Photodegradation of (CH3CH2)2S and CH3CH2SCH3 initiated by OH radicals at atmospheric pressure. Product yields and mechanism in NOx free air

Oksdath‐Mansilla, Gabriela; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

doi:10.1016/j.atmosenv.2012.02.086

Cited by 13 publications

(13 citation statements)

References 35 publications

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“…The oxidation of MES in the atmosphere starts with the formation of radicals after the abstraction of a hydrogen atom from the parent molecule by OH radical . X—H (X = C, O) bond energies are needed to analyze the initial steps of MES partial oxidation, and these are needed to evaluate the peroxy radicals formed by association of the initial radical with 3 O 2 .…”

Section: Resultsmentioning

confidence: 99%

“…Investigations to MES partial oxidation in the atmosphere are important for understanding its initial oxidation steps. Mansilla et al experimentally investigated the degradation of MES under photochemical atmospheric conditions, and Zheng et al studied the oxidation at higher temperatures. Cao et al have performed detailed computational studies to investigate initiation reaction steps of MES by the OH radicals .…”

Section: Introductionmentioning

confidence: 99%

“…In 2011, Zheng et al developed an elementary reaction mechanism for diethyl sulfide oxidation and performed kinetic modeling to determine important reaction paths and products versus temperature and time. Mansilla et al performed experiments in a photochemical chamber where they reported on loss of MES and formation of formaldehyde, acetaldehyde, formic acid, and SO 2 . They suggested a reaction mechanism of reaction of OH with CH 3 SCH 3 generated radicals on the carbons of MES, which then react with O 2 to form peroxy radicals.…”

Section: Introductionmentioning

confidence: 99%

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Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

Song

Bozzelli

2017

J of Physical Organic Chem

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Hydroperoxides and the corresponding peroxy radicals are important intermediates during the partial oxidation of methyl ethyl sulfide (CH3SCH2CH3) in both atmospheric chemistry and in combustion. Structural parameters, internal rotor potentials, bond dissociation energies, and thermochemical properties (ΔHfo, So and Cp(T)) of 3 corresponding hydroperoxides CH2(OOH)SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH of methyl ethyl sulfides, and the radicals formed via loss of a hydrogen atom are important to understanding the oxidation reactions of MES. The lowest energy molecular structures were identified using the density functional B3LYP/6‐311G(2d,d,p) level of theory. Standard enthalpies of formation (ΔHfo298) for the radicals and their parent molecules were calculated using the density functional B3LYP/6‐31G(d,p), B3LYP/6‐31 + G(2d,p), and the composite CBS‐QB3 ab initio methods. Isodesmic reactions were used to determine ∆Hfo values. Internal rotation potential energy diagrams and rotation barriers were investigated using the B3LYP/6‐31G(d,p) level theory. Contributions for So298 and Cp(T) were calculated using the rigid rotor harmonic oscillator approximation based on the structures and vibrational frequencies obtained by the density functional calculations, with contributions from torsion frequencies replaced by internal rotor contributions. The recommended values for enthalpies of formation of the most stable conformers of CH3SCH2CH2, CH2(OOH)SCH2CH3, CH3SCH(OOH)CH3, and CH3SCH2CH2OOH are −14.0, −33.0, −37.2, and −32.7 kcal/mol, respectively. Group additivity values were developed for estimating properties of structurally similar and larger sulfur‐containing peroxides. Groups for use in group additivity estimation of sulfur peroxide thermochemical properties were developed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

Song

Bozzelli

2017

J of Physical Organic Chem

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“…CCSD(T)), and may underestimate the reaction barrier, 11,12 DFT has been widely used in studying the molecular properties, the reaction mechanism such as oxidation reaction [13][14][15] and the binding energy because of the less computational intensity and moderate accuracy. [16][17][18][19][20][21][22][23][24][25][26][27][28][29] In the present work, all of the electronic structure calculations were performed using the Gaussian 09 suite.…”

Section: Methods Of Calculationmentioning

confidence: 99%

First principle simulation on oxidation mechanism of diethyl ether by nitrogen dioxide

Yuan

Hu²,

Chi³

et al. 2015

J. Theor. Comput. Chem.

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The oxidation mechanism of diethyl ethers by NO 2 was carried out using density functional theory (DFT) at the B3LYP/6-31þG (d, p) level. The oxidation process of ether follows four steps. First, the diethyl ether reacts with NO 2 to produce HNO 2 and diethyl ether radical with an energy barrier of 20.62 kcal Á mol À1 . Then, the diethyl ether radical formed in the¯rst step directly combines with NO 2 to form CH 3 CH(ONO)OCH 2 CH 3 . In the third step, the CH 3 CH (ONO)OCH 2 CH 3 was further decomposed into the CH 3 CH 2 ONO and CH 3 CHO with a moderately high energy barrier of 32.87 kcal Á mol À1 . Finally, the CH 3 CH 2 ONO continues to react with NO 2 to yield CH 3 CHO, HNO 2 and NO with an energy barrier of 28.13 kcal Á mol À1 . The calculated oxidation mechanism agrees well with Nishiguchi and Okamoto's experiment and proposal.

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“…According to the recent studies by Mansilla et al 54 and Cao et al 15 , the partial oxidation of MES in the atmosphere in the absence of NO x or Cl radicals begins from the abstraction of one hydrogen atom from each MES molecule by a hydroxyl radical 8,13,54,55 :…”

Section: Reaction Pathways and Geometries Of Optimized Transition Statesmentioning

confidence: 99%

Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide, CH₃SCH₂CH₂•, with O₂ to CH₃SCH₂CH₂OO•

Song

Bozzelli

2019

Int J of Chemical Kinetics

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Oxidation of methyl ethyl sulfide (CH 3 SCH 2 CH 3 , methylthioethane, MES) under atmospheric and combustion conditions is initiated by hydroxyl radicals, MES radicals, generated after loss of a H atom via OH abstraction, will further react with O 2 to form chemically activated and stabilized peroxyl radical adducts. The kinetics of the chemically activated reaction between the CH 3 SCH 2 CH 2 • radical and molecular oxygen are analyzed using quantum Rice-Ramsperger-Kassel theory for k(E) with master equation analysis and a modified strong-collision approach to account for further reactions and collisional deactivation. Thermodynamic properties of reactants, products, and transition states are determined by the B3LYP/6-31+G(2d,p), M062X/6-311+G(2d,p), B97XD/6-311+G(2d,p) density functional theory, and CBS-QB3, G3MP2B3, and G4 composite methods. The reaction of CH 3 SCH 2 CH 2 • with O 2 forms an energized peroxy adduct CH 3 SCH 2 CH 2 OO• with a calculated well depth of 34.1 kcal mol −1 at the CBS-QB3 level of theory. Thermochemical properties of reactants, transition states, and products obtained under CBS-QB3 level are used for calculation of kinetic parameters. Reaction enthalpies are compared between the methods. The temperature and pressure-dependent rate coefficients for both the chemically activated reactions of the energized adduct and the thermally activated reactions of the stabilized adducts are presented. Stabilization and isomerization of the CH 3 SCH 2 CH 2 OO• adduct are important under high pressure and low temperature.At higher temperatures and atmospheric pressure, the chemically activated peroxy adduct reacts to new products before stabilization. Addition of the peroxyl oxygen radical to the sulfur atom followed by sulfur-oxygen double bond formation and elimination of the methyl radical to form S(= O)CCO• + CH 3 (branching) is a potentially important new pathway for other alkyl-sulfide peroxy radical systems under thermal or combustion conditions. K E Y W O R D Skinetics, methyl ethyl sulfide, oxidation, thermochemistry 618

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Photodegradation of (CH3CH2)2S and CH3CH2SCH3 initiated by OH radicals at atmospheric pressure. Product yields and mechanism in NOx free air

Cited by 13 publications

References 35 publications

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

First principle simulation on oxidation mechanism of diethyl ether by nitrogen dioxide

Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide, CH₃SCH₂CH₂•, with O₂ to CH₃SCH₂CH₂OO•

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Photodegradation of (CH3CH2)2S and CH3CH2SCH3 initiated by OH radicals at atmospheric pressure. Product yields and mechanism in NOx free air

Cited by 13 publications

References 35 publications

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH, and radicals

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH2SCH2CH3, CH3SCH(OOH)CH3, CH3SCH2CH2OOH, and radicals

First principle simulation on oxidation mechanism of diethyl ether by nitrogen dioxide

Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide, CH3SCH2CH2•, with O2 to CH3SCH2CH2OO•

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Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

Structures and thermochemistry of methyl ethyl sulfide and its hydroperoxides: HOOCH₂SCH₂CH₃, CH₃SCH(OOH)CH₃, CH₃SCH₂CH₂OOH, and radicals

Reaction kinetics and thermochemistry of the chemically activated and stabilized primary ethyl radical of methyl ethyl sulfide, CH₃SCH₂CH₂•, with O₂ to CH₃SCH₂CH₂OO•