Experimental and Theoretical Studies of Rate Coefficients for the Reaction O(3P) + C2H5OH at High Temperatures

Wu, Chih Wei; Lee, Yuan‐Pern; Xu, Shaojie; Lin, Ming‐Chang

doi:10.1021/jp068977z

Cited by 35 publications

(23 citation statements)

References 52 publications

(101 reference statements)

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“…The mechanism now estimates the abstraction from n-butanol by hydroxyl using the G3 calculations of Zhou et al 33 To the best of our knowledge, there are no published calculations for abstraction from n-butanol by atomic oxygen. Thus, for abstraction from the d-, a-, and hydroxyl positions of n-butanol by atomic oxygen, the rate coefficients are now estimated using the calculations of Wu et al 34 for abstraction from the b-, a-, and hydroxyl positions of ethanol, respectively. For abstraction from the gand b-positions of n-butanol by atomic oxygen, Cohen and Westberg's experimental branching ratio for abstraction from the secondary carbons of n-butane by atomic oxygen to abstraction from the primary carbons of n-butane by atomic oxygen 35 is employed.…”

Section: Combustion Chemistry Modelingmentioning

confidence: 99%

High-temperature oxidation chemistry of n-butanol – experiments in low-pressure premixed flames and detailed kinetic modeling

Hansen

Harper

Green

2011

Phys. Chem. Chem. Phys.

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An automated reaction mechanism generator is used to develop a predictive, comprehensive reaction mechanism for the high-temperature oxidation chemistry of n-butanol. This new kinetic model is an advancement of an earlier model, which had been extensively tested against earlier experimental data (Harper et al., Combust. Flame, 2011, 158, 16-41). In this study, the model's predictive capabilities are improved by targeting isomer-resolved quantitative mole fraction profiles of flame species in low-pressure flames. To this end, a total of three burner-stabilized premixed flames are isomer-selectively analyzed by flame-sampling molecular-beam time-of-flight mass spectrometry using photoionization by tunable vacuum-ultraviolet synchrotron radiation. For most species, the newly developed chemical kinetic model is capable of accurately reproducing the experimental trends in these flames. The results clearly indicate that n-butanol is mainly consumed by H-atom abstraction with H, O, and OH, forming predominantly the α-C(4)H(9)O radical (CH(3)CH(2)CH(2)˙CHOH). Fission of C-C bonds in n-butanol is only predicted to be significant in a similar, but hotter flame studied by Oßwald et al. (Combust. Flame, 2011, 158, 2-15). The water-elimination reaction to 1-butene is found to be of no importance under the premixed conditions studied here. The initially formed isomeric C(4)H(9)O radicals are predicted to further oxidize by reacting with H and O(2) or to decompose to smaller fragments via β-scission. Enols are detected experimentally, with their importance being overpredicted by the model.

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Section: Combustion Chemistry Modelingmentioning

confidence: 99%

High-temperature oxidation chemistry of n-butanol – experiments in low-pressure premixed flames and detailed kinetic modeling

Hansen

Harper

Green

2011

Phys. Chem. Chem. Phys.

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“…Since ethanol is more reactive with O( 3 P) than acetonitrile, a lower yield of 1‐octanol and 1,2‐epoxyoctane was expected. [ 1,42 ] When DBSeO was irradiated in ethanol with 500 mM 1‐octene, the total product yield of 1‐octanal and 1,2‐epoxyoctane dropped to 4%. Irradiation of 4 in ethanol with 500 mM 1‐octene with UVA light resulted in 4Se ; however, GC‐FID analysis showed neither a 1‐octanal nor a 1,2‐epoxyoctane peak.…”

Section: Resultsmentioning

confidence: 99%

Visible light‐induced photodeoxygenation of polycyclic selenophene Se‐oxides

Chintala

Throgmorton

Maness

et al. 2020

J of Physical Organic Chem

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Photodeoxygenation of dibenzothiophene S‐oxide (DBTO) is believed to produce ground‐state atomic oxygen [O(3P)] in solution. Compared with other reactive oxygen species (ROS), O(3P) is a unique oxidant as it is potent and selective. Derivatives of DBTO have been used as O(3P)‐precursors to oxidize variety of molecules, including plasmid DNA, proteins, lipids, thiols, and other small organic molecules. Unfortunately, the photodeoxygenation of DBTO requires ultraviolet irradiation, which is not an ideal wavelength range for biological systems, and has a low quantum yield of approximately 0.003. In this work, benzo[b]naphtho[1,2‐d]selenophene Se‐oxide, benzo[b]naphtho[2,1‐d]selenophene Se‐oxide, dinaphtho[2,3‐b:2’,3’‐d]selenophene Se‐oxide, and perylo[1,12‐b,c,d]selenophene Se‐oxide were synthesized, and their ability to utilize visible light for generating O(3P) was interrogated. Benzo[b]naphtho[1,2‐d]selenophene Se‐oxide produces O(3P) upon irradiation centered at 420 nm. Additionally, benzo[b]naphtho[1,2‐d]selenophene Se‐oxide, benzo[b]naphtho[2,1‐d]selenophene Se‐oxide, and dinaphtho[2,3‐b:2’,3’‐d]selenophene Se‐oxide produce O(3P) when irradiated with UVA light and have quantum yields of photodeoxygenation ranging from 0.009 to 0.33. This work increases the utility of photodeoxygenation by extending the range of wavelengths that can be used to generate O(3P) in solution.

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“…e predictions by ethanol submodel were also compared with mole fractions of species measured in stirred and flow reactors. In this paper, by combining complex calculation with recently obtained rate constants, the ethanol submechanism was updated by adjusting the Arrhenius coefficients of some elementary reactions, as shown in Table 1 and [19][20][21][22].…”

Section: Base Mechanism and Case Settingsmentioning

confidence: 99%

An Experimental and Modeling Study on the Combustion of Gasoline-Ethanol Surrogates for HCCI Engines

Yin

Liu

Yang

et al. 2022

Security and Communication Networks

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As an effective clean fuel, ethanol has the characteristics of improving antiknock quality and reducing emissions. It is an ideal antiknock additive for Homogeneous Charge Compression Ignition (HCCI) engines. The oxidation of gasoline-ethanol surrogates in HCCI engines is a very complex process which is dominated by the reaction kinetics. This oxidation process directly determines the performance and emissions of HCCI engines. Coupling the computational fluid dynamic (CFD) model with the gasoline-ethanol surrogate mechanism can be used for fuel design, so the construction of a reduced mechanism with high accuracy is necessary. A mechanism (278 species, 1439 reactions) at medium and low temperatures and experiments in a HCCI engine for the oxidation of gasoline-ethanol surrogates were presented in this paper. Directed relation graph with error propagation (DRGEP) method and quasi-steady-state assumption (QSSA) method were used in order to get a reduced model. Then, the kinetics of the vital reactions related to the formation and consumption of H and OH were adjusted. To validate the model, the HCCI experiments for the oxidation of gasoline-ethanol surrogates were conducted under different operating conditions. The verification result indicated that the present model can predict the oxidation process of gasoline-ethanol effectively.

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Experimental and Theoretical Studies of Rate Coefficients for the Reaction O(³P) + C₂H₅OH at High Temperatures

Cited by 35 publications

References 52 publications

High-temperature oxidation chemistry of n-butanol – experiments in low-pressure premixed flames and detailed kinetic modeling

High-temperature oxidation chemistry of n-butanol – experiments in low-pressure premixed flames and detailed kinetic modeling

Visible light‐induced photodeoxygenation of polycyclic selenophene Se‐oxides

An Experimental and Modeling Study on the Combustion of Gasoline-Ethanol Surrogates for HCCI Engines

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