Arnas Lucassen

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

In this paper we report the detection and identification of the keto-hydroperoxide (hydroperoxymethyl formate, HPMF, HOOCH2OCHO) 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. On the basis of experimentally observed ionization thresholds and fragmentation appearance energies, interpreted with the aid of ab initio calculations, we have identified HPMF and its conceivable decomposition products HC(O)O(O)CH (formic acid anhydride), HC(O)OOH (performic acid), and HOC(O)OH (carbonic acid). Other intermediates that were detected and identified include HC(O)OCH3 (methyl formate), cycl-CH2-O-CH2-O- (1,3-dioxetane), CH3OOH (methyl hydroperoxide), HC(O)OH (formic acid), and H2O2 (hydrogen peroxide). We show that the theoretical characterization of multiple conformeric structures of some intermediates is required when interpreting the experimentally observed ionization thresholds, and a simple method is presented for estimating the importance of multiple conformers at the estimated temperature (∼100 K) of the present molecular beam. We also discuss possible formation pathways of the detected species: for example, supported by potential energy surface calculations, we show that performic acid may be a minor channel of the O2 + ĊH2OCH2OOH reaction, resulting from the decomposition of the HOOCH2OĊHOOH intermediate, which predominantly leads to the HPMF.

Identification of tetrahydrofuran reaction pathways in premixed flames

Abstract Premixed low-pressure tetrahydrofuran/oxygen/argon flames are investigated by photoionization molecular-beam mass spectrometry using vacuum-ultraviolet synchrotron radiation. For two equivalence ratios (φ = 1.00 and 1.75), mole fractions are measured as a function of distance from the burner for almost 60 intermediates with molar masses ranging from 2 (H2) to 88 (C4H6O2), providing a broad database for flame modeling studies. The isomeric composition is resolved by comparisons between experimental photoionization efficiency data and theoretical simulations, based on calculated ionization energies and Franck-Condon factors. Special emphasis is put on the resolution of the first reaction steps in the fuel destruction. The photoionization experiments are complemented by electron-ionization molecular-beam mass-spectrometry measurements that provide data with high mass resolution. For three additional flames with intermediate equivalence ratios (φ = 1.20, 1.40 and 1.60), mole fractions of major species and photoionization efficiency spectra of intermediate species are reported, extending the database for the development of chemical kinetic models.

Formation of oxygenated and hydrocarbon intermediates in premixed combustion of 2-methylfuran

Abstract This paper focuses on the combustion chemistry of 2-methylfuran (2-MF), a potential biofuel, and it is built on the previous work of Tran et al. [Combust. Flame 161 (2014) 766]. In their work, they had combined detailed flame chemistry modeling with flame speciation data based on flame-sampling molecular beam mass spectrometry (MBMS) with electron ionization and gas chromatography with MS detection. In this work, we significantly extend those previous studies by in-situ isomer-resolving species identification and quantification. Specifically, we have determined the detailed chemical structure of a premixed laminar 2-MF flame using flame-sampling high-resolution MBMS with synchrotron-generated vacuum-ultraviolet radiation. Mole fraction profiles of 60 intermediate, reactant, and product species were measured in order to assess the pollutant potential of this possible next-generation biofuel. Special emphasis is paid towards the fuels ability to form aromatic and oxygenated intermediates during incomplete combustion processes, with the latter species representing a variety of different classes including alcohols, ethers, enols, ketones, aldehydes, acids, and ketenes. Whenever possible the experimental data are compared to the results of model calculations using the 2-MF combustion chemistry model of Tran et al., but it should be noted that many newly detected species are not included in the calculations. The experimental data presented in this work provides guidance towards to development of a next-generation 2-MF combustion chemistry model.

Progress in Fixed-Photon-Energy Time-Efficient Double Imaging Photoelectron/Photoion Coincidence Measurements in Quantitative Flame Analysis

Abstract Photoelectron photoion coincidence (PEPICO) spectroscopy as an attractive new technique for combustion analysis was used in a fixed-photon-energy configuration to provide quantitative species profiles in laminar premixed flames. While such measurements are conventionally performed with molecular-beam mass spectrometry (MBMS) using electron ionization (EI) or vacuum ultraviolet (VUV) photoionization (PI) with synchrotron radiation, these techniques have some limitations. The possibility to record photoelectron spectra (PES) simultaneously with photoionization data, providing fingerprint information for reliable species identification, presents a significant advantage of PEPICO spectroscopy especially in complex reactive mixtures. The multiplex approach presented here, enhanced by the imaging capabilities of the electron and ion detection in the so-called double-imaging PEPICO scheme (i2PEPICO), provides, in different experimental situations, an unprecedentedly detailed combustion analysis regarding both species identification and quantification. Problems and perspectives of the present fixed-photon-energy PEPICO approach will be discussed.

Isomer Identification in Flames with Double-Imaging Photoelectron/Photoion Coincidence Spectroscopy (i2PEPICO) using Measured and Calculated Reference Photoelectron Spectra

Abstract Double-imaging photoelectron/photoion coincidence (i2PEPICO) spectroscopy using a multiplexing, time-efficient, fixed-photon-energy approach offers important opportunities of gas-phase analysis. Building on successful applications in combustion systems that have demonstrated the discriminative power of this technique, we attempt here to push the limits of its application further to more chemically complex combustion examples. The present investigation is devoted to identifying and potentially quantifying compounds featuring five heavy atoms in laminar, premixed low-pressure flames of hydrocarbon and oxygenated fuels and their mixtures. In these combustion examples from flames of cyclopentene, iso-pentane, iso-pentane blended with dimethyl ether (DME), and diethyl ether (DEE), we focus on the unambiguous assignment and quantitative detection of species with the sum formulae C5H6, C5H7, C5H8, C5H10, and C4H8O in the respective isomer mixtures, attempting to provide answers to specific chemical questions for each of these examples. To analyze the obtained i2PEPICO results from these combustion situations, photoelectron spectra (PES) from pure reference compounds, including several examples previously unavailable in the literature, were recorded with the same experimental setup as used in the flame measurements. In addition, PES of two species where reference spectra have not been obtained, namely 2-methyl-1-butene (C5H10) and the 2-cyclopentenyl radical (C5H7), were calculated on the basis of high-level ab initio calculations and Franck-Condon (FC) simulations. These reference measurements and quantum chemical calculations support the early fuel decomposition scheme in the cyclopentene flame towards 2-cyclopentenyl as the dominant fuel radical as well as the prevalence of branched intermediates in the early fuel destruction reactions in the iso-pentane flame, with only minor influences from DME addition. Furthermore, the presence of ethyl vinyl ether (EVE) in DEE flames that was predicted by a recent DEE combustion mechanism could be confirmed unambiguously. While combustion measurements using i2PEPICO can be readily obtained in isomer-rich situations, we wish to highlight the crucial need for high-quality reference information to assign and evaluate the obtained spectra.