Temperature-dependent kinetics of the atmospheric reaction between CH<sub>2</sub>OO and acetone

Wang, Pengbiao; Truhlar, Donald G.; Xia, Yu; Long, Bo

doi:10.1039/d2cp01118b

Cited by 15 publications

(27 citation statements)

References 97 publications

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“…Therefore, B3LYP/MG3S cannot be used to obtain quantitative enthalpy of activation at 0 K in the CH 2 OO + H 2 O 2 reaction. In addition, CBS-QB3 gives a small MUD of 0.45 kcal/mol in the CH 2 OO + H 2 O 2 reaction in Table , while CBS-QB3 has a larger MUD of 1.48 kcal/mol in the CH 2 OO + CH 3 COCH 3 reaction . Moreover, G4 gives a lower MUD of 0.43 kcal/mol, while G3 and W1BD have larger MUDs of 1.34 kcal/mol, 1.32 kcal/mol, respectively.…”

Section: Resultsmentioning

confidence: 93%

“…In addition, CBS-QB3 gives a small MUD of 0.45 kcal/mol in the CH 2 OO + H 2 O 2 reaction in Table 1, while CBS-QB3 has a larger MUD of 1.48 kcal/mol in the CH 2 OO + CH 3 COCH 3 reaction. 109 Moreover, G4 gives a lower MUD of 0.43 kcal/mol, while G3 and W1BD have larger MUDs of 1.34 kcal/mol, 1.32 kcal/mol, respectively. In particular, W1BD has a small MUD of 0.57 kcal/mol for barrier height without zero-point vibrational energies involved in Table S6.…”

Section: Methodsmentioning

confidence: 94%

“…Previous studies have shown that post-CCSD(T) calculations are required to obtain quantitative barrier heights in Criegee reactions. 40,56,92,108,109 Here, the calculated results show that the contribution of post-CCSD(T) calculations is approximately 0.6 kcal/mol for the enthalpies of activation at 0 K in the CH 2 OO + H 2 O 2 reaction because the MUD of W2X/ CCSD(T)-F2a/cc-pVTZ-F12 is 0.58 kcal/mol, compared to W3X-L/CCSD(T)-F2a/cc-pVTZ-F12 in Table 1. In addition, the contribution of post-CCSD(T) calculations is more significant for the enthalpies of reaction at 0 K than the enthalpies of activation at 0 K in Table S5.…”

Section: Methodsmentioning

confidence: 99%

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Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

2022

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Criegee intermediates (CIs) are generated from the ozonolysis of unsaturated hydrocarbons in the atmosphere. They have an important role in determining the implications of atmospheric bimolecular reactions with other atmospheric species. The reaction between CH2OO and H2O2 plays a crucial role in understanding how CIs impact the HO x budget in the atmosphere. The reaction mechanism and kinetics are critical to atmospheric modeling, which is a prominent challenge in present-day climate change modeling. This is particularly true for bimolecular reactions that involve complex reaction sequences. Here, we report the mechanism and quantitative kinetics of the CH2OO + H2O2 reaction by using a novel dual-level strategy that contains W3X-L//CCSD(T)-F12a/cc-pVTZ-F12 for the transition state theory and M11-L/MG3S functional method for direct dynamics calculations using canonical variational transition state theory with small-curvature tunneling to obtain both recrossing effects and tunneling. The present work shows that the CH2OO + H2O2 reaction has a negative temperature dependency with the decrease in the rate constant of CH2OO + H2O2 from 1.31 × 10–13 cm3 molecule–1 s–1 to 3.80 × 10–14 cm3 molecule–1 s–1 between 200 and 350 K. The calculated results also show that the CH2OO + H2O2 reaction can have an impact on the H2O2 profile under certain atmospheric conditions. The present findings should have implications for the quantitative kinetics of Criegee intermediates with other hydroperoxides.

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Section: Resultsmentioning

confidence: 93%

Section: Methodsmentioning

confidence: 94%

Section: Methodsmentioning

confidence: 99%

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Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

2022

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“…Bimolecular reaction of CIs with carbonyl species such as formaldehyde and acetone can also produce SOZs. 1 − 4 The formation of SOZs occurs not only in the gas phase but also in bulk liquid phases 5 and at gas–liquid/solid interfaces. 6 − 8 SOZs are categorized as both organic peroxides and reactive oxygen species.…”

Section: Introductionmentioning

confidence: 99%

“…These reactions are mediated by carbonyl oxides known as Criegee intermediates (CIs), which can undergo intramolecular rearrangement to form 1,2,4-trioxolanes, known as secondary ozonides (SOZs). Bimolecular reaction of CIs with carbonyl species such as formaldehyde and acetone can also produce SOZs. − The formation of SOZs occurs not only in the gas phase but also in bulk liquid phases and at gas–liquid/solid interfaces. − SOZs are categorized as both organic peroxides and reactive oxygen species . Because of their ubiquity, SOZs are deemed to play key roles in atmospheric, environmental, and biological chemistry …”

Section: Introductionmentioning

confidence: 99%

Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media

et al. 2022

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1,2,4-Trioxolanes, known as secondary ozonides (SOZs), are key products of ozonolysis of biogenic terpenoids. Functionalized terpenoid-derived SOZs are readily taken up into atmospheric aerosols; however, their condensed-phase fates remain unknown. Here, we report the results of a time-dependent mass spectrometric investigation into the liquid-phase fates of C 10 and C 13 SOZs synthesized by ozonolysis of a C 10 monoterpene alcohol (α-terpineol) in water:acetone (1:1 = vol:vol) mixtures. Isomerization of Criegee intermediates and bimolecular reaction of Criegee intermediates with acetone produced C 10 and C 13 SOZs, respectively, which were detected as their Na + -adducts by positive-ion electrospray mass spectrometry. Use of CD 3 COCD 3 , D 2 O, and H 2 18 O solvents enabled identification of three types of C 13 SOZs (aldehyde, ketone, and lactol) and other products. These SOZs were surprisingly stable in water:acetone (1:1) mixtures at T = 298 K, with some persisting for at least a week. Theoretical calculations supported the high stability of the lactol-type C 13 SOZ formed from the aldehyde-type C 13 SOZ via intramolecular rearrangement. The present results suggest that terpenoid-derived SOZs can persist in atmospheric condensed phases, potentially until they are delivered to the epithelial lining fluid of the pulmonary alveoli via inhaled particulate matter, where they may exert hitherto unrecognized adverse health effects.

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Temperature‐dependent kinetics of the reactions of CH₂OO with acetone, biacetyl, and acetylacetone

Cornwell

Enders

Harrison

et al. 2022

Int J of Chemical Kinetics

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Temperature‐dependent rate constants for the reactions of CH2OO with acetone (Ac), biacetyl (BiAc), and acetylacetone (AcAc) have been measured over the range 275–335 K using a flash photolysis, transient absorption spectroscopy technique. The measurements were performed at a total pressure of ∼80 Torr in N2 bath gas, which corresponds to the high‐pressure limit for these reactions. All three reactions show linear Arrhenius plots with negative temperature dependences. Rate constants increase in the order Ac < AcAc « BiAc across the temperature range; at 295 K the rate constants are kAc = (4.8 ± 0.4) × 10–13 cm3 s–1, kAcAc = (8.0 ± 0.7) × 10–13 cm3 s–1, and kBiAc = (1.10 ± 0.09) × 10–11 cm3 s–1. Sensitivity to temperature, characterized by the magnitude of the negative activation energy, increases in the order AcAc < BiAc < Ac (Ea/R values of –1830 ± 170 K, –1260 ± 170 K, and –460 ± 180 K, respectively). CBS‐QB3 calculations show that the Ac and BiAc reactions proceed via formation of an entrance channel complex followed by 1,3‐dipolar cycloaddition to form secondary ozonide products via a submerged transition state. For the BiAc reaction, the rate limiting step appears to be rearrangement of a long‐range van der Waals complex into the short‐range complex that subsequently leads directly to the cycloaddition transition state with a very low energy barrier. The calculations show that two reaction pathways are competitive for AcAc with nearly identical transition state free energies (ΔG° = +10.1 kcal mol–1 at 298 K) found for cycloaddition at the C=O and at the C=C site of the dominant enolone tautomer. The weak temperature dependence observed is likely due to competition between these pathways.

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Temperature-dependent kinetics of the atmospheric reaction between CH₂OO and acetone

Abstract: Criegee intermediates are important oxidants produced in the ozonolysis of alkenes in the atmosphere. Quantitative kinetics of the reactions of Criegee intermediates are required for atmospheric modeling. However, the experimental...

Cited by 15 publications

References 97 publications

Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media

Temperature‐dependent kinetics of the reactions of CH₂OO with acetone, biacetyl, and acetylacetone

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Temperature-dependent kinetics of the atmospheric reaction between CH2OO and acetone

Abstract: Criegee intermediates are important oxidants produced in the ozonolysis of alkenes in the atmosphere. Quantitative kinetics of the reactions of Criegee intermediates are required for atmospheric modeling. However, the experimental...

Cited by 15 publications

References 97 publications

Quantitative Kinetics of the Reaction between CH2OO and H2O2 in the Atmosphere

Quantitative Kinetics of the Reaction between CH2OO and H2O2 in the Atmosphere

Stability of Terpenoid-Derived Secondary Ozonides in Aqueous Organic Media

Temperature‐dependent kinetics of the reactions of CH2OO with acetone, biacetyl, and acetylacetone

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Product

Resources

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Temperature-dependent kinetics of the atmospheric reaction between CH₂OO and acetone

Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

Quantitative Kinetics of the Reaction between CH₂OO and H₂O₂ in the Atmosphere

Temperature‐dependent kinetics of the reactions of CH₂OO with acetone, biacetyl, and acetylacetone