Kinetics of the reactions of the IO radical with dimethyl sulfide, methanethiol, ethylene, and propylene

Maguin, Françoise; Mellouki, Abdelwahid; Laverdet, G.; Poulet, G.; Bras, G. Le

doi:10.1002/kin.550230306

Cited by 34 publications

(23 citation statements)

References 23 publications

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“…This value is in good agreement with the currently recommended pressure independent value for the rate coefficient of k5(298 K) = 5.2 x lo-'' cm3 molecule-' s-l [17]. It has been discussed in the literature that the rate coefficient for the reaction may be pressure dependent and could be a factor of 2 slower under the conditions employed in this study [14,16,17,19,20]. However, we prefer to use the value of k5 obtained in this study for the evaluation of the experimental data; use of a value of 2.5 x lo-" cm3 molecule-' s-' for ks in the data evaluation would lower kl by ca.…”

Section: Resultssupporting

confidence: 79%

“…They obtained an upper limit of kl < 3.5 x cm3 molecule-' s-' for the rate coefficient which is approximately three orders of magnitude lower than the previously reported values [13,14]. Maguin et al [16] have reinvestigated the reaction using an improved DF-MS technique over that employed in the previous study of the reaction in their laboratory by Martin et al [14]. With the new improved experimental set-up they were able to directly monitor I 0 at low concentrations and the wall reactivity of I0 observed in the early study was greatly reduced.…”

Section: Introductionmentioning

confidence: 63%

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Kinetic studies of the reactions of IO, BrO, and ClO with dimethylsulfide

Barnes

Bastian

Becker

et al. 1991

Int J of Chemical Kinetics

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The kinetics of the reactions of 10, BrO, and C10 with DMS have been investigated at 298 K and total pressures of 0.5-6.8 mbar He using the discharge flow-mass spectrometry technique to monitor the halogen oxide radicals. Rate coefficients of (8.8 (2.7 f 0.5) x cm3 molecule-' 8-l have been obtained for the reactions of 10, BrO, and C10 with DMS, respectively. The result for I 0 with DMS is in good agreement with two other recent studies on this reaction but is nearly three orders of magnitude slower than two earlier studies, one of which was from this laboratory. The earlier studies are now thought to be in error because of heterogeneous and secondary chemistry occurring in the systems investigated. The rate coefficient for BrO with DMS is in excellent agreement with a previously reported preliminary value from this laboratory. However, the rate coefficient for C10 with DMS is a factor of 4 lower than our previously determined value. The new data are considered more reliable in view of the much improved experimental technique in the present study. DMSO was detected as a product in all of these reactions. A semi-quantitative determination of the DMSO yield was only possible in the case of the reaction of I0 with DMS where a yield of 84 f 40% was found.2.1) x and (9.5 2 2.0) x

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Section: Resultssupporting

confidence: 79%

Section: Introductionmentioning

confidence: 63%

Kinetic studies of the reactions of IO, BrO, and ClO with dimethylsulfide

Barnes

Bastian

Becker

et al. 1991

Int J of Chemical Kinetics

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“…It appears that other atmospheric oxidants such as O $ , NO # , and IO do not react with DMS fast enough to be important initiators (see . Recent work (Dunlea et al 1997) in our laboratory has placed an upper limit of 3i10 −"& cm$ molecule −" s −" for the rate constant for the IOjDMS reaction ; this limit is a factor of 2-5 lower than the previously reported values (Daykin & Wine 1990 ;Barnes et al 1991 ;Maguin et al 1991 ;DeMore et al 1994). The role of halogen atoms in the oxidation of DMS, especially in the polar regions, is still uncertain and is worthy of investigation.…”

Section: Methods (A) Initiation Of the Atmospheric Oxidation Of Reducmentioning

confidence: 76%

Oxidation of atmospheric reduced sulphur compounds: perspective from laboratory studies

Ravishankara

Rudich

Talukdar

et al. 1997

Phil. Trans. R. Soc. Lond. B

102

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Results of laboratory experiments which address the course of the OHjDMS (dimethyl sulphide) reaction in the atmosphere are presented. It is shown that OH reacts via a complex sequence of reactions to produce CH $ S and other products, and argued that NO $ is unlikely to be an important oxidizer of DMS in the marine boundary layer because it is very efficiently taken up by water droplets. A simplified mechanism for the oxidation of DMS in the troposphere is presented. This mechanism explains some of the field observations on the end products of DMS oxidation and their variations with temperature.

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“…The water sample was of triply distilled quality and it was thoroughly outgassed. The iodine (Mallinckrodt, AR grade), trifluoromethyl (1)(2)(3)(4)(5)(6)(7)(8)(9)(10) 1014, (1.5-6) x 10'3, 1 x 1012, (2.6-3.7) x 10'4, iodide (Aldrich, 99%), and ethyl iodide (Fluka, Puris. Grade, >99.5%) were all outgassed by repeated freeze-pump-thaw cycles.…”

Section: Methodsmentioning

confidence: 99%

Discharge Flow-Photoionization Mass Spectrometric Study of HOI: Photoionization Efficiency Spectrum and Ionization Energy

Monks¹,

Stief²,

Tardy³

et al. 1995

J. Phys. Chem.

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Photoionization efficiency (PIE) spectra of HOI were measured over the wavelength range A = 115-130 nm and in the ionization threshold region, A = 123-129 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. HOI was generated, in situ but in varying amounts, by three separate reactions: OH + I,; OH + CF3I; O(3P) + C2HJ The PIE spectra displayed steplike behavior near threshold, and the HO-I stretching frequency in the cation was determined to be 702 f 60 cm-I. A value of (9.811 & 0.020) eV was obtained for the adiabatic ionization energy (IE) of HOI from photoion thresholds, corresponding to the HOI+(X2A") -HOI(X' A') transition. Even though the present result appears to be the first reported determination of IE(HOI), the experimental value is compared to an estimated value previously derived via a trend analysis and it is considered in terms of trends in the series IE(HOX), where X = F, C1, Br, and I. The branching ratio for [HOI]/[IO] in the O(3P) + CzHJ reaction was estimated to be about 8/1 at T = 298 K if we assume that the photoionization efficiencies for HOI and IO are the same at 10.3 eV (A = 120 nm). Also, based on the value for IE(HO1) derived in the present study, a value for IE(I0) % 9.66 & 0.10 eV has been predicted.

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Kinetics of the reactions of the IO radical with dimethyl sulfide, methanethiol, ethylene, and propylene

Cited by 34 publications

References 23 publications

Kinetic studies of the reactions of IO, BrO, and ClO with dimethylsulfide

Kinetic studies of the reactions of IO, BrO, and ClO with dimethylsulfide

Oxidation of atmospheric reduced sulphur compounds: perspective from laboratory studies

Discharge Flow-Photoionization Mass Spectrometric Study of HOI: Photoionization Efficiency Spectrum and Ionization Energy

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