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

Abstract

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.

Photoelectron Photoion Coincidence Spectroscopy Provides Mechanistic Insights in Fuel Synthesis and Conversion

“…For the first time, Bierkandt et al have detected the methylperoxy (H 3 C-OO) radical in a flame (Figure ). Both the photoionization spectrum and the photoelectron spectrum clearly show the presence of this radical (Figure ). Larger alkylperoxy radicals were not detected, but the absence of a mass spectrometric signal does not exclude their presence in the flame.…”

“…Formation of alkyl hydroperoxides in flames was first observed by Zhang et al by photoionization mass spectrometry, but the corresponding radicals remained elusive until recently . Bierkandt et al investigated the low-temperature oxidation in different flames and found compelling evidence for peroxy radical species …”

“…Mass spectrum from the preheat zone of an n -butane/H 2 flame measured at two different photoionization energies. Data taken from ref .…”

“…157 Bierkandt et al investigated the low-temperature oxidation in different flames and found compelling evidence for peroxy radical species. 155 Mass spectra at 10.00 and 10.75 eV from an n-butane/ hydrogen flame, as measured in the preheat zone at a flame temperature of around 700 K, are presented in Figure 19. As the observed signals at m/z 48, 62, 76, and 90 are rather atypical for high-temperature chemistry, those were assigned to the alkyl hydroperoxides formed from the corresponding peroxy radicals.…”

“…Identification of the ethyl hydroperoxide and the methylperoxy radical in flames by photoelectron spectroscopy. Reproduced from ref .…”