Articles you may be interested inRadical-neutral chemical reactions studied at low temperature with VUV synchrotron photoionization mass spectrometry AIP Conf. Proc. 1501, 1365 (2012); 10.1063/1.4769699 Synchrotron photoionization mass spectrometry study of intermediates in fuel-rich 1,2-dimethoxyethane flame Direct identification of propargyl radical in combustion flames by vacuum ultraviolet photoionization mass spectrometry J. Chem. Phys. 124, 074302 (2006); 10.1063/1.2168448 Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source Rev. Sci. Instrum. 76, 094102 (2005); 10.1063/1.2010307Photoionization efficiency spectrum and ionization energy of HSO studied by discharge flow-photoionization mass spectrometryWe report the first use of synchrotron radiation, continuously tunable from 8 to 15 eV, for flame-sampling photoionization mass spectrometry ͑PIMS͒. Synchrotron radiation offers important advantages over the use of pulsed vacuum ultraviolet lasers for PIMS; these include superior signal-to-noise, soft ionization, and access to photon energies outside the limited tuning ranges of current VUV laser sources. Near-threshold photoionization efficiency measurements were used to determine the absolute concentrations of the allene and propyne isomers of C 3 H 4 in low-pressure laminar ethylene-oxygen and benzene-oxygen flames. Similar measurements of the isomeric composition of C 2 H 4 O species in a fuel-rich ethylene-oxygen flame revealed the presence of substantial concentrations of ethenol ͑vinyl alcohol͒ and acetaldehyde. Ethenol has not been previously detected in hydrocarbon flames. Absolute photoionization cross sections were measured for ethylene, allene, propyne, and acetaldehyde, using propene as a calibration standard. PIE curves are presented for several additional reaction intermediates prominent in hydrocarbon flames.
Abstract. The heterogeneous reaction of OH radicals with sub-micron squalane particles, in the presence of O 2 , is used as a model system to explore the fundamental chemical mechanisms that control the oxidative aging of organic aerosols in the atmosphere. Detailed kinetic measurements combined with elemental mass spectrometric analysis reveal that the reaction proceeds sequentially by adding an average of one oxygenated functional group per reactive loss of squalane. The reactive uptake coefficient of OH with squalane particles is determined to be 0.3±0.07 at an average OH concentration of ∼1×10 10 molecules cm −3 . Based on a comparison between the measured particle mass and model predictions it appears that significant volatilization of a reduced organic particle would be extremely slow in the real atmosphere. However, as the aerosols become more oxygenated, volatilization becomes a significant loss channel for organic material in the particle-phase. Together these results provide a chemical framework in which to understand how heterogeneous chemistry transforms the physiochemical properties of particle-phase organic matter in the troposphere.
Fluoride ion batteries are potential “next-generation” electrochemical storage devices that offer high energy density. At present, such batteries are limited to operation at high temperatures because suitable fluoride ion–conducting electrolytes are known only in the solid state. We report a liquid fluoride ion–conducting electrolyte with high ionic conductivity, wide operating voltage, and robust chemical stability based on dry tetraalkylammonium fluoride salts in ether solvents. Pairing this liquid electrolyte with a copper–lanthanum trifluoride (Cu@LaF3) core-shell cathode, we demonstrate reversible fluorination and defluorination reactions in a fluoride ion electrochemical cell cycled at room temperature. Fluoride ion–mediated electrochemistry offers a pathway toward developing capacities beyond that of lithium ion technology.
We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed us-
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