Ion concentration profiles up to mass 557 amu were measured in a sooting acetyleneoxygen flame at an equivalence ratio of 3.0, a total pressure of 2.67 kPa, and an unburned gas velocity of 50 cm s −1. The mass spectrometer was calibrated for mass by seeding flames with isotopes of several metals and by using deuterated acetylene, which also allowed us to measure the number of hydrogen atoms in each hydrocarbon ion. The ion concentration sensitivity of the mass spectrometer was calibrated by comparing the individual ion currents with the ion current obtained in operation as a high-pass mass filter (that is, transmitting only those ions whose masses were greater than a specific mass) and by relating these currents to the total ion concentrations determined using a Langmuir probe. Ion-molecule reactions, including those with large ions, were demonstrated to be rapid under these flame conditions. The question of whether the large ions are produced by reactions of small ions with large neutral molecules or by reactions of large ions with small molecules was resolved in favor of the latter reactions. From the sequential changes in the number of carbon and hydrogen atoms and the carbon-to-hydrogen ratio in ions of increasing mass, we deduced that the types of ion-molecule reactions occurring included not only acetylene addition to growing ions, but also polyacetylene addition (with or without acetylene elimination) and the addition of allene and propyne. From reaction rate considerations, using literature values for neutral species concentrations in the same flame, we concluded that many of the small hydrocarbon molecules observed in this flame, up to and including benzene, could add to large ions to increase the ion mass. This accounts for the extremely rapid growth observed from small ions to very large ions, that is, from 39 amu to about 4500 amu (3 to about 370 carbon atoms) in 1 ms.
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