Products and mechanism of the reaction between NO3 and dimethylsulphide in air

Jensen, N. R.; Hjorth, J.; Lohse, Christian; Skov, Henrik; Restelli, G.

doi:10.1016/0960-1686(91)90272-9

Cited by 55 publications

(42 citation statements)

References 32 publications

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“…These bands were also observed in the FT-IR product study [13] of the reaction between CH3CH2SH and NO3. These spectral features are very similar to those attributed to absorption bands of thionitric acid-S-methyl ester (CH3SNOd, by previous studies [13,21,22,25]. Spectral features at 760, 1313, and 1764 cm-' have tentatively been assigned to CH3CHzS(0),0zNOz; these spectral features were also observed by Mac Leod et al [13].…”

Section: Ch3ch2sh + No3 Reactionsupporting

confidence: 78%

“…is unknown, but we believe that it reacts as the CH,S(O). radical, which has been previously investigated [21,22,25,, thus, leading to the hypothesis of the reaction mechanism illustrated in Figure 5.…”

Section: Ch3ch2sh + No3 Reactionmentioning

confidence: 97%

“…However, when large amounts of NO were added to the system after the CH3SCH3 + NO3 reaction had been allowed to proceed for more than two h, the product yields obtained by the two techniques were similar. This indicates the presence in the gas mixture of a relatively stable peroxynitrate intermediate, CH3S(O), 0 2 N 0 2 , which reacts with liquid HzO in the scrubber to produce CH3S03H (stable spectral features from this peroxynitrate have in fact been observed in the IR spectrum [13,21,22,25,35]). The presence of this stable intermediate could be a n explanation of the large differences in the measured product yield of CH3S03H reported in articles dealing with the oxidation of CH3SCH3 by NO3 and OH.…”

Section: Ch3ch2sh + No3 Reactionmentioning

confidence: 97%

“…In this laboratory previous studies have investigated the reaction between the NO3 radical and CH3SCH3, CH3SH, and CH3SSCH3 [21,22]. The present study deals with the reactions between the NO3 radical and four other reduced organic sulphur compounds; ethyl mercaptan (CH3CH2SH), diethylsulphide ((C H3C H l2 S), diethyldisulphide ( (C H C H2),S ) , and ethyl methyl sulphide (CH3CH2SCH3).…”

Section: Introductionmentioning

confidence: 97%

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Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

Jensen

Hjorth

Lohse

et al. 1992

Int J of Chemical Kinetics

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A 480 L evacuable reaction chamber, equipped with FT-IR spectroscopy on-line and ion chromatography off-line, has been used to study the gas phase reaction between the nitrate radical, NOa, and the reduced organic sulphur compounds CH~CHZSH, ( C H~C H~Z S , (CH~CHZ)ZSZ, and CH&H2SCH3 in air. The products CHaCHZS03H, SOZ, HzS04, CH3CH0, and CH~CHZONOZ were identified and quantified in the reactions of the first three compounds, CH~CHZSH, (CH3CH2),S, and (CH~CHZ)&. The reaction products were CH&HZS03H, CHaSOaH, SOZ, HzS04, CH3CH0, and CH20 in the reaction of CH3CH2SCH3. On the basis ofidentified reaction products and intermediates observed in the infrared spectra, mechanisms are proposed for the reactions between the NO3 radical and the four reduced organic sulphur compounds. The results of this study, together with those from previous experiments performed in this laboratory on CH3SCH3, CHaSH, and CH3SSCH3 lead to the conclusion that all these species, in the reaction with the NO3 radical, follow a similar degradation mechanism producing SO?, H2SO4, R -S03H, R-CHO, and R-CHZONO~, as the main reaction products. The inital step of the reaction of NO3 with R-S-R and R-S-H type (R=CH3, CHZCH3) reduced organic sulphur compounds was found to be H-atom abstraction, probably after the formation of an initial adduct.

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Section: Ch3ch2sh + No3 Reactionsupporting

confidence: 78%

Section: Ch3ch2sh + No3 Reactionmentioning

confidence: 97%

Section: Ch3ch2sh + No3 Reactionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 97%

See 2 more Smart Citations

Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

Jensen

Hjorth

Lohse

et al. 1992

Int J of Chemical Kinetics

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“…A detailed description of the experimental system has been previously published [9]. The spectra were obtained with a Bruker IFS 113v at nominal resolution by co-adding 20 to 50 scans.…”

Section: Methodsmentioning

confidence: 99%

Kinetic study of gas-phase reactions of pinonaldehyde and structurally related compounds

Glasius

Calogirou

Jensen

et al. 1997

Int. J. Chem. Kinet.

108

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Rate constants for the reactions of OH, NO 3 , and O 3 with pinonaldehyde and the structurally related compounds 3-methylbutanal, 3-methylbutan-2-one, cyclobutylmethylketone, and 2,2,3-trimethyl-cyclobutyl-1-ethanone have been measured at using on-line Fourier transform infrared spectroscopy. The rate constants obtained for the reactions with pinonaldehyde were: , , and cm 3 mole-. The results obtained indicate a chemical lifetime of pinonaldehyde in the troposphere of about two hours under typical daytime conditions, .

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Thermal stability of Peroxynitrates

Kirchner

Mayer-Figge

Zabel

et al. 1999

Int. J. Chem. Kinet.

114

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Peroxynitrates are thermally unstable intermediates (at ambient temperatures) in the atmospheric degradation of hydrocarbons. In this work, thermal lifetimes of nine peroxynitrates have been measured as a function of temperature and, for two of them, also, as a function of total pressure. In the presence of excess NO, relative concentrations of the peroxynitrates were followed in a 420 I reaction chamber as a function of time by means of longpath IR absorption using a Fourier transform spectrometer. Original data on the unimolecular decomposition rate constants are presented for the peroxynitrates RO 2 NO 2 with R ϭ C 6 H 11 , CH 3 C(O)CH 2 , C 6 H 5 CH 2 , CH 2 I, CH 3 C(O)OC(H)CH 3 , C 6 H 5 OCH 2 , (CH 3 ) 2 NC(O), C 6 H 5 OC(O), and C 2 H 5 C(O). Thermal lifetimes at room temperature and atmospheric pressure are very short (in the order of seconds) for substituted methyl peroxynitrates (i.e., RЈCH 2 O 2 NO 2 ) but rather long for substituted formyl peroxynitrates (i.e., RЉC(O)O 2 NO 2 ). Kinetic data from this and previous work from our laboratory are used to derive structure-stability relationships which allow an estimate of the thermal lifetimes of peroxynitrates from readily available 13 C n.m.r. shift data.

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Products and mechanism of the reaction between NO3 and dimethylsulphide in air

Cited by 55 publications

References 32 publications

Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

Reactions of the nitrate radical with a series of reduced organic sulphur compounds in air

Kinetic study of gas-phase reactions of pinonaldehyde and structurally related compounds

Thermal stability of Peroxynitrates

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