol 111 (17) ◽  
pp. 3394-3401 ◽  
Author(s):  
Theo Kurtén ◽  
Boris Bonn ◽  
Hanna Vehkamäki ◽  
Markku Kulmala
Keyword(s):  
Sulfuric Acid ◽  
Computational Study ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

scholarly journals Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

2014 ◽  
Vol 14 (22) ◽  
pp. 12143-12153 ◽  
Author(s):  
M. Sipilä ◽  
T. Jokinen ◽  
T. Berndt ◽  
S. Richters ◽  
R. Makkonen ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Relative Humidity ◽  
Organic Acids ◽  
Rate Coefficient ◽  
Atmospheric Oxidation ◽  
Minor Importance ◽  
General Role ◽  
Oxidation Processes ◽  
Criegee Intermediates ◽  
Stabilized Criegee Intermediates

Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO2, atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) /k(sCI + SO2), was determined at relative humidities of 10 and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0–2.4) × 1012 molecules cm−3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO2) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO2.

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