Rate Constants for Reaction of OH Radicals with Acetates and Glycols in the Gas Phase

Hartmann, D.; Gedra, A.; Rhäsa, D.; Zellner, R.

doi:10.1007/978-94-009-3841-0_25

Cited by 12 publications

(15 citation statements)

References 11 publications

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“…Our results do not support this explanation since our experiments were performed at low pressure (35−100 Torr). Hartmann et al have also investigated the temperature dependence of k 4 , and a significant disagreement between their Arrhenius parameters (both A and E/R ) and those reported in this study is observed as shown in Figure . Our values at room temperature and 372 K are, respectively, 22% higher and 24% lower than those obtained by Hartmann et al It is worth noting that the temperature ranges considered in both studies were different.…”

Section: Resultscontrasting

confidence: 66%

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Kinetic Studies of OH Reactions with a Series of Acetates

et al. 1996

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Absolute rate constants have been measured for the gas phase reactions of hydroxyl radicals with a series of aliphatic acetates: methyl acetate (k 1), ethyl acetate (k 2), n-propyl acetate (k 3), n-butyl acetate (k 4), and n-pentyl acetate (k 5). Experiments were carried out using the pulsed laser photolysislaser induced fluorescence technique over the temperature range 243−372 K. The obtained kinetic data were used to derive the Arrhenius expressions, and since the Arrhenius plots were slightly curved they were fitted, using a three-parameter expression. The Arrhenius expressions obtained are: k 1 = (0.53 ± 0.09) × 10-12 exp[−(128 ± 102)/T] ; k 2 = (0.48 ± 0.09) × 10-12 exp[(397 ± 103)/T]; k 3 = (1.03 ± 0.12) × 10-12 exp[(370 ± 69)/T] ; k 4 = (2.10 ± 0.28) × 10-12 exp[(299 ± 81)/T], and k 5 = (2.75 ± 0.46) × 10-12 exp[(302 ± 102)/T] (in units of cm3 molecule-1 s-1). At room temperature, the rate constants obtained (in units of 10-12 cm3 molecule-1 s-1) were as follows: methyl acetate, 0.32 ± 0.03; ethyl acetate, 1.67 ± 0.22; n-propyl acetate, 3.42 ± 0.26 ; n-butyl acetate, 5.52 ± 0.51; n-pentyl acetate, 7.34 ± 0.91. Our results are compared with the previous determinations and discussed in terms of structure−activity relationships.

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Section: Resultscontrasting

confidence: 66%

“…30%. Hartmann et al . and Wallington et al reported a value around 4.2 × 10 -12 , while more recently Williams et al obtained 5.71 × 10 -12 (in cm 3 molecule -1 s -1 ).…”

Section: Resultsmentioning

confidence: 93%

Kinetic Studies of OH Reactions with a Series of Acetates

et al. 1996

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“…10.9 ± 0.5 RR Stemmler et al 14.1 ± 2.8 RR this work 11.4 ± 1.0 PLP-LIF this work C 2 H 5 OCH 2 CH 2 OH 14.5 ± 0.4 LP-RF Hartmann et al 18.7 ± 2.0 FP-RF Dagaut et al …”

Section: Resultsmentioning

confidence: 90%

“…The major fate of oxygenated organic compounds released into the troposphere is through reaction with hydroxyl radicals. To date, relatively few studies have been carried out on the gas-phase reactions of hydroxyl radicals with polyfunctional oxygenated organic, − although rate data for the reactions of OH radicals with various polyalcohols, polyethers, and hydroxyethers ,− have been reported. The purpose of this work was to determine rate constant data for the reaction of OH radicals with a series of diethers and hydroxyethers using both a laser flash photolysis technique and a conventional relative rate method.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Studies on the Reactions of Hydroxyl Radicals with Diethers and Hydroxyethers

Porter¹,

Wenger²,

Treacy³

et al. 1997

J. Phys. Chem. A

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Rate constants for the reactions of OH radicals with a series of diethers and hydroxyethers have been determined at 298 ± 2 K. Rate measurements were made using a pulsed laser photolysis resonance fluorescence technique at total pressures of ∼100 Torr and a conventional photolytic relative rate method at atmospheric pressure. The temperature dependencies of the rate constants for four diethers were also studied over the temperature range 230−372 K using pulsed laser photolysis resonance fluorescence. The rate data for reaction of OH with the diethers show significant deviations from simple structure−activity relationships. Evidence is presented that suggests that these deviations may be a consequence of stabilization of the reaction transition states by hydrogen bonding.

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“…Glycol ethers are used as solvents (3,4) and are hence liable to be released into the atmosphere where they may contribute to the formation of photochemical air pollution in urban and regional areas (5). Glycol ethers react with OH radicals (6)(7)(8)(9)(10)(11)(12) and NO3 radicals (12,13), with the OH radical reactions being calculated to be the dominant tropospheric loss process and with calculated lifetimes of approximately 1 day or less (11,12). However, to date there have been few reported studies of the products and mechanisms of the OH radical-initiated reactions of glycol ethers, with product studies having been reported for 2-ethoxyethanol (14) and 2-butoxyethanol (15).…”

Section: Introductionmentioning

confidence: 99%

Products of the Gas-Phase Reactions of the OH Radical with 1-Methoxy-2-propanol and 2-Butoxyethanol

Tuazon

Aschmann

Atkinson

1998

Environ. Sci. Technol.

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Glycol ethers are used as solvents and are hence liable to be released to the atmosphere, where they react and contribute to the formation of photochemical air pollution. In this work, products of the gas-phase reactions of the OH radical with 1-methoxy-2-propanol and 2-butoxyethanol in the presence of NO have been investigated at 298 ( 2 K and 740 Torr total pressure of air by gas chromatography, in situ Fourier transform infrared spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry. The products observed from 1-methoxy-2propanol were methyl formate, methoxyacetone, and acetaldehyde with molar formation yields of 0.59 ( 0.05, 0.39 ( 0.04, and 0.56 ( 0.07, respectively. The products observed and quantified from 2-butoxyethanol were n-butyl formate, 2-hydroxyethyl formate, propanal, 3-hydroxybutyl formate, and an organic nitrate (attributed to CH 3 CH 2 CH 2 -CH 2 OCH(ONO 2 )CH 2 OH and its isomers), with molar formation yields of 0.57 ( 0.05, 0.22 ( 0.05, 0.21 ( 0.02, 0.07 ( 0.03, and 0.10 ( 0.03, respectively. An additional product of molecular weight 132, attributed to one or more hydroxycarbonyl products, was also observed from the 2-butoxyethanol reaction by atmospheric pressure ionization mass spectrometry. For both glycol ethers, the majority of the reaction products and reaction pathways are accounted for, and detailed reaction mechanisms are presented which account for the observed products.

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Rate Constants for Reaction of OH Radicals with Acetates and Glycols in the Gas Phase

Cited by 12 publications

References 11 publications

Kinetic Studies of OH Reactions with a Series of Acetates

Kinetic Studies of OH Reactions with a Series of Acetates

Kinetic Studies on the Reactions of Hydroxyl Radicals with Diethers and Hydroxyethers

Products of the Gas-Phase Reactions of the OH Radical with 1-Methoxy-2-propanol and 2-Butoxyethanol

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