A Multiple Shock Tube and Chemical Kinetic Modeling Study of Diethyl Ether Pyrolysis and Oxidation

Yasunaga, Kōjirō; Gillespie, F.C.; Simmie, John M.; Curran, Henry J.; Kuraguchi, Yuma; Hoshikawa, Hiroki; Yamane, Masatsugu; Hidaka, Yoshiaki

doi:10.1021/jp104070a

Cited by 111 publications

(148 citation statements)

References 38 publications

(66 reference statements)

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“…Also, much less is known about the reaction of oxygen-centered radicals compared to carbon-centered ones. We treated this reaction with the same rate as a C 2 H 5 radical adding to ethylene [30]. Further investigation is needed into this important reaction type which also controls the decomposition of ester radicals.…”

Section: Radical Decompositionmentioning

confidence: 99%

An experimental and modeling study of diethyl carbonate oxidation

Nakamura

Curran

Córdoba

et al. 2015

Combustion and Flame

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Diethyl carbonate (DEC) is an attractive biofuel that can be used to displace petroleum-derived diesel fuel, thereby reducing CO 2 and particulate emissions from diesel engines. A better understanding of DEC combustion characteristics is needed to facilitate its use in internal combustion engines. Towards this goal, ignition delay times for DEC were measured at conditions relevant to internal combustion engines using a rapid compression machine (RCM) and a shock tube. The experimental conditions investigated covered a wide range of temperatures (660-1300 K), a pressure of 30 bar, and equivalence ratios of 0.5, 1.0 and 2.0 in air.To provide further understanding of the intermediates formed in DEC oxidation, species concentrations were measured in a jet-stirred reactor at 10 atm over a temperature range of 500-1200 K and at equivalence ratios of 0.5, 1.0 and 2.0. These experimental measurements were used to aid the development and validation of a chemical kinetic model for DEC.The experimental results for ignition in the RCM showed near negative temperature coefficient (NTC) behavior. Six-membered alkylperoxy radical (R 2 ) isomerizations are conventionally thought to initiate low-temperature branching reactions responsible for NTC behavior, but DEC has no such possible 6-and 7-membered ring isomerizations. However, its molecular structure allows for 5-, 8-and 9-membered ring R 2 isomerizations. To provide accurate rate constants for these ring structures, ab initio computations for R 2 QOOH isomerization reactions were performed. These new R 2 isomerization rate constants have been implemented in a chemical kinetic model for DEC oxidation. The model simulations have been compared with ignition delay times measured in the RCM near the NTC region. Results of the 3 simulation were also compared with experimental results for ignition in the high-temperature region and for species concentrations in the jet-stirred reactor. Chemical kinetic insights into the oxidation of DEC were made using these experimental and modeling results.

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Section: Radical Decompositionmentioning

confidence: 99%

An experimental and modeling study of diethyl carbonate oxidation

Nakamura

Curran

Córdoba

et al. 2015

Combustion and Flame

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“…is a C-CHO stretching vibration ν(C-CHO), and it suggests that HCHO and CH 3 CHO have been produced [9,[48][49][50][51][52][53][54]. The absorption peak at ν = 1147 cm −1 is a C-O-C stretching vibration ν(C-O-C) of diethyl ether, and this means that diethyl ether molecule has been absorbed on the surface.…”

Section: 2mentioning

confidence: 99%

“…Possible equations describing the process may be written as follows [54]: . And that at ν = 2347 cm −1 is a CO 2 stretching vibration ν(CO 2 ).…”

Section: 2mentioning

confidence: 99%

“…The peaks at ν = 1490 cm −1 and 1386 cm −1 are the CH 2 , CH 3 deformation vibrations δ(CH 2 ), δ(CH 3 ), respectively. These features can be attributed to the A possible reaction mechanism of diethyl ether at 380°C and 400°C may be written using equation 5 to equation 12 as well as the following [54] Fig. 7 shows DRFT-IR spectra of 200 ppm diethyl ether adsorption on the SnO 2 film and thermal decomposition of ethyl ether after 10 min at different temperatures.…”

Section: 2mentioning

confidence: 99%

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Gas-sensing properties and in-situ diffuse-reflectance Fourier-transform infrared spectroscopy study of diethyl ether adsorption and reactions on SnO₂ film

Wang

Huang

Song

2017

Materials Science-Poland

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Diethyl ether is a common industrial reagent and medical anesthetic. It is necessary to carry out real-time monitoring of this molecule due to its harmful effects on human health. In this paper, a highly sensitive diethyl ether SnO 2 gas-sensing material has been prepared by a sol-gel method. The gas sensitivity was tested by a home-made gas-sensing equipment. The surface adsorption and reaction processes between the SnO 2 gas-sensing film and the diethyl ether have been studied by in situ diffuse-reflectance Fourier-transform infrared spectroscopy (DRFT-IR) at different temperatures. The results show that the SnO 2 gas-sensing material has high sensitivity to diethyl ether, and the lowest detection limit can reach 1 ppm. Furthermore, ethyl (CH 3 CH 2 •), oxoethyl (CH 3 CH 2 O•), ethanol (CH 3 CH 2 OH), formaldehyde (HCHO), acetaldehyde (CH 3 CHO), ethylene (C 2 H 4 ), H 2 O and CO 2 surface species are formed during diethyl ether adsorption at different temperatures. A possible mechanism of the reaction process is discussed.

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“…Satisfactory agreement was achieved with substantial low temperature chemical reaction additions to the comprehensive DEE sub-mechanism, as discussed below. Yasunaga et al [37,38] presented a DEE chemical kinetic model for high temperature pyrolysis and oxidation conditions. Werler et al [39] later validated the model against high temperature shock tube measurements and made modifications to rates of hydrogen abstraction by HO 2 radicals to better predict their data.…”

Section: Chemical Kineticsmentioning

confidence: 99%

Experimental and Numerical Investigation of Ethanol/Diethyl Ether Mixtures in a CI Engine

Vedharaj¹,

Vallinayagam²,

Ali³

et al. 2016

SAE Technical Paper Series

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The auto-ignition characteristics of diethyl ether (DEE)/ethanol mixtures are investigated in compression ignition (CI) engines both numerically and experimentally. While DEE has a higher derived cetane number (DCN) of 139, ethanol exhibits poor ignition characteristics with a DCN of 8. DEE was used as an ignition promoter for the operation of ethanol in a CI engine. Mixtures of DEE and ethanol (DE), i.e., DE75 (75% DEE + 25% ethanol), DE50 (50% DEE + 50% ethanol) and DE25 (25% DEE + 75% ethanol), were tested in a CI engine. While DE75 and DE50 auto-ignited at an inlet air pressure of 1.5 bar, DE25 failed to auto-ignite even at boosted pressure of 2 bar. The peak in-cylinder pressure for diesel and DE75 were comparable, while DE50 showed reduced peak in-cylinder pressure with delayed start of combustion (SOC). Numerical simulations were conducted to study the engine combustion characteristics of DE mixture. A comprehensive detailed chemical kinetic model was created to represent the combustion of DE mixtures. The detailed mechanism was then reduced using standard direct relation graph (DRG-X) method and coupled with 3D CFD code, CONVERGE, to simulate the experimental data. The simulation results showed that the effects of physical properties on DE50 combustion are negligible. Simulations of DE50 mixture revealed that the combustion is nearly homogenous, while diesel (n-heptane used as a surrogate) and DE75 showed similar combustion behavior with flame liftoff and diffusion controlled combustion. Diesel exhibited auto-ignition at an equivalence ratio of 2, while DE75 and DE50 showed auto-ignition in the equivalence ratio range of 1-1.5 and 0-1, respectively. The experiments and numerical simulations demonstrate how the high reactivity of DEE supports the auto-ignition of ethanol, while ethanol acts as a radical scavenger.

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A Multiple Shock Tube and Chemical Kinetic Modeling Study of Diethyl Ether Pyrolysis and Oxidation

Cited by 111 publications

References 38 publications

An experimental and modeling study of diethyl carbonate oxidation

An experimental and modeling study of diethyl carbonate oxidation

Gas-sensing properties and in-situ diffuse-reflectance Fourier-transform infrared spectroscopy study of diethyl ether adsorption and reactions on SnO₂ film

Experimental and Numerical Investigation of Ethanol/Diethyl Ether Mixtures in a CI Engine

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A Multiple Shock Tube and Chemical Kinetic Modeling Study of Diethyl Ether Pyrolysis and Oxidation

Cited by 111 publications

References 38 publications

An experimental and modeling study of diethyl carbonate oxidation

An experimental and modeling study of diethyl carbonate oxidation

Gas-sensing properties and in-situ diffuse-reflectance Fourier-transform infrared spectroscopy study of diethyl ether adsorption and reactions on SnO2 film

Experimental and Numerical Investigation of Ethanol/Diethyl Ether Mixtures in a CI Engine

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Gas-sensing properties and in-situ diffuse-reflectance Fourier-transform infrared spectroscopy study of diethyl ether adsorption and reactions on SnO₂ film