Reactions of OH radicals with inorganic compounds in the gas phase

Paraskevopoulos, G.; Singleton, D. L.

doi:10.1007/bf03155688

Cited by 10 publications

(2 citation statements)

References 253 publications

(461 reference statements)

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“…Note that in the case of NO 2 as scavenger, coefficient a contains a term proportional to [NO 2 ]. For the respective rate constant (OH + NO 2 + M), measurements in the absence of aromatic yielded 2.4×10 −12 cm 3 s −1 at 133 mbar in Ar at 319 K, in good agreement with the literature (Paraskevopoulos and Singleton, 1988…”

Section: Aromatic-oh + Nosupporting

confidence: 89%

“…For the case of NO as scavenger, the rate constant of the interfering reaction with OH is determined in the absence of aromatics to be 0.95×10 −12 cm 3 s −1 at 320-343 K with 133 mbar of Ar as third body, in good agreement with literature data of Anastasi and Smith (1979) and reviewed by Paraskevopoulos and Singleton (1988). This loss of OH increases mainly τ −1 1 but also τ −1 2 and I 1 /I 2 .…”

Section: Behaviour Of the Adducts In The Presence Of Nosupporting

confidence: 88%

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Consecutive reactions of aromatic–OH adducts with NO, NO2 and O2: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Koch¹,

Knispel²,

Elend³

et al. 2006

Preprint

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Abstract. Consecutive reactions of adducts, resulting from OH radicals and aromatics, with the tropospheric scavenger molecules O2, NO and NO2 have been studied for benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline by observing decays of OH at temperatures where the thermal back-decomposition to OH is faster than 3 s−1, typically between 300 and 340 K. The experimental technique was resonance fluorescence with flash photolysis of water as source of OH. Biexponential decays were observed in the presence of either O2 or NO, and triexponential decays were obtained in the presence of NO2. The kinetic analysis was performed by fitting the relevant rate constants of the reaction mechanism to whole sets of decays obtained at various concentrations of aromatic and scavenger. In the case of hexamethylbenzene, the biexponential decays suggest the existence of the ipso-adduct, and the slightly higher necessary temperatures show that it is even more stable. In addition, smog chamber experiments at O2 concentrations from atmospheric composition down to well below 100 ppm have been carried out for benzene, toluene and p-xylene. The drop of the effective rate constant of removal by OH occurs at reasonable O2 levels, given the FP/RF results. Comparison of the adduct reactivities shows for all aromatics of this study that the reaction with O2 predominates over that with NO2 under all tropospheric conditions, and that a reaction with NO may only occur after the reaction with O2.

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Section: Aromatic-oh + Nosupporting

confidence: 89%

Section: Behaviour Of the Adducts In The Presence Of Nosupporting

confidence: 88%

Consecutive reactions of aromatic–OH adducts with NO, NO2 and O2: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Koch¹,

Knispel²,

Elend³

et al. 2006

Preprint

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Adduct Formation of OH Radicals with Benzene, Toluene, and Phenol and Consecutive Reactions of the Adducts with NO_x and O₂

Knispel

Koch

Siese

et al. 1990

Ber Bunsenges Phys Chem

176

228

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The formation of the adducts of OH with benzene, toluene and phenol and consecutive reactions of the adducts with NO, NO2 and O2 are investigated in the temperature range from ∼298–374 K employing the flash photolysis/resonance fluorescence technique in Ar at 133 mbar. Biexponential decays of OH can be observed over at least 2 orders of magnitude in the presence of the aromatics, and the three reaction channels: abstraction of H by OH, addition of OH and unimolecular decomposition of the adduct are distinguished in overlapping temperature ranges. Rate constants and preliminary Arrhenius parameters are obtained for these channels for benzene, toluene, and phenol. The reactions of the adducts with NO are very slow and can be neglected (<10−13 cm3 s−1) in all three cases. Values of ∼3·10−11 cm3 s−1 are obtained for the rate constants of the reactions of the adducts with NO2, almost independent of reactant and temperature. Preliminary determinations of the adduct reactivities against O2 ∼ 2 · 10−16 (benzene‐OH) and ∼5 · 10−16 cm3 s−1 (toluene‐OH) near room temperature indicate that this path predominates under tropospheric conditions. The results for O2 are confirmed by direct observations of the adduct benzene‐OH by the cw UV‐laser longpath absorption technique.

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ChemInform Abstract: Reactions of Hydroxyl Radicals with Inorganic Compounds in the Gas Phase

Paraskevopoulos¹,

Singleton²

1989

ChemInform

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Reactions of OH radicals with inorganic compounds in the gas phase

Cited by 10 publications

References 253 publications

Consecutive reactions of aromatic–OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Consecutive reactions of aromatic–OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Adduct Formation of OH Radicals with Benzene, Toluene, and Phenol and Consecutive Reactions of the Adducts with NO_x and O₂

ChemInform Abstract: Reactions of Hydroxyl Radicals with Inorganic Compounds in the Gas Phase

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Reactions of OH radicals with inorganic compounds in the gas phase

Cited by 10 publications

References 253 publications

Consecutive reactions of aromatic–OH adducts with NO, NO&lt;sub&gt;2&lt;/sub&gt; and O&lt;sub&gt;2&lt;/sub&gt;: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Consecutive reactions of aromatic–OH adducts with NO, NO&lt;sub&gt;2&lt;/sub&gt; and O&lt;sub&gt;2&lt;/sub&gt;: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Adduct Formation of OH Radicals with Benzene, Toluene, and Phenol and Consecutive Reactions of the Adducts with NOx and O2

ChemInform Abstract: Reactions of Hydroxyl Radicals with Inorganic Compounds in the Gas Phase

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Consecutive reactions of aromatic–OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Consecutive reactions of aromatic–OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Adduct Formation of OH Radicals with Benzene, Toluene, and Phenol and Consecutive Reactions of the Adducts with NO_x and O₂