Atmospheric photochemistry of alkyl nitrates

Turberg, Michael; Giolando, Dean M.; Tilt, C.; Soper, T.; Mason, Sharon; Davies, Mansel; Klingensmith, P.; Takacs, G. A.

doi:10.1016/1010-6030(90)87063-h

Cited by 41 publications

(19 citation statements)

References 54 publications

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“…We calibrated our detection system for CH 3 O by measuring CH 3 O produced via the 193 nm photolysis of a known concentration of CH 3 ONO 2 in N 2 . The quantum yield for CH 3 O production from the photodissociation of CH 3 ONO 2 at 193 nm (Φ ∼ 0.7) 23 and the absorption cross section (σ ) 1.6 × 10 -17 cm 2 molecule -1 ) 31 were used to quantify the CH 3 O produced. On the basis of our detection limit for CH 3 O (1 × 10 11 cm -3 ), an assumed uncertainty of 5% in the absorption cross section measurements, and an assumed uncertainty of 20% in the quantum yield of CH 3 O from CH 3 ONO 2 , a conservative upper limit for the yield of CH 3 O in reaction 2 of 0.03 was obtained.…”

Section: Experiments and Resultsmentioning

confidence: 99%

Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products

et al. 1996

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The rate coefficients for the reactions of O( 3 P) with CF 3 I (1) and CH 3 I (2) were measured between 213 and 364 K to be: k 1 (T) ) (7.9 ( 0.8) x 10 -12 exp [-(175 ( 40)/T] and k 2 (T) ) (1.0 ( 0.2) x 10 -11 exp[(160 ( 50)/T] cm 3 molecule -1 s -1 . The rate coefficients for the reaction of O( 3 P) with CD 3 I, (CH 3 ) 2 CHCH 2 I, (CH 3 ) 2 -CHI, CF 3 CH 2 I, CF 3 CHFI, and CF 3 CF 2 I at 298 K were also measured. The yields of the IO and CF 3 O products in reaction 1 at 298 K were found to be 0.83 ( 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 ( 0.04), OH (0.16 ( 0.05), H (0.07 ( 0.02), CH 3 O (<0.03), and HI (<0.05). IO, OH, and CH 3 O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF 3 O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, ∆ f H°(298.15 K)(IO) <28.8 kcal mol -1 , was obtained from an interpretation of our data.

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Section: Experiments and Resultsmentioning

confidence: 99%

Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products

et al. 1996

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“…The rate coefficients for HO attack on the alkyl nitrates <C4 are considerably lower than the reactions of HO with the corresponding unsubstituted alkane [Atkinson et al, 1982a;Becker and Wirtz, 1989;Liu et al, 1990]. Hence their lifetimes are determined largely by their photolysis rates in the atmosphere for the nitrates <C4 and both by HO attack and photolysis for nitrates >C5; these can be long, of the order of days to months in the planetary boundary layer, depending upon the structure of the nitrate [Luke and Dickerson, 1988;Luke et al, 1989;Roberts and Fajer, 1989;Turberg et al, 1990;Roberts, 1990]. By contrast, organic nitrates with multiple functional groups may be more rapidly photolyzed than alkyl nitrates [Trainer et al, 1991].…”

Section: Brewer Et Al [1984] Have Estimated From One-dimensionalmentioning

confidence: 99%

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Fehsenfeld¹,

Calvert²,

Fall³

et al. 1992

Global Biogeochemical Cycles

874

503

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Vegetation provides a major source of reactive carbon entering the atmosphere. These compounds play an important role in (1) shaping global tropospheric chemistry, (2) regional photochemical oxidant formation, (3) balancing the global carbon cycle, and (4) production of organic acids which contribute to acidic deposition in rural areas. Present estimates place the total annual global emission of these compounds between approximately 500 and 825 Tg yr−1. The volatile olefinic compounds, such as isoprene and the monoterpenes, are thought to constitute the bulk of these emissions. However, it is becoming increasingly clear that a variety of partially oxidized hydrocarbons, principally alcohols, are also emitted. The available information concerning the terrestrial vegetation as sources of volatile organic compounds is reviewed. The biochemical processes associated with these emissions of the compounds and the atmospheric chemistry of the emitted compounds are discussed.

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“…These studies also suggest that the rate of these reactions strongly depends on the organic nitrate chemical structure and that additional work is needed to better understand these processes. In the gas phase, photolysis and reaction with the OH radical are expected to dominate the fate of organic nitrates (Roberts, 1990;Turberg et al, 1990). In a previous study, we measured the photolysis frequencies and the rate constants for the OH oxidation of three carbonyl nitrates (α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone), and we showed that photolysis is the dominant sink for these compounds (Suarez-Bertoa et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone

Picquet‐Varrault

Suarez-Bertoa

Duncianu³

et al. 2020

Atmos. Chem. Phys.

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Abstract. Multifunctional organic nitrates, including carbonyl nitrates, are important species formed in NOx-rich atmospheres by the degradation of volatile organic compounds (VOCs). These compounds have been shown to play a key role in the transport of reactive nitrogen and, consequently, in the ozone budget; they are also known to be important components of the total organic aerosol. However, very little is known about their reactivity in both the gas and condensed phases. Following a previous study that we published on the gas-phase reactivity of α-nitrooxy ketones, the photolysis and reaction with OH radicals of 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone (which are a β-nitrooxy ketone and γ-nitrooxy ketone, respectively) were investigated for the first time in simulation chambers. The photolysis frequencies were directly measured in the CESAM chamber, which is equipped with a very realistic irradiation system. The jnitrate/jNO2 ratios were found to be (5.9±0.9)×10-3 for 4-nitrooxy-2-butanone and (3.2±0.9)×10-3 for 5-nitrooxy-2-pentanone under our experimental conditions. From these results, it was estimated that ambient photolysis frequencies calculated for typical tropospheric irradiation conditions corresponding to the 1 July at noon at 40∘ N (overhead ozone column of 300 and albedo of 0.1) are (6.1±0.9)×10-5 s−1 and (3.3±0.9)×10-5 s−1 for 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone, respectively. These results demonstrate that photolysis is a very efficient sink for these compounds with atmospheric lifetimes of few hours. They also suggest that, similarly to α-nitrooxy ketones, β-nitrooxy ketones have enhanced UV absorption cross sections and quantum yields equal to or close to unity and that γ-nitrooxy ketones have a lower enhancement of cross sections, which can easily be explained by the larger distance between the two chromophore groups. Thanks to a product study, the branching ratio between the two possible photodissociation pathways is also proposed. Rate constants for the reaction with OH radicals were found to be (2.9±1.0)×10-12 and (3.3±0.9)×10-12 cm3 molecule−1 s−1, respectively. These experimental data are in good agreement with rate constants estimated by the structure–activity relationship (SAR) of Kwok and Atkinson (1995) when using the parametrization proposed by Suarez-Bertoa et al. (2012) for carbonyl nitrates. Comparison with photolysis rates suggests that the OH-initiated oxidation of carbonyl nitrates is a less efficient sink than photodissociation but is not negligible in polluted areas.

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Atmospheric photochemistry of alkyl nitrates

Cited by 41 publications

References 54 publications

Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products

Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone

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Atmospheric photochemistry of alkyl nitrates

Cited by 41 publications

References 54 publications

Reactions of O(3P) with Alkyl Iodides: Rate Coefficients and Reaction Products

Reactions of O(3P) with Alkyl Iodides: Rate Coefficients and Reaction Products

Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry

Photolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanone

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Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products

Reactions of O(³P) with Alkyl Iodides: Rate Coefficients and Reaction Products