Spectroscopic Characterization of the Reaction Products between the Criegee Intermediate CH<sub>2</sub>OO and HCl

Cabezas, Carlos; Endo, Yasuki

doi:10.1002/cphc.201700446

Cited by 17 publications

(10 citation statements)

References 29 publications

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“…This indicates that the pre-reactive complex in the latter two reactions promptly reacts, in agreement with low reaction barrier predicted by theoretical calculations [68,117,143]. No systematic experiments have been performed for yield measurement of MFOHPs at ambient conditions from the insertion reactions.…”

Section: Figuresupporting

confidence: 80%

“…They were also able to observe decomposition of one of the HPMF conformers to formic acid anhydride, consistent with previous static chamber studies. Endo and co-workers have observed MFOHP products from CH2OO + HCl [143], CH2OO + HCOOH [144] and CH2OO + H2O/(H2O)2 [101] reactions using Fourier transform microwave spectroscopy. They were also able to observe pre-reactive complex formation in the CH2OO + H2O/(H2O)2 reaction system [142], as shown in Figure 9, but not in the CH2OO + HCl [143] and CH2OO + HCOOH reaction systems [144].…”

Section: Figurementioning

confidence: 99%

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Criegee intermediates: production, detection and reactivity

Chhantyal-Pun

Khan

Taatjes

et al. 2020

International Reviews in Physical Chemistry

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In the context of tropospheric chemistry, Criegee intermediates denote carbonyl oxides with biradical / zwitterionic character (R1R2COO) that form during the ozonolysis of alkenes. First discovered almost 70 years ago, stabilized versions of Criegee intermediates formed via collisional removal of excess energy have interesting kinetic and mechanistic properties. The direct production and detection of these intermediates were not reported in the literature until 2008. However, recent advances in their generation through the ultraviolet irradiation of the corresponding diiodoalkanes in excess O2 and detection by various spectroscopic techniques (photoionization, ultraviolet, infrared, microwave and mass spectrometry) have shown that these species can react rapidly with closed shell molecules, in many cases at or exceeding the classical gas-kinetic limit, via multiple reaction pathways. These reactions can be complex, and laboratory measurements of products and the temperature and pressure dependence of the reaction kinetics have also revealed unusual behaviour. The potential role of these intermediates in atmospheric chemistry is significant, altering models of the oxidising capacity of the Earth's atmosphere and the rate of generation of secondary organic aerosol.

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Section: Figuresupporting

confidence: 80%

Section: Figurementioning

confidence: 99%

Criegee intermediates: production, detection and reactivity

Chhantyal-Pun

Khan

Taatjes

et al. 2020

International Reviews in Physical Chemistry

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“…In reactions with CO, NO, SO 2 , and NO 2 , ,,, CI acts as an oxygen atom donor. In reactions with atmospheric species contain hydrogen atoms, such as H 2 O, NH 3 , CH 4 , HCl et al, ,,− it inserts itself into the O–H, N–H, or C–H bond, forming a substituted peroxide. All of these possible reaction mechanisms have been applied to the CI + acrolein reaction.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH₂OO with Acrolein

et al. 2018

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The detailed reaction mechanism and kinetics of Criegee intermediate CH 2 OO with acrolein were investigated. CH 2 OO may add to the CO or CC double bond of acrolein to form a five-membered ring adducts, and it may also insert the terminal oxygen atom or insert itself into the C−H bond of acrolein. The addition reactions are more favorable in energy than the insertion reactions. The master equation calculation show that the most competitive reaction channel is the 1,3-cycloaddition of CH 2 OO across the CO double bond forming the secondary ozonide (SOZ). The lowest energy pathway for SOZ decomposition involves the formation of the singlet biradical intermediate by ring fission, the H-shift isomerization and the dissociation to products. The calculated overall rate constant decreases as the temperature increases from 200 to 500 K, and at 298 K, it is 4.31 × 10 −12 cm 3 molecule −1 s −1 . The branching ratio of collisionally stabilized SOZ increases with the increase of pressure. At low pressure, some of SOZ decompose to HCOOH + acrolein or HCHO + acrylic acid. The pressure dependence of this reaction is in agreement with the previous theoretical and experimental observations for the reaction of CH 2 OO with acetaldehyde.

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“…Subsequent reaction and formation of the alkoxy radical would be expected to yield a carbonyl and NO 2 . The main products of reaction of SCI with the inorganic acid HCl have been predicted to be chlorohydroperoxides (Reaction R10) (Foreman et al, 2016;Vereecken, 2017), with these products observed experimentally for CH 2 OO + HCl (Cabezas and Endo, 2017;Taatjes et al, 2021) and CH 3 CHOO + HCl (Cabezas and Endo, 2018). The main product of reaction with HNO 3 has been predicted to be hydroperoxy nitrates (Reaction R11) (Foreman et al, 2016;Raghunath et al, 2017;Vereecken, 2017).…”

Section: Bimolecular Reactions Of Scimentioning

confidence: 88%

Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

Newland

Mouchel‐Vallon

Valorso³

et al. 2022

Atmos. Chem. Phys.

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Abstract. Reaction with ozone is an important atmospheric removal process for alkenes. The ozonolysis reaction produces carbonyls and carbonyl oxides (Criegee intermediates, CI), which can rapidly decompose to yield a range of closed shell and radical products, including OH radicals. Consequently, it is essential to accurately represent the complex chemistry of Criegee intermediates in atmospheric models in order to fully understand the impact of alkene ozonolysis on atmospheric composition. A mechanism construction protocol is presented which is suitable for use in automatic mechanism generation. The protocol defines the critical parameters for describing the chemistry following the initial reaction, namely the primary carbonyl/CI yields from the primary ozonide fragmentation, the amount of stabilisation of the excited CI, the unimolecular decomposition pathways, rates and products of the CI, and the bimolecular rates and products of atmospherically important reactions of the stabilised CI (SCI). This analysis implicitly predicts the yield of OH from the alkene–ozone reaction. A comprehensive database of experimental OH, SCI and carbonyl yields has been collated using reported values in the literature and used to assess the reliability of the protocol. The protocol provides estimates of OH, SCI and carbonyl yields with root mean square errors of 0.13 and 0.12 and 0.14, respectively. Areas where new experimental and theoretical data would improve the protocol and its assessment are identified and discussed.

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Spectroscopic Characterization of the Reaction Products between the Criegee Intermediate CH₂OO and HCl

Cited by 17 publications

References 29 publications

Criegee intermediates: production, detection and reactivity

Criegee intermediates: production, detection and reactivity

Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH₂OO with Acrolein

Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

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Spectroscopic Characterization of the Reaction Products between the Criegee Intermediate CH2OO and HCl

Cited by 17 publications

References 29 publications

Criegee intermediates: production, detection and reactivity

Criegee intermediates: production, detection and reactivity

Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH2OO with Acrolein

Estimation of mechanistic parameters in the gas-phase reactions of ozone with alkenes for use in automated mechanism construction

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Spectroscopic Characterization of the Reaction Products between the Criegee Intermediate CH₂OO and HCl

Theoretical Study on the Reaction Mechanism and Kinetics of Criegee Intermediate CH₂OO with Acrolein