Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Schütze, Nicole; Zhong, Xiaoyin; Kirschbaum, Stefan; Bejan, Iustinian; Barnes, Ian; Benter, Thorsten

doi:10.1016/j.atmosenv.2009.08.011

Cited by 24 publications

(30 citation statements)

References 32 publications

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“…where 9,16 k OH ethene is the rate coefficient for the reaction of ethylene with OH radicals at 298 K, and the value was 8.64 × 10 −12 cm 3 molecule −1 s −1 . 33 Based on these values, the POCPs of M2MP and M2MB were calculated to be 17 and 22, respectively.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In addition to this, Ifang et al 10 studied the rate coefficient for the reaction of M2MP with Cl atoms at 298 K using RR−Fourier-transform infrared (FTIR) spectroscopy and RR−gas chromatography (GC)−flame ionization detection (FID) techniques relative to ethylene (C 2 H 4 ) and propyl ethanoate (C 5 H 10 O 2 ). The rate coefficients (in units of cm 3 molecule −1 s −1 ) were reported as k = (3.72 ± 0.43) × 10 On the other hand, the reaction of methyl-2-methyl butanoate (M2MB) with Cl atoms was investigated for the first time by Schuẗze et al 16 at 298 K with respect to three reference compounds [C 2 H 6 , C 2 H 4 , and toluene (C 7 H 8 )] using the RR technique. The 298 K rate coefficient was reported as k = (9.41 ± 1.39) × 10 −11 cm 3 molecule −1 s −1 .…”

Section: ■ Introductionmentioning

confidence: 99%

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Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Kaipara

Rajakumar

2020

ACS Earth Space Chem.

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The relative rate technique coupled with gas chromatography (GC)–flame ionization detection was used to investigate the kinetics of the reaction of methyl-2-methyl propionate (M2MP) and methyl-2-methyl butanoate (M2MB) with the Cl atom between 268 and 363 K and at 760 Torr of N2 as a diluent gas. Temperature-dependent Arrhenius expressions were obtained as k 268–363K M2MP+Cl = [(7.15 ± 1.16) × 10–12 exp((566 ± 50)/T)] cm3 molecule–1 s–1 and k 268–363K M2MB+Cl = [(6.88 ± 0.80) × 10–12 exp((794 ± 125)/T)] cm3 molecule–1 s–1. The rate coefficients (in units of cm3 molecule–1 s–1) at 298 K were measured to be k 298K M2MP+Cl = (4.61 ± 1.28) × 10–11 and k 298K M2MB+Cl = (9.44 ± 1.90) × 10–11. In addition to this, the measured kinetics were also compared with the kinetics computed using the canonical variational transition state theory/small curvature tunneling /interpolated single-point energies method. The degradation mechanism was also postulated using GC–mass spectrometry and GC–infrared spectrometry as the analytical methods. Furthermore, the atmospheric lifetimes of the test molecules were estimated and are presented in this article.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Kaipara

Rajakumar

2020

ACS Earth Space Chem.

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“…For example, Cl atoms react with alkenes via the addition of Cl atoms to the double bonds and abstraction of allylic hydrogen atoms . Cl atoms react with alkylnaphthalenes, alkylbenzenes, and methyl alkyl esters via abstraction of hydrogen atoms from the substituent alkyl groups . Cl atoms react with furan via addition of Cl atoms to the double bond of furan .…”

Section: Resultsmentioning

confidence: 99%

Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Wei

Mandin

Ramalho

2017

Int. J. Chem. Kinet.

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Indoor semivolatile organic compounds (SVOCs) originate from indoor and outdoor sources. These SVOCs partition among different phases and available surfaces, which increases their residence time indoors to several years. SVOCs may also react with indoor oxidants, such as hydroxyl radicals (OH), nitrate radicals (NO3), and ozone. In the present study, the second‐order reaction rate constants of 72 SVOCs in indoor air (gas and particle phases) at room temperature and ambient air pressure were retrieved from the literature. The pseudo–first‐order reaction rate constants of these SVOCs were calculated for the indoor concentration ranges of OH, NO3, and ozone. Then, the extent to which the chemical reaction had a meaningful impact on the removal of SVOCs from the indoor environment was quantitatively analyzed. The orders of magnitude of the second‐order rate constant ranged between 10−15 and 10−10 cm3/(molecule·s) for OH/SVOC reactions, 10−17 and 10−12 cm3/(molecule·s) for NO3/SVOC reactions, and 10−20 and 10−16 cm3/(molecule·s) for ozone/SVOC reactions in indoor air. Assuming that the highest indoor reactant concentrations were 1.8 × 106 molecules/cm3 (7.3 × 10−5 ppb) for OH, 2.5 × 108 molecules/cm3 (10−2 ppb) for NO3, and 1.4 × 1012 molecules/cm3 (58 ppb) for ozone, the highest pseudo–first‐order rate constants in the gas phase for the studied reactions of OH/SVOCs (n = 72), NO3/SVOCs (n = 3), and ozone/SVOCs (n = 14) reached 1.5 h−1 (OH/benzo[a]pyrene), 0.41 h−1 (NO3/acenaphthene), and 1.0 h−1 (ozone/aldrin and ozone/heptachlor), respectively. The pseudo–first‐order rate constants in the particle phase for the studied reactions of OH/SVOCs (n = 13), NO3/SVOCs (n = 6), and ozone/SVOCs (n = 14) at the high indoor reactant concentrations reached 0.09 h−1 (OH/DEHP), 5.8 h−1 (NO3/pyrene), and 11 h−1 (ozone/benzo[a]pyrene), respectively. These results indicate that the chemical reactions of some SVOCs in indoor air have a meaningful impact compared to the air exchange rate, which should be considered in future studies on indoor air quality modeling.

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“…Note that the unattributed fraction is usually below the measurement uncertainty. 2.66E-11 PTR-ToF-MS Butanoic acid methyl ester; acetic acid methylethyl ester, 2-methylpropanoic acid methylester, npropyl acetate; 1-hydroxy-2methyl-3-butanone; 1-hydroxy-3methyl-2-butanone; 5-hydroxy-2pentanone; pentanoic acid; C5-diol (ISOPOOH conversion product on metal surfaces (Mentler, 2018)) average Schütze et al, 2010;Ferrari et al, 1996;Aschmann et al, 2000;NCBI, 2006;St Clair et al, 2016…”

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confidence: 99%

Supplementary material to "Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure"

Pfannerstill¹,

Reijrink²,

Edtbauer³

et al. 2020

Preprint

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Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Cited by 24 publications

References 32 publications

Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Supplementary material to "Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure"

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Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Cited by 24 publications

References 32 publications

Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Temperature-Dependent Kinetics of the Reactions of Methyl-2-methyl Propionate and Methyl-2-methyl Butanoate with Cl Atoms under Tropospheric Conditions

Reactivity of Semivolatile Organic Compounds with Hydroxyl Radicals, Nitrate Radicals, and Ozone in Indoor Air

Supplementary material to &quot;Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure&quot;

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Supplementary material to "Total OH reactivity over the Amazon rainforest: variability with temperature, wind, rain, altitude, time of day, season, and an overall budget closure"