Reaction of Ethylene with Hydroxyl Radicals:  A Theoretical Study

Senosiain, Juan P.; Klippenstein, Stephen J.; Miller, James A.

doi:10.1021/jp0566820

Cited by 168 publications

(419 citation statements)

References 91 publications

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“…This expression is typical of what we have found for small molecules interacting with weak colliders [75][76][77][78][79][80][81][82][83][84][85].…”

Section: H + N 2 Osupporting

confidence: 73%

The role of NNH in NO formation and control

Klippenstein

Harding

Glarborg³

et al. 2011

Combustion and Flame

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356

268

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One of the remaining issues in our understanding of nitrogen chemistry in combustion is the chemistry of NNH. This species is known as a key intermediate in Thermal DeNO x , where NH 3 is used as a reducing agent for selective non-catalytic reduction of NO. In addition, NNH has been proposed to facilitate formation of NO from thermal fixation of molecular nitrogen through the socalled NNH mechanism. The importance of NNH for formation and reduction of NO depends on its thermal stability and its major consumption channels. In the present work, we study reactions on the NNH + O, NNH + O 2 , and NH 2 + O 2 potential energy surfaces using methods previously developed by Miller, Klippenstein, Harding, and their co-workers. Their impact on Thermal DeNO x and the NNH mechanism for NO formation is investigated in detail.

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“…This expression is typical of what we have found for small molecules interacting with weak colliders [75][76][77][78][79][80][81][82][83][84][85].…”

Section: H + N 2 Osupporting

confidence: 73%

The role of NNH in NO formation and control

Klippenstein

Harding

Glarborg³

et al. 2011

Combustion and Flame

Self Cite

356

268

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“…In the pyrolysis and oxidation of saturated alcohols, they are produced by hydrogen abstraction from the carbon atom in alpha position of the hydroxyl group followed by subsequent β-scission [1]. They are also formed in the oxidation of hydrocarbons [21,22], for example C2H4 + •OH ⇌ •CH2CH2OH ⇌ CH2=CHOH + •H [23] and C3H6 + •OH ⇌ CH3•CHCH2OH ⇌ CH3CH=CHOH + •H [24] and [25]. Enols may isomerize to their corresponding aldehydes by keto-enol tautomerization, which is catalyzed by hydrogen atoms, hydroperoxy radicals [26] and carboxylic acids [27] in the gas phase.…”

Section: Introductionmentioning

confidence: 99%

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Bruycker

Herbinet

Carstensen

et al. 2016

Combustion and Flame

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. Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol. Combustion and Flame, Elsevier, 2016, 171, pp.237-251. 1 Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol AbstractThe reactivity of unsaturated alcohols with a C=C double bond in the β-and γ-positions to the hydroxyl group is not well established. The pyrolysis and oxidation of two such unsaturated alcohols have been studied, i.e. 3-methyl-2-butenol (prenol) and 3-methyl-3-butenol (isoprenol). Experiments at three equivalence ratios, i.e. φ = 0.5, φ = 1.0 and φ = ∞ (pyrolysis), were performed using an isothermal jet-stirred quartz reactor at temperatures ranging from 500 to 1100 K, a pressure of 0.107 MPa and a residence time of 2 s. The reactant and product concentrations were quantified using gas chromatography. A kinetic model has been developed using the automatic network generation tool "Genesys". Several important rate coefficients are obtained from new quantum chemical calculations. Overall, there is a good agreement between model calculated mole fraction profiles and experimental data. Reaction path analysis reveals that isoprenol consumption is dominated by a unimolecular reaction to formaldehyde and isobutene. At the applied operating conditions, the equivalence ratio has no effect on the isoprenol conversion profile. Pyrolysis and oxidation of prenol is dominated by radical chemistry, with hydrogen abstractions from prenol forming resonantly stabilized radicals as dominating conversion path. Oxidation and decomposition of the resulting radicals are predicted to form 3-methyl-2-butenal and 2-methyl-1,3-butadiene, which have been detected as important products in the reactor effluent.

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“…Recent studies, both theoretical and experimental, have attempted to determine branching ratios of the product channels of the reaction, beginning at the CH 2 CH 2 OH (β-hydroxyethyl) radical adduct. 23,29,30 The CH 2 CH 2 OH radical intermediate may be produced from the photodissociation of 2-haloethanols. Hintsa et al 31 were the first to investigate the photodissociation of 2-bromoethanol at 193 nm, showing that a large fraction of β-hydroxyethyl radicals were formed stable to subsequent dissociation to OH + ethene and attributing it to a large partitioning of energy into rotational energy of the radicals.…”

Section: Introductionmentioning

confidence: 99%

Photoproduct Channels from BrCD₂CD₂OH at 193 nm and the HDO + Vinyl Products from the CD₂CD₂OH Radical Intermediate

et al. 2012

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We present the results of our product branching studies of the OH + C 2 D 4 reaction, beginning at the CD 2 CD 2 OH radical intermediate of the reaction, which is generated by the photodissociation of the precursor molecule BrCD 2 CD 2 OH at 193 nm. Using a crossed laser-molecular beam scattering apparatus with tunable photoionization detection, and a velocity map imaging apparatus with VUV photoionization, we detect the products of the major primary photodissociation channel (Br and CD 2 CD 2 OH), and of the secondary dissociation of vibrationally excited CD 2 CD 2 OH radicals (OH, C 2 D 4 / CD 2 O, C 2 D 3 , CD 2 H, and CD 2 CDOH). We also characterize two additional photodissociation channels, which generate HBr + CD 2 CD 2 O and DBr + CD 2 CDOH, and measure the branching ratio between the C−Br bond fission, HBr elimination, and DBr elimination primary photodissociation channels as 0.99:0.0064:0.0046. The velocity distribution of the signal at m/e = 30 upon 10.5 eV photoionization allows us to identify the signal from the vinyl (C 2 D 3 ) product, assigned to a frustrated dissociation toward OH + ethene followed by D-atom abstraction. The relative amount of vinyl and Br atom signal shows the quantum yield of this HDO + C 2 D 3 product channel is reduced by a factor of 0.77 ± 0.33 from that measured for the undeuterated system. However, because the vibrational energy distribution of the deuterated radicals is lower than that of the undeuterated radicals, the observed reduction in the water + vinyl product quantum yield likely reflects the smaller fraction of radicals that dissociate in the deuterated system, not the effect of quantum tunneling. We compare these results to predictions from statistical transition state theory and prior classical trajectory calculations on the OH + ethene potential energy surface that evidenced a roaming channel to produce water + vinyl products and consider how the branching to the water + vinyl channel might be sensitive to the angular momentum of the β-hydroxyethyl radicals.

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Reaction of Ethylene with Hydroxyl Radicals: A Theoretical Study

Cited by 168 publications

References 91 publications

The role of NNH in NO formation and control

The role of NNH in NO formation and control

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Photoproduct Channels from BrCD₂CD₂OH at 193 nm and the HDO + Vinyl Products from the CD₂CD₂OH Radical Intermediate

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Reaction of Ethylene with Hydroxyl Radicals: A Theoretical Study

Cited by 168 publications

References 91 publications

The role of NNH in NO formation and control

The role of NNH in NO formation and control

Understanding the reactivity of unsaturated alcohols: Experimental and kinetic modeling study of the pyrolysis and oxidation of 3-methyl-2-butenol and 3-methyl-3-butenol

Photoproduct Channels from BrCD2CD2OH at 193 nm and the HDO + Vinyl Products from the CD2CD2OH Radical Intermediate

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Product

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Photoproduct Channels from BrCD₂CD₂OH at 193 nm and the HDO + Vinyl Products from the CD₂CD₂OH Radical Intermediate