Ab initio study of the reaction of OH radical with methyl sulfinic acid (MSIA)

Tian, Yan; Tian, Zhimei; Wei, Wen-mei; He, Tianjing; Chen, Dongming; Liu, Fan-Chen

doi:10.1016/j.chemphys.2007.04.009

Cited by 11 publications

(9 citation statements)

References 31 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%

“…Yet, there are no reports on the atmospheric removal of PSIA with • OH. However, there have been various theoretical and experimental studies on the atmospheric reactions of methanesulfinic acid (MSIA) with • OH. − Kukui et al have studied the reaction of MSIA + • OH using a high-pressure turbulent flow reactor coupled to an ion molecule reaction mass spectrometer. They reported that the dominant reaction path of MSIA + • OH involved the formation of the CH 3 S(O) 2 radical, followed by its rapid decomposition via C–S single bond cleavage to form sulfur dioxide (SO 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…The global rate coefficient for this reaction at 298 K was reported as 7.7 × 10 –10 cm 3 molecule –1 s –1 . In another study, Tian et al investigated the various possible reaction paths for MSIA + • OH at the CCSD(T)/6-311+G(2d,p)//B3LYP/6-31+G(2d, p) level. Their findings also suggested that • OH association with MSIA, followed by decomposition leading to the formation of CH 3 S(O) 2 + H 2 O, is a feasible reaction path.…”

Section: Introductionmentioning

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: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

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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“…Thus, the reaction involving MSIA can occur in gas phase, in aqueous phase and on the surface of aqueous atmospheric media. The OH radical and O 3 are thought as the main oxidants in oxidizing the MSIA 5,6,18,28,29 . The ab initio and density functional theory (DFT) calculations are useful tools for mechanism research.…”

Section: Introductionmentioning

confidence: 99%

“…Tian et al . 28 have used DFT method to study the reaction of OH radical with methanesulfinic acid (MSIA). They found that the association-decomposition reaction (MSIA + OH → adduct → CH 3 SO 2 + H 2 O → CH 3 + SO 2 + H 2 O) is more favorable than direct CH 3 radical-abstraction reaction (MSIA + OH → adduct → CH 3 + H 2 SO 3 → CH 3 + SO 2 + H 2 O).…”

Section: Introductionmentioning

confidence: 99%

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

Zhang

Sun

2019

Sci Rep

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Methanesulfinic acid (MSIA) is an important intermediate in the oxidation of dimethyl sulfide (DMS) in the marine boundary layer. The oxidation of MSIA by ozone in the gas phase to form methanesulfonic acid (MSA) was investigated using theoretical calculations in this paper. Three pathways can be found for the reaction of MSIA with ozone. The highest energy barrier is 13.02 kcal mol−1 in the most favorable pathway. By comparing the reaction rate of MSIA + O3 with that of MSIA + OH, it can be concluded that the oxidation of MSIA by O3 to form MSA is of minor significance relative to its oxidation by OH radical in the gas phase. This study can provide some information for the theoretical and experimental studies in the significantly heterogeneous and aqueous-phase oxidation of MSIA by O3.

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Gasphasenbildung von Schwefliger Säure (H₂SO₃) in der Atmosphäre

Berndt,

Hoffmann,

Tilgner

et al. 2024

Angewandte Chemie

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Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical‐initiated gas‐phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295 ± 0.5 K and 1 bar of air with a molar yield of [[EQUATION]] %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH + CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O + H2SO3) < 3 × 10‐18 cm3 molecule‐1 s‐1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

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Ab initio study of the reaction of OH radical with methyl sulfinic acid (MSIA)

Cited by 11 publications

References 31 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

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

Gasphasenbildung von Schwefliger Säure (H₂SO₃) in der Atmosphäre

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Ab initio study of the reaction of OH radical with methyl sulfinic acid (MSIA)

Cited by 11 publications

References 31 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

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

Gasphasenbildung von Schwefliger Säure (H2SO3) in der Atmosphäre

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Gasphasenbildung von Schwefliger Säure (H₂SO₃) in der Atmosphäre