Absolute cross-sections for dissociative photoionization of some small esters

Wang, Juan; Yang, Bin; Cool, Terrill A.; Hansen, Nils

doi:10.1016/j.ijms.2010.02.010

Cited by 50 publications

(39 citation statements)

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“…Figure 7 shows the JSR-sampled photoionization efficiency curve for m/z = 60.021 u 86 Methyl formate detection has also been reported by Guo et al 18 and Herrmann et al 21 According to most models, methyl formate can be formed starting with reaction (R1) forming the…”

Section: Detection and Identificationsupporting

confidence: 53%

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

et al. 2015

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In this paper we report the detection and identification of the keto-hydroperoxide (hydroperoxymethyl formate, HPMF, HOOCH 2 OCHO) and other partially oxidized intermediate species arising from the low-temperature (540 K) oxidation of dimethyl ether (DME). These observations were made possible by coupling a jet-stirred reactor with molecular-beam sampling capabilities, operated near atmospheric pressure, to a reflectron time-of-flight mass spectrometer that employs single-photon ionization via tunable synchrotron-generated vacuum-ultraviolet radiation. Based on experimentally observed ionization thresholds and fragmentation appearance energies, interpreted with the aid of ab initio calculations, we have identified HPMF and its

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Section: Detection and Identificationsupporting

confidence: 53%

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

et al. 2015

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“…53−57 The mole fraction profiles were derived with eq 1 by using published photoionization cross sections. 45,47,51 These new data shown here can serve as validation targets for present and future mechanisms, and consequently, we compared our experimental data with modeling results using the three mechanisms mentioned above.…”

Section: Resultsmentioning

confidence: 99%

Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

et al. 2016

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This work provides new temperature-dependent mole fractions of elusive intermediates relevant to the lowtemperature oxidation of dimethyl ether (DME). It extends the previous study of Moshammer et al. [J. Phys. Chem. A 2015, 119, 7361−7374] in which a combination of a jet-stirred reactor and molecular beam mass spectrometry with singlephoton ionization via tunable synchrotron-generated vacuumultraviolet radiation was used to identify (but not quantify) several highly oxygenated species. Here, temperature-dependent concentration profiles of 17 components were determined in the range of 450−1000 K and compared to up-to-date kinetic modeling results. Special emphasis is paid toward the validation and application of a theoretical method for predicting photoionization cross sections that are hard to obtain experimentally but essential to turn mass spectral data into mole fraction profiles. The presented approach enabled the quantification of the hydroperoxymethyl formate (HOOCH 2 OCH 2 O), which is a key intermediate in the low-temperature oxidation of DME. The quantification of this ketohydroperoxide together with the temperature-dependent concentration profiles of other intermediates including H 2 O 2 , HCOOH, CH 3 OCHO, and CH 3 OOH reveals new opportunities for the development of a next-generation DME combustion chemistry mechanism.

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“…Particularly, we always used the PICSs measured using the photon beam with similar energy resolution as that of our flame study. For example, the PICSs of C 2 H 2 , C 2 H 4 , C 3 H 4 -a, C 3 H 4 -p, CH 3 CHO, CH 2 CO, CH 3 OCH 3 , C 4 H 2 , C 4 H 4 , C 4 H 6 measured by Cool et al [35], Wang et al [36] and Yang et al [37] at the same beamline at the ALS were selected, which were claimed to be within an uncertainty of 20%.…”

Section: Low-pressure Laminar Premixed Flamementioning

confidence: 99%

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

Sun

Yang

Hansen

et al. 2016

Combustion and Flame

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Dimethyl carbonate (DMC) is a promising oxygenated additive or substitute for hydrocarbon fuels, because of the absence of C-C bonds and the large oxygen content in its molecular structure. To better understand its chemical oxidation and combustion kinetics, flow reactor pyrolysis at different pressures (40, 200 and 1040 mbar) and low-pressure laminar premixed flames with different equivalence ratios (1.0 and 1.5) were investigated. Mole fraction profiles of many reaction intermediates and products were obtained within estimated experimental uncertainties. From theoretical calculations and estimations, a detailed kinetic model for DMC pyrolysis and high-temperature combustion consisting of 257 species and 1563 reactions was developed. The performance of the kinetic model was then analyzed using detailed chemical composition information, primarily from the present measurements. In addition, it was examined against the chemical structure of an opposed-flow diffusion flame, relying on global combustion properties such as the ignition delay times and laminar burning velocities. These extended comparisons yielded overall satisfactory agreement, demonstrating the applicability of the present model over a wide range of high-temperature conditions. . Introduction Oxygenated hydrocarbon fuels derived from biomass are attracting considerable attention either as replacements of, or additives to, conventional hydrocarbon fuels in internal combustion engines. They offer potential benefits as renewable fuels, with a long-term zero CO 2 debt, and the tendency to reduce soot formation [1][2][3]. Dimethyl carbonate [CH 3 OC(=O)OCH 3 , DMC], being non-toxic and highly miscible with diesel fuels, is one of such promising clean fuels. Carbon-carbon bonds are absent in the DMC molecular structure which contains three oxygen atoms. In a diesel engine study, Miyamoto et al. [2] found that the extent of soot reduction mainly depended on the amount of oxygen present in the fuel. Furthermore, when the oxygen content of the fuel was above 25% by mass, soot emission fell beyond detection. Although the fuel's structure and the particular combustion conditions are of non-negligible influence on the emissions, it is worthwhile to consider the high oxygen content (53% by mass) of DMC: it suggests that DMC addition in small amounts could achieve significant soot reduction. From laboratory experiments [4,5] to practical engine operations [6-9], extensive studies have been conducted on the effects of adding DMC to hydrocarbon fuels. Specifically, Rubino and Thomson [4] used a counter-flow propane/air diffusion flame to study the inhibition of soot precursor formation by adding oxygenated compounds including DMC. They observed a remarkable reduction of soot precursors such as acetylene (C 2 H 2 ) and benzene (C 6 H 6 ), as well as a linear relationship between the C 2 H 2 concentration and the additive's oxygen and C-C bond content. Furthermore, Chen et al. [5] found that concentrations of most C 1 -C 5 hydrocarbon intermediates decreased in low-p...

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Absolute cross-sections for dissociative photoionization of some small esters

Cited by 50 publications

References 65 publications

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

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Absolute cross-sections for dissociative photoionization of some small esters

Cited by 50 publications

References 65 publications

Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Detection and Identification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Quantification of the Keto-Hydroperoxide (HOOCH2OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether

An experimental and kinetic modeling study on dimethyl carbonate (DMC) pyrolysis and combustion

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Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Detection and Identification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Intermediates during Low-Temperature Oxidation of Dimethyl Ether

Quantification of the Keto-Hydroperoxide (HOOCH₂OCHO) and Other Elusive Intermediates during Low-Temperature Oxidation of Dimethyl Ether