Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Lv, Guochun; Zhang, Chenxi; Sun, Xiaomin

doi:10.1038/s41598-018-36405-0

Cited by 16 publications

(21 citation statements)

References 47 publications

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“…The energies calculated at the CCSD(T)//M06-2X level for all of the conformers presented in Figure suggest that PSIA-I is the most stable (∼0.3–0.5 kcal mol –1 ) compared to the other possible conformers. The relative position of the OH group with respect to S(O) for the most stable conformer of PSIA-I is in good agreement with that of the structure of MSIA reported in the literature. ,, Therefore, only the stable conformer (PSIA-I) was considered in the present calculations to study the reaction mechanism of PSIA with OH radicals under atmospheric conditions.…”

Section: Resultssupporting

confidence: 84%

“…The relative position of the OH group with respect to S(O) for the most stable conformer of PSIA-I is in good agreement with that of the structure of MSIA reported in the literature. 17,32,33 Therefore, only the stable conformer (PSIA-I) was considered in the present calculations to study the reaction mechanism of PSIA with OH radicals under atmospheric conditions. The geometry optimization and frequency calculations for these five conformers were performed using the B3LYP method coupled with the aug-cc-pV(T+d)Z basis set.…”

Section: Resultsmentioning

confidence: 99%

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Atmospheric Oxidation of Propanesulfinic Acid Initiated by OH Radicals: Reaction Mechanism, Energetics, Rate Coefficients, and Atmospheric Implications

Arathala

Musah

2021

ACS Earth Space Chem.

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The atmospheric oxidation mechanism and energetics of propanesulfinic acid (CH 3 CH 2 CH 2 S(O)OH, PSIA) initiated by OH radicals have been investigated at the CCSD(T)/aug-cc-pVTZ// M06-2X/aug-cc-pVTZ level of theory. The PSIA + • OH reaction proceeds through (i) H-atom abstraction and (ii) • OH addition pathways. The calculated energies indicate that the barrier height for the abstraction of H-atom from the −OH moiety of PSIA leading to the formation of CH 3 CH 2 CH 2 S(O) 2 + H 2 O is estimated to be −4.7 kcal mol −1 relative to that of the separated reactants. The rate coefficients were determined for all possible reaction paths by RRKM-ME calculations using Master equation solver for multienergy well reactions (Mesmer) code in the atmospherically relevant temperatures between 200 and 320 K and bath gas pressures between 0.1 and 10 atm. The calculated bimolecular rate coefficients suggest that the formation of CH 3 CH 2 CH 2 S(O) 2 + H 2 O is predominant compared to the other possible reaction paths in the studied temperature range. The total rate coefficient for the PSIA + • OH reaction was found to be ∼8.40 × 10 −11 cm 3 molecule −1 s −1 at T = 298 K and P = 1 atm. In addition, branching ratios, thermochemical parameters, atmospheric lifetime, and global warming potentials were determined. Overall, the results indicate that the atmospheric removal of PSIA with • OH results in the formation of sulfur dioxide (SO 2 ) from C−S single bond fission in the CH 3 −CH 2 −CH 2 − S(O) 2 radical, which is formed by H-atom abstraction from the OH group of PSIA. Thus, the SO 2 product does not originate from the direct elimination of SO 2 from unimolecular dissociation of PSIA. The formed SO 2 , propylene (C 3 H 6 ), sulfurous acid (H 2 SO 3 ), and hydroperoxyl (HO 2 ) radical are major products that may contribute to global warming and aerosol formation.

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Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Atmospheric Oxidation of Propanesulfinic Acid Initiated by OH Radicals: Reaction Mechanism, Energetics, Rate Coefficients, and Atmospheric Implications

Arathala

Musah

2021

ACS Earth Space Chem.

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“…14−16 While ozone (O 3 ) is another oxidizing species present in the atmosphere of the marine boundary layer, its reactions with VOSCs are quite slow compared with those of OH and Cl radicals. 7 To reveal a more complete picture regarding the environmental fate and impact of the plant-derived thiosulfinate congener series, an understanding of the reactions of DPTS with Cl radical is required.…”

Section: Introductionmentioning

confidence: 99%

“…As such, natural source VOSCs may have a major impact on the global sulfur cycle. S-containing compounds such as hydrogen sulfide (H 2 S), methane thiol (CH 3 SH), and dimethyl sulfide [(DMS), (CH 3 ) 2 S] are known to play a crucial role in tropospheric chemistry as their atmospheric oxidation can lead to the formation of acid rain and climate change. , Regardless of their source, VOSCs in the atmosphere can undergo degradation through photolysis and/or reaction with several oxidants [e.g., • OH, • Cl, NO x , and ozone (O 3 )], leading to their removal or conversion into other compounds which themselves serve as atmospheric pollutants. − Thus, the emitted VOSCs and their oxidation products contribute to global warming, acid precipitation, cloud formation, and the formation of secondary organic aerosols (SOAs) …”

Section: Introductionmentioning

confidence: 99%

“…Based on the results of the DPTS + • OH and DMTS + • OH/ • Cl studies, the atmospheric removal of these VOSCs is mostly due to the reactions with OH and Cl radicals, although the reactions involving the OH radical are more dominant. The importance of the Cl radical reactions is mainly due to the significant concentrations of Cl radicals that are present over the marine boundary layer. − While ozone (O 3 ) is another oxidizing species present in the atmosphere of the marine boundary layer, its reactions with VOSCs are quite slow compared with those of OH and Cl radicals . To reveal a more complete picture regarding the environmental fate and impact of the plant-derived thiosulfinate congener series, an understanding of the reactions of DPTS with Cl radical is required.…”

Section: Introductionmentioning

confidence: 99%

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Oxidation of Dipropyl Thiosulfinate Initiated by Cl Radicals in the Gas Phase: Implications for Atmospheric Chemistry

Arathala

Musah

2021

ACS Earth Space Chem.

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The reaction mechanism for chlorine radical (•Cl)-initiated atmospheric oxidation of dipropyl thiosulfinate (DPTS) in the gas phase was investigated using ab initio/density functional theory electronic structure calculations. The DPTS + •Cl reaction proceeds by H-abstraction and substitution pathways. The results indicate that the Cl radical adds to the S-atom of the sulfinyl [S(O)] group of DPTS, which is followed by cleavage of the S(O)–S single bond, leading to the formation of propanesulfinyl chloride and propanethiyl radical (PTR). The barrier height for this reaction was estimated to be −12.2 kcal mol–1 relative to the separated starting reactants. The rate coefficients were calculated for all possible H-abstraction and substitution paths using the master equation solver for the multi-energy well reactions (MESMER) kinetic code in the atmospherically relevant temperature range of 200–300 K and at 1 atm pressure. The rate coefficient data for all reaction paths indicate that the formation of propanesulfinyl chloride and PTR from the DPTS + •Cl reaction is the major path. The rate coefficient for this reaction was estimated to be ∼6.00 × 10–10 cm3 molecule–1 s–1 at 298 K and 1 atm pressure. The overall rate coefficient for the DPTS + •Cl reaction in the same temperature range was found to be ∼8.14 × 10–10 cm3 molecule–1 s–1 at 298 K. The atmospheric lifetime of DPTS was calculated to be ∼3 h in the temperatures between 200 and 300 K and at 1 atm. In addition, the branching ratio fractions for each reaction were determined and the atmospheric implications are discussed. Overall, the results reveal that while the primary products of the DPTS + Cl radical reaction are short-lived, the compounds formed from their subsequent oxidative degradation do contribute to global warming and have the potential to exhibit adverse environmental impacts.

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An Electronic Structure Study of the Conversion from 1,2‐Diphenylacetylene to (E)‐1,2‐Diphenylethene Using a Bidentate Ru(II)−NC Catalyst

Curichimba

Haiduke

2022

Eur J Inorg Chem

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The {(C 5 H 4 N)(C 6 H 4 )}RuCl(CO)(PPh 3 ) 2 catalyst has been shown to be highly efficient and selective for semi-hydrogenation reactions with a wide range of internal alkynes containing electronwithdrawing and electron-donating groups to E-alkenes. In this work, the reaction mechanism previously proposed by experimentalists to the formation of (E)-1,2-diphenylethene from 1,2diphenylacetylene (Organometallics, 2020, 39, 862) is evaluated by using the Density Functional Theory. Our calculations show the existence of four new intermediates to avoid steric hindrance issues and to explain the releasing of the (Z)-1,2diphenylethene and (E)-1,2-diphenylethene products at the end of the first and second cycles, respectively. Besides, by using the energetic span model, the turnover frequency (TOF)determining transition state (TDTS) and intermediate (TDI) are found in the first cycle, providing an energetic span for the catalytic cycle of 16.8 kcal/mol at 383.15 K. This result assures that the reaction can really proceed by this mechanism.

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Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Cited by 16 publications

References 47 publications

Atmospheric Oxidation of Propanesulfinic Acid Initiated by OH Radicals: Reaction Mechanism, Energetics, Rate Coefficients, and Atmospheric Implications

Atmospheric Oxidation of Propanesulfinic Acid Initiated by OH Radicals: Reaction Mechanism, Energetics, Rate Coefficients, and Atmospheric Implications

Oxidation of Dipropyl Thiosulfinate Initiated by Cl Radicals in the Gas Phase: Implications for Atmospheric Chemistry

An Electronic Structure Study of the Conversion from 1,2‐Diphenylacetylene to (E)‐1,2‐Diphenylethene Using a Bidentate Ru(II)−NC Catalyst

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