Methane Formation by Flame-Generated Hydrogen Atoms in the Flame Ionization Detector

The precombustion degradation of organic compounds in the flame ionization detector has been studied (1) by heating the additives in hydrogen in a quartz capillary and analyzing the reaction products by GC and (2) by following the degradation of the additives in a hydrogen flame, by means of a thin fused silica probe inserted from the bottom of the flame and connected to the ion source of a mass spectrometer. The results show that the thermic hydrogenolysis of hydrocarbons at flame temperatures produces mixtures of methane, ethene, and ethyne. In the flame, however, ethyne, benzene, isobutane, and conceivably all hydrocarbons are quantitatively converted into methane at temperatures below 600 C, that is, before the proper combustion has started. The splitting of the C-C bonds is preceded by hydrogenation of double and triple bonds and aromatic rings. The reactions, no doubt, are caused by hydrogen atoms, which are formed in the burning hydrogen and which diffuse into the inner core of the flame. The quantitative formation of methane appears to explain the "equal per carbon" rule for the detector response of hydrocarbons, since all carbons are "exchanged" for methane molecules.