OH yields from the CH3CO+O2 reaction using an internal standard

Carr, Scott A.; Baeza‐Romero, M. T.; Blitz, Mark A.; Pilling, Michael J.; Heard, Dwayne E.; Seakins, Paul W.

doi:10.1016/j.cplett.2007.07.099

Cited by 43 publications

(74 citation statements)

References 22 publications

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“…A similar disparity in the experimentally determined OH yields was seen for the analogous CH 3 CO + O 2 reaction [5,[13][14][15][16]. In our prior study [5], we established significantly smaller OH yields using the DF method compared with the PLP results of Blitz et al [13].…”

Section: Pressure Dependence Of the Oh Yield For C 2 H 5 Co + Osupporting

confidence: 69%

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

Zügner

Szilágyi

Zádor

et al. 2010

Chemical Physics Letters

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Section: Pressure Dependence Of the Oh Yield For C 2 H 5 Co + Osupporting

confidence: 69%

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

Zügner

Szilágyi

Zádor

et al. 2010

Chemical Physics Letters

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“…24,31,[36][37][38][39] The CH3OCH2 or OH radical precursor(s), reactant (O2), and buffer gas (He or N2) were premixed in a mixing manifold before being flowed through the reaction cell.…”

Section: Methodsmentioning

confidence: 99%

Analysis of the Kinetics and Yields of OH Radical Production from the CH₃OCH₂ + O₂ Reaction in the Temperature Range 195–650 K: An Experimental and Computational study

et al. 2014

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ReuseUnless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. have been measured over the temperature and pressure ranges of 195 -650 K and 5 -500 Torr by detecting the hydroxyl radical using laser induced fluorescence following the excimer laser photolysis (248 nm) of CH3OCH2Br. The reaction proceeds via the formation of an energised CH3OCH2O2 adduct, which either dissociates to OH + 2 H2CO or is collisionally stabilised by the buffer gas. At temperatures above 550 K, a secondary source of OH was observed consistent with thermal decomposition of stabilized CH3OCH2O2 radicals. In order to quantify OH production from the CH3OCH2 + O2 reaction, extensive relative and absolute OH yield measurements were performed over the same (T, P) conditions as the kinetic experiments. The reaction was studied at sufficiently low radical concentrations (~10 11 cm -3 ) that secondary (radical + radical) reactions were unimportant and the rate coefficients could be extracted from simple bi-or tri-exponential analysis. Ab initio (CBS-GB3) / master equation calculations (using the program MESMER) of the CH3OCH2 + O2 system were also performed to better understand this combustion-related reaction as well as be able to extrapolate experimental results to higher temperatures and pressures. To obtain agreement with experimental results (both kinetics and yield data), energies of the key transition states were substantially reduced (by 20 -40 kJ mol -1 ) from their ab initio values and the effect of hindered rotations in the CH3OCH2 and CH3OCH2OO intermediates were taken into account.The optimised master equation model was used to generate a set of pressure and temperature dependent rate coefficients for the component nine phenomenological reactions that describe the CH3OCH2 + O2 system, including four well-skipping reactions. The rate coefficients were fitted to Chebyshev polynomials over the temperature and density ranges 200 to 1000 K and 1×10 17 to 1×10 23 molecule cm -3respectively for both an N2 and He bath gas. Comparisons with an existing autoignition mechanism show that the well-skipping reactions are important at a pressure of 1 bar but are not significant at 10 bar. The 3 main differences derive from the calculated rate coefficient for the CH3OCH2OO CH2OCH2OOH reaction, wh...

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“…The values listed were taken from the reviews of Lightfoot et al, [32] Tyndall et al [33] and Atkinson et al, [26] except for Reaction (R12), which will be discussed below. Recent measurements by Tyndall et al [34] and Carr et al [35] have shown that the reaction of CH 3 CO with O 2 produces OH in one channel with a yield close to unity at zero pressure [Reaction (R4a)]:…”

Section: Computer Simulationsmentioning

confidence: 99%

Photolysis of Acetaldehyde in Air: CH₄, CO and CO₂Quantum Yields

2010

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The quantum yields for CO and CH(4), formed in the photolysis of about 200 μmol mol(-1) of acetaldehyde in air at atmospheric pressure, were determined at 15 wavelengths in the range: 250-330 nm. The quantum yields for CO(2) were determined at nine wavelengths in the range: 250-315 nm. The products are mainly assigned to three primary processes: I) CH(3)CHO*→CH(3)+HCO, II) CH(3)CHO*→CH(4)+CO, III) CH(3)CHO*→CH(3)CO+H, with dissociation occurring from the initially populated S(1) singlet state of acetaldehyde. The pressure dependence of the quantum yields at wavelengths of 270, 304.4, and 313 nm exhibits a Stern-Volmer behavior in all cases. Collisional quenching is shown to deactivate the singlet state S(1) by pressure-induced intersystem crossing to the neighboring triplet state, which is subsequently rapidly quenched by oxygen. Quenching coefficients as a function of excitation energy are obtained by comparison with literature data; the wavelength dependence of individual primary quantum yields is also derived. CO(2) quantum yields at 304.4 and 313 nm were found to increase with rising CH(3)CHO concentrations due to secondary reactions. The reaction mechanism responsible for this effect was explored by means of computer simulations.

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OH yields from the CH3CO+O2 reaction using an internal standard

Cited by 43 publications

References 22 publications

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

Analysis of the Kinetics and Yields of OH Radical Production from the CH₃OCH₂ + O₂ Reaction in the Temperature Range 195–650 K: An Experimental and Computational study

Photolysis of Acetaldehyde in Air: CH₄, CO and CO₂Quantum Yields

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OH yields from the CH3CO+O2 reaction using an internal standard

Cited by 43 publications

References 22 publications

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

OH yields for C2H5CO+O2 at low pressure: Experiment and theory

Analysis of the Kinetics and Yields of OH Radical Production from the CH3OCH2 + O2 Reaction in the Temperature Range 195–650 K: An Experimental and Computational study

Photolysis of Acetaldehyde in Air: CH4, CO and CO2Quantum Yields

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Analysis of the Kinetics and Yields of OH Radical Production from the CH₃OCH₂ + O₂ Reaction in the Temperature Range 195–650 K: An Experimental and Computational study

Photolysis of Acetaldehyde in Air: CH₄, CO and CO₂Quantum Yields