FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene

Niki, H.; Maker, P. D.; Savage, C. M.; Breitenbach, L. P.; Hurley, M. D.

doi:10.1021/j100288a035

Cited by 203 publications

(245 citation statements)

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“…This is likely to be a significant atmospheric sink for syn-SCIs because of their slow reaction with water vapour. Previous studies have identified the hydroperoxide rearrangement as dominant for SCIs with a syn configuration, determining their overall unimolecular decomposition rate (Niki et al, 1987;Rickard et al, 1999;Martinez and Herron, 1987;Johnson and Marston, 2008). This route has been shown to be a substantial non-photolytic source of atmospheric oxidants (Niki et al, 1987;Alam et al, 2013).…”

Section: Stabilised Criegee Intermediate Kineticsmentioning

confidence: 97%

“…Previous studies have identified the hydroperoxide rearrangement as dominant for SCIs with a syn configuration, determining their overall unimolecular decomposition rate (Niki et al, 1987;Rickard et al, 1999;Martinez and Herron, 1987;Johnson and Marston, 2008). This route has been shown to be a substantial non-photolytic source of atmospheric oxidants (Niki et al, 1987;Alam et al, 2013). CIs formed in the anti configuration are thought to primarily undergo rearrangement and possibly decomposition via a dioxirane intermediate ("the acid/ester channel"), producing a range of daughter products and contributing to the observed overall HO x radical yield (Johnson and Marston, 2008;Alam et al, 2013).…”

Section: Stabilised Criegee Intermediate Kineticsmentioning

confidence: 99%

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Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO2, H2O and dimethyl sulfide

et al. 2015

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Abstract. Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO 2 and NO 2 in the atmosphere; however the significance of this chemistry for SO 2 processing (affecting sulfate aerosol) and NO 2 processing (affecting NO x levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO 2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO 2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H 2 O. Under excess SO 2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + H 2 O) / k(SCI + SO 2 ), of 3.1 (±0.5) × 10 −5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO 2 ) is 3.0 (±3.2) × 10 11 cm −3 . Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprenederived SCIs are unlikely to make a substantial contribution to gas-phase SO 2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO 2 removal in the isopreneozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO 2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS) / k(SCI + SO 2 ), of 3.5 (±1.8). This result suggests that SCIs may contribute to the oxidation of DMS in the atmosphere and that this process could therefore influence new particle formation in regions impacted by emissions of unsaturated hydrocarbons and DMS.

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Section: Stabilised Criegee Intermediate Kineticsmentioning

confidence: 97%

Section: Stabilised Criegee Intermediate Kineticsmentioning

confidence: 99%

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO2, H2O and dimethyl sulfide

et al. 2015

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“…OH generation from excited Criegee biradicals is mainly assumed to occur by the 'hydroperoxide mechanism', involving isomerisation by a 1,4 H atom shift followed by decomposition of the resulant α, β-unsaturated hydroperoxide intermediate, as first proposed by Niki et al (1987):…”

Section: The Reactions Of the Excited Criegee Biradicalsmentioning

confidence: 99%

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

et al. 2003

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Abstract. Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g., α-and β-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the α-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in α-pinene/NO X photo-oxidation experiments carried out in the European Photoreactor (EU-PHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM.

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“…Products from the O 3 -and OH-initiated TME oxidation are formaldehyde, methanol and acetone as well as some minor compounds (Niki et al, 1987;Tuazon et al, 1997Tuazon et al, , 1998. The vapor pressures of these species are too high to take part into aerosol nucleation and growth processes and so are omitted from the model.…”

Section: Modeling Of Voc Oxidationmentioning

confidence: 99%

New particle formation from the oxidation of direct emissions of pine seedlings

et al. 2009

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Abstract. Measurements of particle formation following the gas phase oxidation of volatile organic compounds (VOCs) emitted by Scots pine (Pinus sylvestris L.) seedlings are reported. Particle formation and condensational growth both from ozone (O 3 ) and hydroxyl radical (OH) initiated oxidation of pine emissions (about 20-120 ppb) were investigated in a smog chamber. During experiments, tetramethylethylene (TME) and 2-butanol were added to control the concentrations of O 3 and OH. Particle formation and condensational growth rates were interpreted with a chemical kinetic model. Scots pine emissions mainly included α-pinene, β-pinene, 3 -carene, limonene, myrcene and β-phellandrene, composing more than 95% of total emissions. Modeled OH concentrations in the O 3 -and OH-induced experiments were on the order of ∼10 6 molecules cm −3 . Our results demonstrate that OH-initiated oxidation of VOCs plays an important role in the nucleation process during the initial new particle formation stage. The highest average particle formation rate of 360 cm −3 s −1 was observed for the OH-dominated nucleation events and the lowest formation rate of less than 0.5 cm −3 s −1 was observed for the case with only O 3 present as an oxidant. In contrast to the particle formation process, ozonolysis of monoterpenes appears to be much more efficient to the aerosol growth process following nucleation.Correspondence to: L. Q. Hao (liqing@uku.fi) Higher contributions of more oxygenated products to the SOA mass loadings from OH-dominated oxidation systems were found as compared to the ozonolysis systems. Comparison of mass and volume distributions from the aerosol mass spectrometer and differential mobility analyzer yields estimated SOA effective densities of 1.34±0.06 g cm −3 for the OH+O 3 oxidation systems and 1.38±0.03 g cm −3 for the O 3 dominated chemistry.

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FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene

Abstract: result by pulse radiolysis of solid PMMA.16 Consequently, if mechanism 3 is valid, positive charge may transfer in the polymer to react with the polymer anion.

Cited by 203 publications

References 1 publication

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

New particle formation from the oxidation of direct emissions of pine seedlings

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FTIR spectroscopic study of the mechanism for the gas-phase reaction between ozone and tetramethylethylene

Abstract: result by pulse radiolysis of solid PMMA.16 Consequently, if mechanism 3 is valid, positive charge may transfer in the polymer to react with the polymer anion.

Cited by 203 publications

References 1 publication

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O and dimethyl sulfide

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O and dimethyl sulfide

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

New particle formation from the oxidation of direct emissions of pine seedlings

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Product

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Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO<sub>2</sub>, H<sub>2</sub>O and dimethyl sulfide