Kinetic Study of the Reactions of CH2ClO2 with Itself and with HO2, and Theoretical Study of the Reactions of CH2ClO, between 251 and 600 K

Catoire, Valéry; Lesclaux, R.; Lightfoot, Philip; Rayez, Marie-Thérèse

doi:10.1021/j100062a027

Cited by 46 publications

(96 citation statements)

References 8 publications

(15 reference statements)

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“…To investigate these observations more thoroughly, the rate of formation of IO was mea- Figure 5. Ultraviolet absorption spectra of the CH 2 ClO 2 [32] (~) and CH 2 BrO 2 [33] (*) peroxy species, and species X (&) as determined herein. Note that the absorption intensity of species X has been converted to an absorption cross-section by normalisation to the lower limit estimated at 327.2 nm (1.7 10 À18 cm 2 molecule À1 ).…”

Section: à3mentioning

confidence: 99%

A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

et al. 2010

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The CH(2)I+O(2) reaction has been studied using laser flash photolysis followed by absorption spectroscopy, laser-induced fluorescence spectroscopy and mass spectrometry. The rates of formation of IO and CH(2)O were found to be dependent upon the concentration of CH(2)I(2) under pseudo-first-order conditions ([O(2)]≫[CH(2)I(2)]), demonstrating that IO and CH(2)O are not formed directly from the title reaction, in contrast to recent investigations by Enami et al. It is proposed that the reaction proceeds via the formation of the peroxy radical species CH(2)IO(2), which undergoes self-reaction to form CH(2)IO, and which decomposes to CH(2)O+I, and that in laboratory systems IO is formed via the reaction I+CH(2)IO(2). The absorption spectrum of a species assigned to CH(2)IO(2) was observed in the range 310-400 nm with a maximum absorption at 327.2 nm of σ≥1.7×10(-18) cm(2) molecule(-1). A modelling study enabled the room temperature rate coefficients for the CH(2)IO(2)+CH(2)IO(2) self-reaction and the I+CH(2)IO(2) reaction to be confined within the ranges (6-12)×10(-11) cm(3) molecule(-1) s(-1), and (1-2)×10(-11) cm(3) molecule(-1) s(-1), respectively. In the atmosphere, CH(2)IO(2) will slowly react with other radicals to release iodine atoms, which can then form IO via reaction with ozone. Slow formation of IO means that lower concentrations are formed, which leads to a lower propensity to form particles as the precursor molecule OIO forms at a rate which is dependent on the square of the IO concentration.

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Section: à3mentioning

confidence: 99%

A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

et al. 2010

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“…The atmospheric oxidation of methyl chloride proceeds via formation of the chloromethoxy radical, CH 2 ClO. [2][3][4][5][6] In all previous studies 2- 6 of CH 3 Cl oxidation, CH 2 ClO radicals were produced via Cl-initiated oxidation of CH 3 Cl in the absence of NO, i.e., via reactions 1-4…”

Section: Introductionmentioning

confidence: 99%

FT-IR Product Studies of the Cl-Initiated Oxidation of CH₃Cl in the Presence of NO

Bilde

Tyndall²,

Wallington³

et al. 1999

J. Phys. Chem. A

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The Cl-atom initiated oxidation of CH 3 Cl has been studied at 296 K using two different FTIR/environmental chamber systems. In the presence of NO, the carbon-bearing products observed are HCOCl, HCHO, and CO, with yields in 700 Torr of air of (56 ( 10), (32 ( 6), and (12 ( 5)%, respectively. This product distribution is different from previous studies conducted in the absence of NO, in which a nearly 100% yield of HCOCl was obtained. The different product distribution observed in the presence of NO is attributed to the formation and subsequent decomposition of chemically activated CH 2 ClO radicals, formed in the exothermic reaction of CH 2 ClO 2 with NO.

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“…To study the kinetics of the reaction of BrC(CH 3 ) 2 C(CH 3 ) 2 O 2 with HO 2 , the oxygen was added in large excess (ϳ600 Torr) thus favoring the formation of HO 2 by reaction (7) and avoiding reaction (4). Note that in this method BrC(CH 3 ) 2 C(CH 3 ) 2 O 2 and HO 2 radicals were generated in equal concentrations.…”

Section: Methodsmentioning

confidence: 99%

“…Due to the strong absorptions of TME and HBr below 240 nm, combined with the transmission cutoff of the dichroic mirror between 235 and 265 nm, we were unable to use the method adopted in our former studies of the RO 2 ϩ HO 2 reactions [4,20,21], where pairs of traces, recorded at wavelengths specific to each radical, were analyzed simultaneously. Therefore, radical decays were only monitored at 270 nm.…”

Section: Kinetics Of the Reaction Of Brc(ch 3 ) 2 C(ch 3 ) 2 O 2 Withmentioning

confidence: 99%

Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

Villenave

Lesclaux

2000

Int J Chem Kinet

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Kinetic Study of the Reactions of CH2ClO2 with Itself and with HO2, and Theoretical Study of the Reactions of CH2ClO, between 251 and 600 K

Cited by 46 publications

References 8 publications

A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

FT-IR Product Studies of the Cl-Initiated Oxidation of CH₃Cl in the Presence of NO

Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

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Kinetic Study of the Reactions of CH2ClO2 with Itself and with HO2, and Theoretical Study of the Reactions of CH2ClO, between 251 and 600 K

Cited by 46 publications

References 8 publications

A Multidimensional Study of the Reaction CH2I+O2: Products and Atmospheric Implications

A Multidimensional Study of the Reaction CH2I+O2: Products and Atmospheric Implications

FT-IR Product Studies of the Cl-Initiated Oxidation of CH3Cl in the Presence of NO

Kinetic studies of the self-reaction and reaction with HO2 of a tertiary ?-brominated peroxy radical between 298 and 393 K

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Product

Resources

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A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

A Multidimensional Study of the Reaction CH₂I+O₂: Products and Atmospheric Implications

FT-IR Product Studies of the Cl-Initiated Oxidation of CH₃Cl in the Presence of NO