Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

Walavalkar, Mohini P.; Sharma, Ashima; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, Prakash D.; Bajaj, P.N.

doi:10.1016/j.atmosenv.2012.10.039

Cited by 22 publications

(49 citation statements)

References 30 publications

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“…A similar trend is also observable for the reaction of Cl atoms with the series of 3-alken-1-ols (blue) with 3-buten-1-ol [62], (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol ( [39] and this work), (Z)-3-hepten-1-ol, and (Z)-3-octen-1-ol [39]. The activation effect of the chain length on the rate constants was also observed in previous works for the reaction of Cl atoms with linear alcohols [63] and alkenes [22,[64][65][66].…”

Section: Effect Of the Chain Lengthsupporting

confidence: 86%

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

et al. 2020

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The reactions of five structurally similar unsaturated alcohols, i.e., (Z)-2-penten-1-ol, (E)-2-hexen-1-ol, (E)-3-hexen-1-ol, (Z)-3-hexen-1-ol, and 1-octen-3-ol, with Cl atoms in the gas phase, were investigated at 296 ± 2 K and 1 atm by the relative-rate kinetic technique using a 600-L Teflon reaction chamber. Selected ion flow tube mass spectrometry (SIFT-MS) was used simultaneously to monitor the decay of the alcohols of interest and selected reference compounds. Tetrahydrofuran (THF), propan-1-ol, and octane were used as reference compounds. Chlorine atoms were produced by the photolysis of molecular chlorine (Cl 2 ) using broadband actinic lamps near 365 nm. The estimated rate constant values (in 10 −10 cm 3 ·molecule −1 ·s −1 ) followed the order 2.99 ± 0.53 ((Z)-2-penten-1-ol) < 3.05 ± 0.59 ((E)-3-hexen-1-ol) < 3.15 ± 0.58 ((Z)-3-hexen-1-ol) < 3.41 ± 0.65 ((E)-2-hexen-1-ol) < 4.03 ± 0.77 (1-octen-3-ol). The present work provides the first value of the rate constant for the reaction of 1-octen-3-ol with Cl atoms. The results are discussed and interpreted in relation to other studies where literature data are available. The structure-activity relationship and the atmospheric implications are discussed as well.

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Section: Effect Of the Chain Lengthsupporting

confidence: 86%

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

et al. 2020

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“…formaldehyde, acetone)36, oxidation of alkenes proceeds via addition of Cl and results in the formation of chlorinated products (e.g. formyl chloride and chloroacetone)3738, creating a relatively long-lived (>1 month) Cl reservoir. These chlorinated secondary products of hydrocarbon oxidation by OH are not included in current inventories, which so far only consider the products of halocarbon oxidation by OH5.…”

Section: Discussionmentioning

confidence: 99%

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

Baker

Sauvage

Thorenz

et al. 2016

Sci Rep

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The chlorine radical is a potent atmospheric oxidant, capable of perturbing tropospheric oxidative cycles normally controlled by the hydroxyl radical. Significantly faster reaction rates allow chlorine radicals to expedite oxidation of hydrocarbons, including methane, and in polluted environments, to enhance ozone production. Here we present evidence, from the CARIBIC airborne dataset, for extensive chlorine radical chemistry associated with Asian pollution outflow, from airborne observations made over the Malaysian Peninsula in winter. This region is known for persistent convection that regularly delivers surface air to higher altitudes and serves as a major transport pathway into the stratosphere. Oxidant ratios inferred from hydrocarbon relationships show that chlorine radicals were regionally more important than hydroxyl radicals for alkane oxidation and were also important for methane and alkene oxidation (>10%). Our observations reveal pollution-related chlorine chemistry that is both widespread and recurrent, and has implications for tropospheric oxidizing capacity, stratospheric composition and ozone chemistry.

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“…Rate coefficients, in cm 3 molecule -1 s -1 , at 296 ± 2 K and 1 atm, for the reactions of OH radicals with alkenes are: k OH,propene = 3.0 × 10 -11 , 14 k OH,ethylene = 8.5 × 10 -12 , k OH,1-butene = 3.1 × 10 -11 , k OH,cis-2-butene = 5.6 × 10 -11 , k OH,1-pentene = 3.1 × 10 -11 , k OH,2-methyl-2-butene = 8.7 × 10 -11 , k OH,2,3-dimethyl-2-butene = 1.1 × 10 . 21 The Cl and OH reactions with alkenes and the corresponding rate coefficients are collected in two different groups. In the first group, hydrogen atoms connected to carbon atoms at the double bound are replaced by methyl groups (ethylene, propene, cis-2-butene, 2-methyl-2-butene and 2,3-dimethyl-2-butene) and an increase on the rate coefficients, from k OH,ethylene to k OH,2,3-dimethyl-2-butene (or from k Cl,propene to k Cl,2-methyl-2-butene ), is observed, as evidenced in Figure 3.…”

Section: Reactivity and Reaction Mechanismmentioning

confidence: 99%

Rate Coefficient for the Reaction of Cl Atoms with cis-3-Hexene at 296 ± 2 K

Barbosa¹,

Barrera²,

Jara‐Toro³

et al. 2017

J. Braz. Chem. Soc.

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The rate coefficient of the cis-3-hexene + Cl atoms reaction at 296 ± 2 K and 750 ± 10 Torr was determined using the relative rate technique. The reaction was investigated using an 80 L Teflon reaction bag and a gas chromatograph coupled with flame-ionization detection. Chlorine atoms were produced by the photolysis of trichloroacetyl chloride. No previous experimental data was available in the literature, to the best of our knowledge. The mean second-order rate coefficient value found was (4.13 ± 0.51) × 10 -10 cm 3 molecule -1 s -1. The experimental value agrees with the rate coefficient estimated by structure-reactivity analysis, 4.27 × 10 -10 cm 3 molecule -1 s -1. Moreover, both addition and hydrogen abstraction channels contribute to the global kinetics, with branching ratios 70:30. Effective lifetime with respect to Cl atoms is predicted as 67.2 hours; however, the cis-3-hexene + Cl channel is suggested to be non-negligible at atmospheric conditions. Other atmospheric implications are discussed.

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Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

Cited by 22 publications

References 30 publications

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

Kinetic Measurements of Cl Atom Reactions with C5–C8 Unsaturated Alcohols

Evidence for strong, widespread chlorine radical chemistry associated with pollution outflow from continental Asia

Rate Coefficient for the Reaction of Cl Atoms with cis-3-Hexene at 296 ± 2 K

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