Isomer-sensitive characterization of low temperature oxidation reaction products by coupling a jet-stirred reactor to an electron/ion coincidence spectrometer: case of <i>n</i>-pentane

Bourgalais, Jérémy; Gouid, Zied; Herbinet, Olivier; Garcia, Gustavo A.; Arnoux, Philippe; Wang, Zhandong; Tran, Luc-Sy; Vanhove, Guillaume; Hochlaf, M.; Nahon, Laurent; Battin‐Leclerc, Frédérique

doi:10.1039/c9cp04992d

Cited by 29 publications

(58 citation statements)

References 98 publications

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“…As is shown in [5], the species indicated in the mass spectrum of ketohydroperoxides, respectively. In the following, an isomer identification attempt is done for m/z 118 corresponding to KHPs and 100 corresponding to diones.…”

Section: Attempts Of Determination Of the Isomeric Distribution Of Kementioning

confidence: 89%

“…This approach already gave good results for understanding the structure of biological molecules up to m/z 136 [19]. In [5],…”

Section: Calculation Methodsmentioning

confidence: 98%

“…The used set-up, based upon the undulator-based DESIRS VUV beamline [12] of synchrotron SOLEIL(see Fig. S2 (SM)), was described in [5]). The SAPHIRS end-station [13] is equipped with the double-imaging photoelectron/photoion (i 2 PEPICO) spectrometer DELICIOUS III [14].…”

Section: Experimental Facilitymentioning

confidence: 99%

“…The JSR mounted inside SAPHIRS is similar to that used in [11] (same geometry, heating devices and temperature control, and gas feeding). The reactor sphere includes a quartz nozzle with a 100-μm hole in order to create the molecular beam and is connected to two concentric quartz tubes mounted into a flange carrying all the gas inlets and outlets, which is itself mounted on a 3-axes manipulator [5].…”

Section: Experimental Facilitymentioning

confidence: 99%

“…Previous work in flames [4] and a Jet-Stirred Reactor (JSR) [5] evidenced an interesting potential of PIMS using the PhotoElectron PhotoIon COincidence (PEPICO) technique for identifying isomers through the energy analysis of the correlated photoelectron. Therefore, the first purpose of this paper is to analyze the coincident mass-tagged Threshold PhotoElectron Spectra (TPES [6] [7]) of ketohydroperoxides and their related products measured during an investigation of n-pentane oxidation (lean mixtures with dilution in helium) in JSR.…”

Section: Introductionmentioning

confidence: 99%

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Chemistry deriving from OOQOOH radicals in alkane low-temperature oxidation: A first combined theoretical and electron-ion coincidence mass spectrometry study

Battin‐Leclerc

Bourgalais

Gouid

et al. 2021

Proceedings of the Combustion Institute

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While there is consensus on the fact that OOQOOH radicals, produced by two oxygen additions from alkyl radicals, are the heart of the low-temperature oxidation of alkanes, the determination of the isomeric distribution and the quantification of their derived products (ketohydroperoxides and diones) are still a challenge. For the first time, heavy oxygenated products produced during alkane oxidation have been investigated using electron/ion coincidence mass spectrometry. The investigated prototype reaction is n-pentane oxidation carried out in a jet-stirred reactor (temperatures from 585 to 665 K, pressure of 1.1 bar, lean mixture). Identification attempts were made for m/z 100 and 118 species using coincident mass-tagged Slow PhotoElectron Spectra obtained by electron-ion coincidence mass spectrometry combined with first principle computations, consisting in the determination of their adiabatic ionization energies and the Franck-Condon envelope of the photoionization spectra. 4hydroperoxypentan-2-one has been confirmed as the dominant obtained ketohydroperoxide, as predicted by up-to-date kinetic models. However, difficulties due to fragmentation has made impossible the identification of the ketohydroperoxides present in lower amounts. In parallel, C5H8O2 isomers were identified, showing the possible formation, in addition to diones, of species with a ketone and an enol function. In addition, we provide new information on the first steps of the fragmentation pathways of C5 ketohydroperoxides. From the shape of their corresponding peaks on mass spectra and the energy and temperature dependence of their signal, ions at m/z 43, 57 and 85 have been identified as fragments from ketohydroperoxides. Taking into account these fragmentations lowers, by more than a factor of 10, the previously observed deviation between experiments and modeling for ketohydroperoxide mole fractions. The formation of the C1-C2 carboxylic acids, predicted from Korcek decomposition, was also observed, but with a favored formation of acetic acid versus formic acid that what was predicted for propane.

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Section: Attempts Of Determination Of the Isomeric Distribution Of Kementioning

confidence: 89%

“…This approach already gave good results for understanding the structure of biological molecules up to m/z 136 [19]. In [5],…”

Section: Calculation Methodsmentioning

confidence: 98%

Section: Experimental Facilitymentioning

confidence: 99%

Section: Experimental Facilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chemistry deriving from OOQOOH radicals in alkane low-temperature oxidation: A first combined theoretical and electron-ion coincidence mass spectrometry study

Battin‐Leclerc

Bourgalais

Gouid

et al. 2021

Proceedings of the Combustion Institute

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Photoelectron Photoion Coincidence Spectroscopy of Biradicals

Fischer

Hemberger

2023

ChemPhysChem

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The electronic structure of biradicals is characterized by the presence of two unpaired electrons in degenerate or near‐degenerate molecular orbitals. In particular, some of the most relevant species are highly reactive, difficult to generate cleanly and can only be studied in the gas phase or in matrices. Unveiling their electronic structure is, however, of paramount interest to understand their chemistry. Photoelectron photoion coincidence (PEPICO) spectroscopy is an excellent approach to explore the electronic states of biradicals, because it enables a direct correlation between the detected ions and electrons. This permits to extract unique vibrationally resolved photoion mass‐selected threshold photoelectron spectra (ms‐TPES) to obtain insight in the electronic structure of both the neutral and the cation. In this review we highlight most recent advances on the spectroscopy of biradicals and biradicaloids, utilizing PEPICO spectroscopy and vacuum ultraviolet (VUV) synchrotron radiation.

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Observation of low‐temperature chemistry products in laminar premixed low‐pressure flames by molecular‐beam mass spectrometry

Bierkandt

Oßwald

Gaiser

et al. 2021

Int J of Chemical Kinetics

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The formation of typical low‐temperature oxidation products is observed in laminar premixed low‐pressure flames investigated by photoionization molecular‐beam mass spectrometry at the Swiss Light Source. The C1–C4 alkyl hydroperoxides can be identified in n‐butane‐ and 2‐butene‐doped hydrogen flames by their photoionization efficiency spectra at m/z 48, 62, 76, and 90. C1–C3 alkyl hydroperoxides are also observed in a propane‐doped hydrogen flame and in a neat propane flame. In addition, threshold photoelectron spectra reveal the presence of the alkyl hydroperoxides. In the 2‐butene/H2 flame, the photoionization spectrum at m/z 88 also enables the identification of butenyl hydroperoxides by comparison with calculated ionization energies of the alkenyl hydroperoxides and a literature spectrum. The low‐temperature species are formed close to the burner surface with maximum mole fractions at 0.25–0.75 mm above the burner. At 0.5 mm, even the methylperoxy radical (CH3OO) is measured for the first time in a laminar premixed flame. The rate of production analyses show that consumption of the hydroperoxyalkyl radicals results in the formation of cyclic ethers. In the n‐butane/H2 flame, ethylene oxide, oxetane, and methyloxirane are identified. Besides expected small oxygenated species, for example, formaldehyde or acetaldehyde, the larger C4 oxygenates butanone (C2H5COCH3) and 2,3‐butanedione (C4H6O2) are formed in the two C4 hydrocarbon‐doped hydrogen flames. Quantification of alkyl hydroperoxides with estimated photoionization cross sections based on the corresponding alcohols, which have similar photoelectron structures to the alkyl hydroperoxides, shows that mole fractions are on the order of 10−5–10−6 in the n‐butane/H2 flame. Measurements are corroborated by simulations, which also predict the presence of some peroxides in detectable concentrations, that is, mole fractions larger than 10−7, under the investigated conditions. The observation of peroxide species and cyclic ethers in the investigated laminar premixed flames give new insights into the contribution of low‐temperature combustion chemistry in a flame.

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Isomer-sensitive characterization of low temperature oxidation reaction products by coupling a jet-stirred reactor to an electron/ion coincidence spectrometer: case of n-pentane

Abstract: Using a tunable vacuum ultraviolet synchrotron beam line and first principle computations, a jet-stirred reactor was coupled for the first time to a photoionization mass spectrometer using electron/ion coincidence imaging.

Cited by 29 publications

References 98 publications

Chemistry deriving from OOQOOH radicals in alkane low-temperature oxidation: A first combined theoretical and electron-ion coincidence mass spectrometry study

Chemistry deriving from OOQOOH radicals in alkane low-temperature oxidation: A first combined theoretical and electron-ion coincidence mass spectrometry study

Photoelectron Photoion Coincidence Spectroscopy of Biradicals

Observation of low‐temperature chemistry products in laminar premixed low‐pressure flames by molecular‐beam mass spectrometry

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