Abstract
The reactions of vinyl radicals with hydrogen and oxygen atoms have been studied at low pressures (0.3–4 mbar) and temperature (293 K) using fast discharge flow reactors and a Laval nozzle reactor. Samples were withdrawn continuously by molecular beam sampling and the stable and labile species were determined by mass spectrometers. Specific detection was obtained either by a mass spectrometer with electron impact ionization (4.5–29.5 eV, 70 eV) and/or high resolution or by a time-of-flight mass spectrometer with multiphoton ionization and/or electron impact ionization. A high detection sensitivity was achieved using modulation techniques, single ion counting and signal averaging. Vinyl radicals were produced via the reaction (1a) C2H4+F→C2H3+HF(1a)→C2H3F+H(1b) The relative rate constants of the radical + atom reactions were measured using the reactions H and O+neo−C5H11 as the standard. This leads to C2H3+H→products(2)k2=(3±2)x1013cm3/mols and for C2H3+O→products(5)k5=(3±2)x1013cm3/mols The mechanisms were found to be C2H3+H→C2H2+H2(2) and C2H3+O→CH3+CO(5a)→CH2CO+H(5b)
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