Kinetics, product distribution and atmospheric implications of the gas-phase oxidation of allyl sulfides by OH radicals

Cardona, Alejandro L.; Gibilisco, Rodrigo G.; Rivela, Cynthia B.; Blanco, Marı́a B.; Patroescu-Klotz, Iulia; Illmann, Niklas; Wiesen, Peter; Teruel, Mariano A.

doi:10.1016/j.chemosphere.2021.132546

Cited by 4 publications

(7 citation statements)

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“…Atmospheric implications were also discussed, and the general conclusion is that both AMS and AES are expected to be rapidly removed from the atmosphere near their emission sources. Reaction with OH radicals is an important atmospheric sink for AMS and AES, with atmospheric lifetimes of 2.75 and 2.02 h, respectively . It is suggested, however, that the oxidation of both sulfides by O 3 could be important at night in highly polluted cities.…”

Section: Discussionmentioning

confidence: 99%

“…Reaction with OH radicals is an important atmospheric sink for AMS and AES, with atmospheric lifetimes of 2.75 and 2.02 h, respectively. 53 It is suggested, however, that the oxidation of both sulfides by O 3 could be important at night in highly polluted cities.…”

Section: Discussionmentioning

confidence: 99%

“…However, it is expected that the reaction with OH radicals is an important atmospheric sink for AMS and AES, atmospheric lifetimes of the products of reaction with OH radicals being 2.75 and 2.02 h, respectively. 53 The oxidation by O 3 , however, could be important at night in highly polluted cities.…”

Section: Computational Approachmentioning

confidence: 99%

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Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals

et al. 2022

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Rate coefficients of the O 3 -initiated oxidation of allyl methyl sulfide (H 2 C�CHCH 2 SCH 3 , AMS) and allyl ethyl sulfide (H 2 C�CHCH 2 SCH 2 CH 3 , AES) were determined at atmospheric conditions by "in situ" FTIR. The relative kinetic experiments were performed using methylcyclohexane (McH) and carbon monoxide (CO) as nascent OH radical scavengers and in the absence of any scavenger, to determine the impact that the formation of OH radicals has on the rate coefficients. In the absence of scavengers, values of k AMS+Od 3 = (5.23 ± 3.57) × 10 −18 and k AES+Od 3 = (5.76 ± 1.80) × 10 −18 cm 3 molecule −1 s −1 were obtained. In the presence of the scavengers, however, the rates decreased to k AMS+Od 3 +McH = (3.92 ± 1.92) × 10 −18 and k AMS+Od 3 +CO = (2.63 ± 0.47) × 10 −18 cm 3 molecule −1 s −1 for AMS, and k AES+Od 3 +McH = (4.78 ± 1.38) × 10 −18 and k AES+Od 3 +CO = (3.50 ± 0.27) × 10 −18 cm 3 molecule −1 s −1 for AES. On the basis of these results, we have decided to recommend the values obtained using CO as scavenger as those best representing the rate coefficient for the reactions of O 3 with AMS and AES. The reaction mechanism was explored using DFT and post-Hartree−Fock computational methods. It is shown that the barrier for the common cyclization to primary ozonide (−3.7 ± 0.1 kcal mol −1 ) followed by other reactions, as well as that for the reaction with the sulfur atom (−5.1 ± 0.1 kcal mol −1 ), is small and quite close, meaning that both reaction paths should contribute significantly to the global reaction rate.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

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Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals

et al. 2022

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“…14 In our recently published experimental work, we determined the rate coefficient of the gas phase degradation of AMS initiated by OH radicals where the main reaction products were detected and quantied. 15 Our ndings led us to assume that the degradation mechanism could be more complex than for other unsaturated compounds, due to the presence of the sulfur atom in the molecule. In the case of alkyl suldes, it has been proposed that in the reaction with OH radicals, those can weakly bind to the sulfur atom, leading to a prereactive complex which has been related to a negative temperature dependence.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, in this work we explore in depth the energetics of the addition reaction mechanism involved in the gas phase degradation of AMS initiated by OH radicals using computational methods, to better understand and complement our previous experimental finding o allyl sulfides. 15…”

Section: Introductionmentioning

confidence: 99%

Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Cardona

Blanco

Teruel

et al. 2023

Environ. Sci.: Atmos.

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Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

Cardona,

Teruel,

Ventura

2024

Chemosphere

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Kinetics, product distribution and atmospheric implications of the gas-phase oxidation of allyl sulfides by OH radicals

Cited by 4 publications

References 47 publications

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals

Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

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Kinetics, product distribution and atmospheric implications of the gas-phase oxidation of allyl sulfides by OH radicals

Cited by 4 publications

References 47 publications

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H2C═CHCH2SR, R = CH3, CH3CH2): The Effect of Nascent OH Radicals

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H2C═CHCH2SR, R = CH3, CH3CH2): The Effect of Nascent OH Radicals

Mechanistic study of the complex photooxidation of allyl methyl sulfide (AMS): reaction paths and products of addition under different atmospheric conditions

Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

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Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H₂C═CHCH₂SR, R = CH₃, CH₃CH₂): The Effect of Nascent OH Radicals