Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO<sub>2</sub>, H<sub>2</sub>O and decomposition under boundary layer conditions

Newland, Mike J.; Rickard, Andrew R.; Alam, Mohammed S.; Vereecken, Luc; Muñoz, Amalia; Ródenas, Milagros; Bloss, William J.

doi:10.1039/c4cp04186k

Cited by 126 publications

(186 citation statements)

References 54 publications

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“…Previous studies of ozonolysis of 2,3-dimethyl-2-butene (tetramethyl ethylene, R 1 = R 2 = R 3 = R 4 = CH 3 ) (20,28,34) have provided some information about the (CH 3 ) 2 COO reactions with H 2 O and with SO 2 . But, the results are far from consistency.…”

Section: Discussionmentioning

confidence: 99%

“…Thus, we may simplify the mechanism by assuming k 2 [M] >> k 3 , unless the pressure is low. (R4) may be a slow reaction, but if there are no other competing processes, the yield of R4 may still be high, as indicated by previous ozonolysis studies (20,28,34). The best fit of Eq.…”

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confidence: 89%

“…Whereas studies (17)(18)(19)(20) (24) have reported that the antiform of methyl-substituted CI (CH 3 CHOO, R 1 = H in Fig. 1) reacts with water vapor much faster than the syn-form (R 1 = CH 3 in Fig.…”

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confidence: 99%

“…1) does. Quantum-chemical investigations (25)(26)(27) as well as studies of alkene ozonolysis (20,28) SO 2 , these CIs may accumulate to higher concentrations and have higher probability to oxidize atmospheric SO 2 . Table 1 shows selected rate coefficients for relevant CI reactions and the effective first-order decay rate coefficients (k eff ) of small CIs under an atmospheric condition.…”

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confidence: 99%

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Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Huang

Chao

Lin

2015

Proc. Natl. Acad. Sci. U.S.A.

228

276

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Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO 2 , which produces SO 3 and subsequently H 2 SO 4 , an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH 3 ) 2 COO with water vapor and with SO 2 were directly measured via UV absorption of (CH 3 ) 2 COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH 3 ) 2 COO is not fast enough (k H2O < 1.5 × 10 −16 cm 3 s −1 ) to consume atmospheric (CH 3 ) 2 COO significantly and (ii) (CH 3 ) 2 COO reacts with SO 2 at a near-gas-kinetic-limit rate (k SO2 = 1.3 × 10 −10 cm 3 s −1 ). These observations imply a significant fraction of atmospheric (CH 3 ) 2 COO may survive under humid conditions and react with SO 2 , very different from the case of the simplest Criegee intermediate CH 2 OO, in which the reaction with water dimer predominates in the CH 2 OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH 3 ) 2 COO with SO 2 , suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere. Ozonolysis of unsaturated hydrocarbons produces highly reactive Criegee intermediates (CIs) (1), which may (i) decompose to radical species like OH radicals or (ii) react with a number of atmospheric species, for example, with SO 2 to form SO 3 and with NO 2 to form NO 3 (2, 3). The SO 2 oxidation by CIs has gained special attentions because the SO 3 product would be converted into H 2 SO 4 , an important constituent of aerosols and acid rain (4-8). For example, Mauldin et al. (4) (2) demonstrated an efficient method to prepare a CI in a laboratory by the reaction of iodoalkyl radical with O 2 (for example, CH 2 I + O 2 → CH 2 OO + I). This method can produce a CI of high enough concentration that allows direct detection. With photoionization mass spectrometry (PIMS) detection, Welz et al. (2) measured the rate coefficients of the simplest CI (CH 2 OO) reactions with SO 2 and NO 2 . Notably, these new rate coefficients, confirmed by a few later investigations (9-11), are orders of magnitude larger than those previously used (12, 13) in atmospheric models (e.g., MCM v3.3, available at mcm.leeds. ac.uk/MCM/browse.htt?species=CH2OO), suggesting a greater role of CIs in atmospheric chemistry. This result also indicates previous ozonolysis analyses may be affected by complicated and partly unknown side reactions and may contain errors in some of the reported rate coefficients.Typical...

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 89%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Huang

Chao

Lin

2015

Proc. Natl. Acad. Sci. U.S.A.

228

276

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“…7 Because SCIs are readily consumed, they have very low steady-state concentrations, 8 and consequently their fate in the atmosphere is not well established. 1 To provide a relatively clean source of SCIs for spectroscopic, 9-21 dynamics, [22][23][24][25][26] and kinetics studies, [27][28][29][30][31][32][33][34][35][36] SCIs are almost exclusively made from photo-oxidation reactions of (R 1 R 2 )CI 2 in the presence of O 2 (where R 1 /R 2 represent hydrogen atoms or alkyl radicals To provide accurate rate constants and to aid experimental measurements, unimolecular decomposition rate constants of syn-CH 3 CHOO under atmospheric conditions are computed here from first principles using Miller's semiclassical transition state theory (SCTST) [41][42][43][44][45] in combination with a two-dimensional master equation (2DME) approach. 7,46 This chemical kinetics analysis is performed using a high accuracy potential energy surface that is constructed with a modification of the HEAT protocol.…”

Section: Introductionmentioning

confidence: 99%

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

Nguyen

McCaslin

McCarthy

et al. 2016

The Journal of Chemical Physics

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The thermal decomposition of syn-ethanal-oxide (syn-CH 3 CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH 3 CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH 3 CHOO. Thus, the title reaction should be included into atmospheric modeling. The fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated. Published by AIP Publishing. [http://dx

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Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

Huang

Wang

Shan

et al. 2023

J Chinese Chemical Soc

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Secondary organic aerosol (SOA) produced by ozonolysis of styrene and other alkene compounds is a major part of fine particles in urban atmospheres. The atmospheric ozonolysis process of styrene is simulated in a smog chamber, and the formed SOA particles are detected on-line by a synchronous radiation vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) in this study. Through molecular ion peaks in the photonionization mass spectra of SOA and the corresponding photoionization efficiency curve, combined with off-line measurement verification of ultraviolet visible and infrared absorption spectra, it is determined that formaldehyde, formic acid, benzene, phenol, benzaldehyde, and benzoic acid are the main constituents of styrene SOA. These provide new information for studying the atmospheric ozonolysis oxidation mechanism of styrene. VUV-PIMS can get over complicated sample preparation procedures, secondary pollution, and other shortcomings of the off-line method and is a useful instrument to measure constituents and unveil the formation process of SOA particles.

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Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO₂, H₂O and decomposition under boundary layer conditions

Cited by 126 publications

References 54 publications

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

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Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions

Cited by 126 publications

References 54 publications

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO 2

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO 2

Communication: Thermal unimolecular decomposition of syn-CH3CHOO: A kinetic study

Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

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Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO₂, H₂O and decomposition under boundary layer conditions

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂