Reactivity of the nitrate radical towards alkynes and some other molecules

Canosa‐Mas, Carlos E.; Smith, Stuart J.; Toby, Sidney; Wayne, Richard P.

doi:10.1039/f29888400247

Cited by 40 publications

(29 citation statements)

References 7 publications

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“…, which agrees with other experimental results [14,15]. These small values for wall-loss rate constants can be ignored in the present experiments.…”

supporting

confidence: 93%

“…The existence of an intercept thus may suggest an additional loss process of NO 3 dependent on the presence of reactant, probably because of a change in k w (the global rate coefficient for wall loss of NO 3 ) when the reactant is present. This behavior has been found elsewhere [17] for reactions of the OH radical and in NO 3 reactions [10,15]. There is no evidence of curvature in the second-order plots.…”

Section: Totalsupporting

confidence: 60%

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A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

Martı́nez¹,

Cabañas²,

Aranda³

et al. 1997

Int. J. Chem. Kinet.

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Absolute rate coefficient for the gas-phase reaction of NO 3 with 3-fluoropropene has been measured using the discharge-flow technique coupled to a LIF detection system for a range of temperatures from 296 K to 430 K. The measured room temperature rate constant is (0.39 Ϯ 0.02) ϫ 10 Ϫ14 molecule Ϫ1 cm 3 s Ϫ1. The Arrhenius expression k ϭ (7.17 Ϯ 3.34) ϫ 10 Ϫ12 exp[Ϫ(2248 Ϯ 169)/T] is proposed for the reaction. The reactivity of alkenes containing halogen atoms is discussed and compared to that of simple alkenes, on the basis of the correlations between the reactivity against NO 3 and the ionization potential of the alkenes.Tropospheric half life of 3-fluoropropene has been estimated at night and during daytime for typical NO 3 and OH trophospheric concentrations.

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“…, which agrees with other experimental results [14,15]. These small values for wall-loss rate constants can be ignored in the present experiments.…”

supporting

confidence: 93%

Section: Totalsupporting

confidence: 60%

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

Martı́nez¹,

Cabañas²,

Aranda³

et al. 1997

Int. J. Chem. Kinet.

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“…A similar reaction rate constant has been measured for acetylene [40]. A similar reaction rate constant has been measured for acetylene [40].…”

Section: )supporting

confidence: 77%

“…k NO 3 (isobutene) = 3.3 × 10 -13 cm 3 molecule -1 s -1 This value was measured by means of an absolute method by Canosa-Mas et al [40], and is in very good agreement with the relative value of Atkinson et al [41]. [41]) and benzene-type aromatic hydrocarbons, e.g., toluene, are much less reactive towards NO 3 : k NO 3 (toluene) = 6.8 × 10 -17 cm 3 molecule -1 s -1…”

Section: )mentioning

confidence: 99%

Abiotic Degradation in the Atmosphere

Klöpffer¹,

Wagner²

2007

Atmospheric Degradation of Organic Substances

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1)A sink is defi ned here as an irreversible chemical, photochemical or biochemical reaction which removes a molecule from the environment; a perfect sink leads to mineralization. Within this defi nition, the transfer to and the temporary fi xation in another compartment (e.g., soil, vegetation or water) without chemical modifi cation is not considered to be a sink [1].2 Photo-degradation in the Homogenous Gas Phase of the Troposphere Chapter 2: Abiotic Degradation in the Atmosphere 28 k OH (T) = (2.25 + 0.46 -0.39) × 10 -18 T 2 exp{(-910 ± 56)/T} cm 3 molecule -1 s -1 k OH (298 K) = 9.43 × 10 -15 cm 3 molecule -1 s -1More interesting for the average OH lifetime is k OH at the (weighted or effective) average temperature of the troposphere. This temperature has been estimated by Warneck [15] in an analysis of the tropospheric CH 4 + OH reaction as eff = 280 K. According to an earlier estimate, based on the lifetime of chlorinated hydrocarbons [34], this temperature may be as low as 260 K. Using the more recent estimate by Warneck, we obtain k OH (280 K) = 6.84 × 10 -15 cm 3 molecule -1 s -1The average tropospheric OH lifetimes of MCF is calculated to be τ OH = 9.3 a This value is higher than the average residence times calculated for MCF, which are based on long-term measurements of MCF concentrations and estimates of the amounts emitted yearly (see Section 5).MCF is photolysed at wavelengths around 200 nm [28] and can therefore act as a source of chlorine atoms in the stratosphere and contribute to ozone destruction. It has been phased out as a result of the Protocol of Montreal and its follow-up agreements.An up-to-date data collection of OH-reaction rate constants can be found in Chapter 3. Earlier critical data collections are mostly attributable to Roger Atkinson, whose group also measured many substances for the fi rst time

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“…The Pyrex windows on the 5.5 cm diameter cell were replaced with quartz equivalents. 19 The uncoated Pyrex flow tube used was 103 cm long and of 3.7 cm i.d. After making two passes through the absorption cell, the emerging beam was focused onto the entrance of a UV-transmitting fiber-optic cable, from where it directly entered the PDA.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Studies of the Reaction between NO₃and OClO atT= 300 K andP= 2−8 Torr

1996

Self Cite

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The kinetics of the reaction between the radicals NO 3 and OClO have been investigated at low pressure and room temperature using three laboratory techniques: discharge stopped-flow, slow-flow, and discharge-flow. In all types of experiment, strong evidence was found to suggest that reaction between the two species occurred on the walls of the reaction cell and led to the release of ClO into the gas phase. No evidence was found for the occurrence of the homogeneous reaction NO 3 + OClO f products, and an upper limit for the rate coefficient for this process of 6 × 10 -17 cm 3 molecule -1 s -1 was determined. These experimental results are in disagreement with those of a previous study and suggest that this gas-phase reaction is unlikely to be of atmospheric importance even in the regions of the nighttime stratosphere where both species coexist.Kinetic Studies of the Reaction between NO 3 and OClO

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Reactivity of the nitrate radical towards alkynes and some other molecules

Cited by 40 publications

References 7 publications

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

Abiotic Degradation in the Atmosphere

Kinetic Studies of the Reaction between NO₃and OClO atT= 300 K andP= 2−8 Torr

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Reactivity of the nitrate radical towards alkynes and some other molecules

Cited by 40 publications

References 7 publications

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

A temperature dependence study of the gas-phase reaction of the nitrate radical with 3-fluoropropene followed by laser induced fluorescence detection

Abiotic Degradation in the Atmosphere

Kinetic Studies of the Reaction between NO3and OClO atT= 300 K andP= 2−8 Torr

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Kinetic Studies of the Reaction between NO₃and OClO atT= 300 K andP= 2−8 Torr