Experimental and theoretical studies of gas phase NO3 and OH radical reactions with formaldehyde, acetaldehyde and their isotopomersElectronic supplementary information (ESI) available: program package FACSIMILE for simulation of the complex set of reactions and the kinetics of the reactor system. Kinetic data from the acetaldehyde studies, the spectral ranges and the compounds included in the subtraction procedures, and a full report of the statistical analyses. Calculated energies of the reactants, inter

D’Anna, Barbara; Bakken, Vidar; Beukes, J.A.; Nielsen, Claus J.; Brudnik, Katarzyna; Jodkowski, Jerzy T.

doi:10.1039/b211234p

Cited by 76 publications

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References 62 publications

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“…The recommended values from Baulch et al [36] and the studies by Vandooren et al [37] and Xu et al [38] also agree with current measurement within their uncertainty limit (a factor of 2). Recent quantum chemistry calculations from D'Anna et al [9] agree less well.…”

Section: Summary Of Resultsmentioning

confidence: 90%

“…Vasudevan et al [8] inferred the rate constant over 934 -1670 K in shock tube experiments by monitoring OH concentration time-histories. D'Anna et al [9] performed quantum chemical calculations for the rate constant. However, despite the richness of experimental studies and theoretical calculations, there is still large scatter in the existing data.…”

Section: Introductionmentioning

confidence: 99%

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High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

Wang

Davidson

Hanson

2015

Proceedings of the Combustion Institute

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The overall rate constants for the reactions of hydroxyl radicals (OH) with a series of aldehydes, formaldehyde (CH 2 O), acetaldehyde (CH 3 CHO), propionaldehyde (C 2 H 5 CHO) and n-butyraldehyde (n-C 3 H 7 CHO), were studied behind reflected shock waves at temperatures of 950-1400 K and pressures of 1-2 atm. OH radicals were produced by rapid thermal decomposition of tert-butyl hydroperoxide (TBHP), and OH time-histories were monitored by narrow-linewidth UV laser absorption of the well-characterized R 1 (5) line in the OH AX (0, 0) band near 306.69 nm. The overall rate constants were inferred by fitting simulated OH profiles to the measured OH time histories using detailed mechanisms of Veloo et al. (2013), USC Mech-II (2007) and GRI Mech 3.0. The measured high-temperature aldehydes + OH rate constants can be expressed in modified Arrhenius equations, in units of cm 3 mol-1 s-1 and K, as k CH2O = 1.02 ൈ 10 T ଵ.ଽଶ exp ሺ779/Tሻ േ 13% k CH3CHO = 4.32 ൈ 10 T ଶ.ଶ exp ሺ716K/Tሻ േ 22% k C2H5CHO = 5.94 ൈ 10 T ଵ.ଽ଼ exp ሺ823K/Tሻ േ 27% k nC3H7CHO = 5.36 ൈ 10 T ଶ. exp ሺ658K/Tሻ േ 25% No pressure dependence was observed in these measurements. The measured rate constant for the formaldehyde + OH reaction is consistent with previous experimental work from Vasudevan et al. (2005) within +/-25%. For C 2-C 4 aldehydes + OH, this study provides the first direct rate constant measurement at high temperatures. More general rate constant expressions covering a much wider temperature range (200-1400 K) were also determined by combining current measurements with existing low temperature data in the literature. These wide-range expressions were seen to be in excellent agreement with most existing experimental data.

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Section: Summary Of Resultsmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

Wang

Davidson

Hanson

2015

Proceedings of the Combustion Institute

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“…The negative temperature dependence observed for k 7 ( T ), the reaction of OH (ν = 1) with CH 3 CHO, suggests that this reaction probably also proceeds via formation of an adduct. Taylor et al 22 and D'Anna et al 39 have interpreted the non‐Arrhenius behavior in k 1 ( T ), which shows a positive temperature dependence at temperatures >550 K, to be due to the increased importance of H atom abstraction from the CH 3 group, leading to the formation of CH 2 CHO and H 2 O reaction products, at the higher temperatures.…”

Section: Resultsmentioning

confidence: 99%

Rate coefficients for the OH + acetaldehyde (CH₃CHO) reaction between 204 and 373 K

Zhu

Talukdar

Burkholder

et al. 2008

Int J of Chemical Kinetics

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The rate coefficient, k 1 , for the gas-phase reaction OH + CH 3 CHO (acetaldehyde) → products, was measured over the temperature range 204-373 K using pulsed laser photolytic production of OH coupled with its detection via laser-induced fluorescence. The CH 3 CHO concentration was measured using Fourier transform infrared spectroscopy, UV absorption at 184.9 nm and gas flow rates. The room temperature rate coefficient and Arrhenius expression obtained are k 1 (296 K) = (1.52 ± 0.15) × 10 −11 cm 3 molecule −1 s −1 and k 1 (T ) = (5.32 ± 0.55) × 10 −12 exp[(315 ± 40)/T] cm 3 molecule −1 s −1 . The rate coefficient for the reaction OH (ν = 1) + CH 3 CHO, k 7 (T) (where k 7 is the rate coefficient for the overall removal of OH (ν = 1)), was determined over the temperature range 204-296 K and is given by k 7 (T) = (3.5 ± 1.4) × 10 −12 exp[(500 ± 90)/T], where k 7 (296 K) = (1.9 ± 0.6) × 10 −11 cm 3 molecule −1 s −1 . The quoted uncertainties are 2σ (95% confidence level). The preexponential term and the room temperature rate coefficient include estimated systematic errors. k 7 is slightly larger than k 1 over the range of temperatures included in this study. The results from this study were found to be in good agreement with previously reported values of k 1 (T) for temperatures <298 K. An expression for k 1 (T), suitable for use in atmospheric models, in the NASA/JPL and IUPAC format, was determined by combining the present results with previously reported values and was found to be k 1 (298 K) = 1.5 × 10 −11 cm 3 molecule −1 s −1 , f (298 K) = 1.1, E/R = 340 K, and E/R (or g) = 20 K over the temperature range relevant to the atmosphere. C 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 635-646, 2008

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“…Neben der Photolyse ist die Reaktion mit OH der hauptsächliche Abbaukanal von Acetaldehyd bei Tag. Verschiedene Untersuchungen der primären Produkte der Reaktion zwischen OH und Acetaldehyd bestätigen die Abstraktion des Aldehyd-Wasserstoffs als überwiegenden Reaktionskanal mit einer Primärausbeute von CH 3 CO von mindestens 95 % bei Raumtemperatur [5,6] und darunter [7].…”

Section: Ergebnisse Und Diskussionunclassified

“…Die Reaktion von Acetaldehyd und dem OH-Radikal läuft beinahe ausschließlich über die Abstraktion des aldehydischen Wasserstoffs ab. Unabhängige Produktstudien kommen zu dem Ergebnis, dass CH 3 CO mit einer Primärausbeute von mindestens 95 % bei Raumtemperatur [5,6] und darunter [7] In keiner bisher veröffentlichten Arbeit wurde für die Reaktion eine Druckabhängigkeit im Bereich zwischen 1 und etwa 1000 mbar gefunden. Die Lebensdauer von intermediären Komplexen in der Reaktion wird dadurch eingegrenzt, da ihre Stabilisierung in der Druckabhängigkeit der Reaktion sichtbar werden würde.…”

Section: Die Reaktion Von Acetaldehyd Und Oh Ohne Wasserunclassified

Kinetik und Dynamik bei tiefen Temperaturen in Lavaldüsenexpansionen

Hansmann¹

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Cited by 76 publications

References 62 publications

High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

Rate coefficients for the OH + acetaldehyde (CH₃CHO) reaction between 204 and 373 K

Kinetik und Dynamik bei tiefen Temperaturen in Lavaldüsenexpansionen

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Cited by 76 publications

References 62 publications

High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

High temperature measurements for the rate constants of C1–C4 aldehydes with OH in a shock tube

Rate coefficients for the OH + acetaldehyde (CH3CHO) reaction between 204 and 373 K

Kinetik und Dynamik bei tiefen Temperaturen in Lavaldüsenexpansionen

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Product

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Rate coefficients for the OH + acetaldehyde (CH₃CHO) reaction between 204 and 373 K