Revised structure activity parameters derived from new rate coefficient determinations for the reactions of chlorine atoms with a series of seven ketones at 290 K and 1 atm

Farrugia, L. N.; Bejan, Iustinian; Smith, Stuart; Medeiros, Diogo J.; Seakins, Paul W.

doi:10.1016/j.cplett.2015.09.055

Cited by 15 publications

(11 citation statements)

References 42 publications

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“…Recently, Farrugia et al revised the SAR for the reaction of Cl atoms with monoketones reported in Calvert et al . We decided to apply and extend this SAR to α‐diketones using the data obtained for Cl + PTD and Cl + HEX in the present work.…”

Section: Discussionmentioning

confidence: 99%

“…Starting with 2,3‐butanedione, a factor F (–COCO–) = 8.33 × 10 −4 can be calculated from the Cl + 2,3‐butanedione rate constant and the group rate coefficient for primary hydrogen ( k prim = 2.84 × 10 −11 cm 3 molecule −1 s −1 ) . Using the group rate coefficient for secondary hydrogen ( k sec = 8.95 × 10 −11 cm 3 molecule −1 s −1 ) and the substituent factors ( F (–CH 3 ) = 1.00, F (–CH 2 –) = 0.8 from Calvert et al and the revised F (–CR 2 CO–) = 0.563 (R = alkyl group or H)) from Farrugia et al , SAR rate constants of 1.6 × 10 −11 and 7.3 × 10 −11 cm 3 molecule −1 s −1 were predicted for PTD and HEX, respectively, in very good agreement with the experimental values (1.6 × 10 −11 and 8.8 × 10 −11 cm 3 molecule −1 s −1 , respectively). Note that we did not use the 1‐CH 3 grouping rate coefficient of 1.05 × 10 −12 cm 3 molecule −1 s −1 , determined by Farrugia et al for ketones substituted at the second position.…”

Section: Discussionmentioning

confidence: 99%

“…Note that the OH + PTD kinetics were already investigated in a previous paper . The structure–activity relationship (SAR) developed by Farrugia et al for Cl + monoketones reaction kinetics was further extended to α‐diketones. This should improve our understanding of the implication of Cl atom chemistry and allow further extension of atmospheric chemistry models for better air quality predictions.…”

Section: Introductionmentioning

confidence: 99%

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Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals

Bouzidi

Djehiche

Coddeville

et al. 2016

Int J of Chemical Kinetics

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Carbonyls play an important role in atmospheric chemistry due to their formation in the photooxidation of biogenic and anthropogenic volatile organic compounds and their high atmospheric reactivity. The Cl-initiated kinetics of two α-diketones (2,3-pentanedione (PTD) and 2,3-hexanedione (HEX)) have been determined as well as the OH + HEX rate constant using atmospheric simulation chamber experiments and the relative rate method. Up to three different reference compounds were used to assess robust results. The following rate constants (in cm 3 molecule −1 s −1 ) have been obtained at 298 K: k(Cl + PTD) = (1.6 ± 0.2) × 10 −11 , k(Cl + HEX) = (8.8 ± 0.4) × 10 −11 , and k(OH + HEX) = (3.6 ± 0.7) × 10 −12 with a global uncertainty of 30%. The present determinations of Cl-and OH-reaction rate constants for HEX constitute first measurements. Using the present measurements, a recently improved structure-activity relationship for Cl + ketone reactions has been updated by introducing an F(-COCO-) factor of 8.33 × 10 −4 . Atmospheric lifetime calculations indicate that chlorine-initiated oxidation may be a significant α-diketone sink in the marine-boundary layer or in places where high Cl concentrations may be found. C

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals

Bouzidi

Djehiche

Coddeville

et al. 2016

Int J of Chemical Kinetics

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“…It is important to note that in the case of the reaction of Cl atoms in the absence of NO x , where the total carbon yield was lower than 100 %, there were many reaction products that could not be quantified, such as dihydroxy and/or hydroxycarbonyl compounds. In the reaction with the NO 3 radical, due to our .0 ± 10.9 99 45.9 ± 1.6 SPME/GC-TOFMS d 2 9 30 -61.5 ± 1.4 FTIR a Rate coefficient of k= 4.8 × 10 −11 (in cm 3 molecule −1 s −1 ) used to correct the concentration of 3,3-dimethyl-2-butanone by loss with the reaction of Cl atoms (Farrugia et al, 2015). Photolysis rate coefficient estimated for 3,3-dimethyl-2-butanone under our experimental conditions, k p = 7 × 10 −5 s −1 .…”

Section: 3dm2butohmentioning

confidence: 99%

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

et al. 2020

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Abstract. The atmospheric fate of a series of saturated alcohols (SAs) was evaluated through kinetic and reaction product studies with the main atmospheric oxidants. These SAs are alcohols that could be used as fuel additives. Rate coefficients (in cm3 molecule−1 s−1) measured at ∼298 K and atmospheric pressure (720±20 Torr) were as follows: k1 ((E)-4-methylcyclohexanol + Cl) = (3.70±0.16) ×10-10, k2 ((E)-4-methylcyclohexanol + OH) = (1.87±0.14) ×10-11, k3 ((E)-4-methylcyclohexanol + NO3) = (2.69±0.37) ×10-15, k4 (3,3-dimethyl-1-butanol + Cl) = (2.69±0.16) ×10-10, k5 (3,3-dimethyl-1-butanol + OH) = (5.33±0.16) ×10-12, k6 (3,3-dimethyl-2-butanol + Cl) = (1.21±0.07) ×10-10, and k7 (3,3-dimethyl-2-butanol + OH) = (10.50±0.25) ×10-12. The main products detected in the reaction of SAs with Cl atoms (in the absence/presence of NOx), OH radicals, and NO3 radicals were (E)-4-methylcyclohexanone for the reactions of (E)-4-methylcyclohexanol, 3,3-dimethylbutanal for the reactions of 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanone for the reactions of 3,3-dimethyl-2-butanol. Other products such as formaldehyde, 2,2-dimethylpropanal, and acetone have also been identified in the reactions of Cl atoms and OH radicals with 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol. In addition, the molar yields of the reaction products were estimated. The products detected indicate a hydrogen atom abstraction mechanism at different sites on the carbon chain of alcohol in the case of Cl reactions and a predominant site in the case of OH and NO3 reactions, confirming the predictions of structure–activity relationship (SAR) methods. Tropospheric lifetimes (τ) of these SAs have been calculated using the experimental rate coefficients. Lifetimes are in the range of 0.6–2 d for OH reactions, 7–13 d for NO3 radical reactions, and 1–3 months for Cl atoms. In coastal areas, the lifetime due to the reaction with Cl decreases to hours. The calculated global tropospheric lifetimes, and the polyfunctional compounds detected as reaction products in this work, imply that SAs could contribute to the formation of ozone and nitrated compounds at local, regional, and even global scales. Therefore, the use of saturated alcohols as additives in diesel blends should be considered with caution.

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“…The work of Aschmann and Atkinson on Cl plus cycloalkanes and cycloketones included analysis in terms of structure–activity relationships (SAR). These were modified by Farrugia et al , who also highlighted some discrepancies in the prior literature. One goal of this work is to explore the extrapolation of the SAR to new compounds.…”

Section: Introductionmentioning

confidence: 99%

Relative Rate Studies of the Reactions of Atomic Chlorine with Acetone and Cyclic Ketones

Herath

Orozco

Clinch

et al. 2017

Int J of Chemical Kinetics

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Rate coefficients have been measured for Cl atom reactions under ambient conditions with acetone and four cyclic ketones. Cl was generated by UV photolysis of Cl 2 , and other species were monitored by FT-IR spectroscopy. The measurements yield k(Cl + acetone) = (2.0 ± 0.7) × 10 −12 , k(Cl + cyclobutanone) = (10.1 ± 0.8) × 10 −11 , k(Cl + cycloheptanone) = (24.0 ± 2.3) × 10 −11 , k(Cl + 2-methyl cyclopentanone) = (15.2 ± 1.2) × 10 −11 , and k(Cl + 2-methyl cyclohexanone) = (11.2 ± 1.0) × 10 −11 cm 3 molecule −1 s −1 , where the uncertainties represent 95% confidence limits. These results are discussed in the context of structure-activity relationships. We also present a prediction for Cl + cyclopropanone based on ab initio properties of the transition state.

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Revised structure activity parameters derived from new rate coefficient determinations for the reactions of chlorine atoms with a series of seven ketones at 290 K and 1 atm

Cited by 15 publications

References 42 publications

Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals

Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

Relative Rate Studies of the Reactions of Atomic Chlorine with Acetone and Cyclic Ketones

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Revised structure activity parameters derived from new rate coefficient determinations for the reactions of chlorine atoms with a series of seven ketones at 290 K and 1 atm

Cited by 15 publications

References 42 publications

Atmospheric Chemistry of α‐Diketones: Kinetics of C5 and C6 Compounds with Cl Atoms and OH Radicals

Atmospheric Chemistry of α‐Diketones: Kinetics of C5 and C6 Compounds with Cl Atoms and OH Radicals

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

Relative Rate Studies of the Reactions of Atomic Chlorine with Acetone and Cyclic Ketones

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Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals

Atmospheric Chemistry of α‐Diketones: Kinetics of C₅ and C₆ Compounds with Cl Atoms and OH Radicals