Hydrocarbon ions in fuel-rich, CH4–C2H2–O2 flames as a probe for the initiation of soot: an experimental approach

Abstract

The natural hydrocarbon ions CnHx± (n ≥ 2, x ≥ 0) present in premixed, fuel-rich, nearly sooting, CH4–C2H2–O2 flames at atmospheric pressure were studied as a probe of the early chemical stages of soot formation. Ion concentration profiles were measured mass-spectrometrically along the flame axis through the reaction zone into the burnt gas downstream. Total ionization profiles were examined for their dependence on both temperature and equivalence ratio, [Formula: see text] Families of individual CnHx− negative ion profiles exhibit concentration peaks in three distinct regions; predominantly oxygenated ions occur upstream, giving way to moderately unsaturated hydrocarbon ions near the end of the reaction zone, leading to highly unsaturated carbonaceous ions further downstream. The concentrations of the downstream ions alternate with the parity of n, the even-n species being larger. Series of CnHx+ positive ion profiles, for a given n, show profile peak positions which move steadily downstream with decreasing x, indicative of progressive dehydrogenation. The positive ion chemistry of these series is essentially independent of n. As [Formula: see text] is increased at constant temperature towards the sooting point, the concentrations of CnHx± ions increase while those of the oxygenated ions decrease; the positive ions show a relative enhancement of species having high values of n.