A Computational Re-examination of the Criegee Intermediate–Sulfur Dioxide Reaction

Kuwata, Keith T.; Guinn, Emily J.; Hermes, Matthew R.; Fernandez, Jenna; Mathison, Jon M.; Huang, Ke

doi:10.1021/acs.jpca.5b06565

Cited by 64 publications

(129 citation statements)

References 115 publications

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“…The rate constants from the reactions of sCI + H 2 O and sCI + (H 2 O) 2 range from 1.0 × 10 −14 to 2.0 × 10 −19 cm 3 molecule −1 s −1 and 1.6 × 10 −11 to 2.6 × 10 −14 cm 3 molecule −1 s −1 , respectively (Table ). The rate coefficients range between (2.0–7.0) × 10 −12 cm 3 molecule −1 s −1 for sCI + NO 2 reaction , , , , (2.4–22.0) × 10 −11 cm 3 molecule −1 s −1 for sCI + SO 2 reaction , and (1.0–6.0) × 10 −10 cm 3 molecule −1 s −1 for sCI + carboxylic acid reaction .

\begin{matrix} true \\ right sCI \to Products \end{matrix}

\begin{matrix} true \\ right sCI + H_{2} normalO \to Products \end{matrix}

\begin{matrix} true \\ right sCI + {(H_{2} normalO)}_{2} \to Products \end{matrix}

\begin{matrix} true \\ right sCI + {NO}_{2} \to {NO}_{3} + carbonyl \end{matrix}

\begin{matrix} true \\ right sCI + {SO}_{2} \to {SO}_{3} + carbonyl \end{matrix}

\begin{matrix} true \\ right sCI + RCOOH \to Products \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

Khan

Morris

Galloway

et al. 2017

Int. J. Chem. Kinet.

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Levels of the stabilized Criegee Intermediate (sCI), produced via the ozonolysis of unsaturated volatile organic compounds (VOCs), were estimated at two London urban sites (Marylebone Road and Eltham) and one rural site (Harwell) in the UK over the period of 1998–2012. The steady‐state approximation was applied to data obtained from the NETCEN (National Environmental Technology Centre) database, and the levels of annual average sCI were estimated to be in the range of 30–3000 molecules cm−3 for UK sites. A consistent diurnal cycle of sCI concentration is estimated for the UK sites with increasing levels during daylight hours, peaking just after midday. The seasonal pattern of sCI shows higher levels in spring with peaks around May due to the higher levels of O3. The ozone weekend effect resulted in higher sCI in UK urban areas during weekend. The sCI data were modeled using the information provided by the Air Quality Improvement Research Program (AQIRP) and found that the modeled production was five‐ to six‐fold higher than our estimated data, and therefore the estimated sCI concentrations in this study are thought to be lower estimates only. Compared with nighttime, 1.3‐ to 1.8‐fold higher sCI exists under daytime conditions. Using the levels of sCI estimated at Marylebone Road, globally the oxidation rates of NO2 + sCI (22.4 Gg/yr) and SO2 + sCI (37.6 Gg/yr) in urban areas can increase their effect in the troposphere and potentially further alter the oxidizing capacity of the troposphere. Further investigations of modeled sCI show that CH3CHOO (64%) and CH2OO (13%) are dominant among all contributing sCI at the UK sites.

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\begin{matrix} true \\ right sCI \to Products \end{matrix}

\begin{matrix} true \\ right sCI + H_{2} normalO \to Products \end{matrix}

\begin{matrix} true \\ right sCI + {(H_{2} normalO)}_{2} \to Products \end{matrix}

\begin{matrix} true \\ right sCI + {NO}_{2} \to {NO}_{3} + carbonyl \end{matrix}

\begin{matrix} true \\ right sCI + {SO}_{2} \to {SO}_{3} + carbonyl \end{matrix}

\begin{matrix} true \\ right sCI + RCOOH \to Products \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

Khan

Morris

Galloway

et al. 2017

Int. J. Chem. Kinet.

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“…Please do not adjust margins Please do not adjust margins (3.9 ± 0.7) × 10 -11 ξ (3.80 ± 0.04) × 10 -11 ξ (3.42 ± 0.42) × 10 -11 ϒ (4.1 ± 0.3) × 10 -11 ξ (3.53 ± 0.29) × 10 -11 ϒ (3.3 ± 0.9) × 10 -11 ϒ 4.0 × 10 -10 (3.68 ± 0.02) × 10 -11 298 298 298 293 295 295 295 295 ± 2 Kurtén et al 68 Kuwata et al 69 Welz et al 56 Chhantyal-Pun et al 21 Stone et al 57 Sheps 24 Liu et al 23 Berndt et al 70…”

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confidence: 98%

Criegee intermediates and their impacts on the troposphere

Khan

Percival

Caravan

et al. 2018

Environ. Sci.: Processes Impacts

148

232

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Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 10 cm to 1 × 10 cm, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found to be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (e.g. hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO to form SO, which can go on to form a significant amount of HSO which is a key atmospheric nucleation species and therefore vital to the formation of clouds. The sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.

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“…If, as suggested by , the secondary ozonide (SOZ) formed from the reaction between larger SCI and SO 2 can stabilize and undergo bimolecular reaction without formation of SO 3 , the difference in the rate coefficients for the different experiments could be partly explained. However, more recent theoretical work (Kuwata et al, 2015) found additional low-lying pathways that make collisional stabilization of the SOZ unlikely. Experiments by Carlsson et al (2012) and Ahrens et al (2014) observed high yields of SO 3 close to unity suggesting that the SOZ is not lost under the conditions used, i.e.…”

Section: Missing H 2 So 4 Oxidantmentioning

confidence: 99%

Identifying Criegee intermediates as potential oxidants in the troposphere

Novelli

Hens

Ernest

et al. 2016

Preprint

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We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCI) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the afore-mentioned campaigns is caused at least partially by SCI. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. The background OH concentration also complements the previously underestimated production rate of sulfuric acid and is consistent with its scavenging through the addition of sulphur dioxide. A central estimate of the SCI concentration of ~ 5 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCI, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere

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A Computational Re-examination of the Criegee Intermediate–Sulfur Dioxide Reaction

Cited by 64 publications

References 115 publications

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

An Estimation of the Levels of Stabilized Criegee Intermediates in the UK Urban and Rural Atmosphere Using the Steady-State Approximation and the Potential Effects of These Intermediates on Tropospheric Oxidation Cycles

Criegee intermediates and their impacts on the troposphere

Identifying Criegee intermediates as potential oxidants in the troposphere

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