Atmospheric Formation of OH Radicals and H2O2 from Alkene Ozonolysis under Humid Conditions

Anglada, Josep M.; Aplincourt, Philippe; Bofill, Josep María; Cremer, Dieter

doi:10.1002/1439-7641(20020215)3:2<215::aid-cphc215>3.3.co;2-v

Cited by 41 publications

(105 citation statements)

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“…Historically, research has focused on the reaction of sCIs with water and it was assumed that HCOOH production was the major reaction pathway. 48 However, recent findings 21,23,24,25,31,34,49 Long et al 19 Lin et al 52 Anglada et al 53 Anglada et al 54 Ryzhkov and Ariya 55 Welz et al 56 Ouyang et al 25 Stone et al 57 Newland et al 27 Chao et al 58 Berndt et al 20 Sheps et al 50 syn-CH3CHOO <4 Long et al 19 Lin et al 52 Anglada et al 53 Anglada et al 54 Ryzhkov and Ariya 55 Taatjes et al 31 Sheps et al 59 Long et al 19 Lin et al 52 Anglada et al 53 Anglada et al 54 Ryzhkov and Ariya 55 Newland et al 29 Taatjes et al 31 Sheps et al 59 Lin et al 60 (CH3)2COO…”

Section: σ(Mvkoo +Macroo)mentioning

confidence: 99%

“…(2.1 ± 0.6) × 10 Anglada et al 53 Anglada et al 54 Ryzhkov and Ariya 55 Newland et al 29 Huang et al 61 Note: ξ The values are from direct monitoring of the sCI decay, ϒ The values are from indirect sCI measurements. ƒ the values from the experiments could not distinguish between the reaction with the water monomer or the dimer reaction.…”

Section: σ(Mvkoo +Macroo)mentioning

confidence: 99%

“…Despite the slow reaction of syn-sCIs, they can go on to provide a source of OH radicals. 54 Alkene ozonolysis favours syn-formation and therefore these reactions can provide an essential source of atmospheric OH, and recent work 53,91 However, the oxidation of NO2 via sCIs was found to be much faster than the reaction of NO + sCI ( Oxidation of SO2 by sCIs was believed to be of little tropospheric importance until relatively recently.…”

Section: 298 297 343mentioning

confidence: 99%

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Criegee intermediates and their impacts on the troposphere

Khan

Percival

Caravan

et al. 2018

Environ. Sci.: Processes Impacts

152

228

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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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Section: σ(Mvkoo +Macroo)mentioning

confidence: 99%

Section: σ(Mvkoo +Macroo)mentioning

confidence: 99%

Section: 298 297 343mentioning

confidence: 99%

See 1 more Smart Citation

Criegee intermediates and their impacts on the troposphere

Khan

Percival

Caravan

et al. 2018

Environ. Sci.: Processes Impacts

152

228

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“…Theoretical calculations on a subset of these possible bimolecular reactions (CH 2 OO with H 2 O, H 2 C¼O, HC(¼O)OH, SO 2 , and CO 2 ) have been done only recently. [3,14,16,69,[85][86][87] These studies indicate that the CH 2 OO is most likely to react with H 2 O, H 2 C¼O, and HC(¼O)OH because of relatively low barriers to addition. Figure 9 depicts proposed mechanisms for the bimolecular reactions of CH 2 OO with H 2 O, H 2 C¼O, and HC(¼O)OH.…”

mentioning

confidence: 94%

First-principles-derived kinetics of the reactions involved in low-temperature dimethyl ether oxidation

Andersen¹,

Carter²

2008

Molecular Physics

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Spin-polarised density functional theory (DFT-B3LYP) energies, harmonic vibrational frequencies, and moments of inertia are used to construct modified Arrhenius rate expressions for elementary steps in chain-propagation and chain-branching pathways for dimethyl ether combustion. Barrierless reactions were treated with variational RRKM theory, and global kinetics were modeled using master equation and perfectly stirred reactor simulations. Our kinetics analysis suggests that the bottleneck along the chain propagation path is the isomerisation of CH 3 OCH 2 OO, contrary to earlier interpretations. Comparing the rate constants for competing decomposition pathways of the key chain-branching intermediate hydroperoxymethyl formate (HPMF), we find that formation of formic acid and the atmospherically relevant Criegee intermediate (CH 2 OO) via a H-bonded adduct may be more favourable than O-O bond scission. Since the latter forms a source of a second OH radical beyond that supplied in chain propagation, which is necessary for explosive combustion, the more favourable pathway to formic acid may inhibit autoignition of the fuel. We predict that the HPMF O-O scission product, OCH 2 OC(¼O)H, most likely directly dissociates to HCO þ HC(¼O)OH. This implies an overabundance of CO at 550-700 K, since HC(¼O)OH is a fairly stable product in this temperature range and facile H abstraction from HCO leads to CO. We find that CO 2 product yields are sensitive to the creation of CH 2 OO and that creation of CH 2 OO is competitive with the O-O scission reaction.

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“…In the gas phase the reaction mechanisms for ozonolysis of ethene, isoprene and various terpenes have been investigated both with experimental studies [6][7][8][9][10] and theoretical calculations [11][12][13][14][15][16]. The fate of the stabilized Criegee intermediate is manifold, it can undergo unimolecular decomposition [11,16,17] or react with surrounding compounds in the atmosphere such as water [7,[17][18][19][20], HO x (=HO + HO 2 ) [21], NO x (=NO + NO 2 ) [22], SO 2 [17,22], CO 2 [17], H 2 SO 4 [23], aldehydes [9,10,17,24], or carboxylic acid [9,24,25]. For example, when the stabilized Criegee intermediates react with an aldehyde, a secondary ozonide (SOZ) is formed.…”

Section: Introductionmentioning

confidence: 99%