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Study of Sulfur Oxidation Products by Pyrolysis High-Resolution Mass Spectrometry

High-temperature oxidations of hydrogen sulfide and methanethiol with O2 and NO2 were investigated using a special flow probe that was coupled to the ion-source housing of a high-resolution mass spectrometer. The direct coupling permitted prompt analysis of oxidation products effusing from the flow probe. Nominally isobaric 32S–16O2 doublets were resolved at a mass resolution of >8,000, which allowed for identification of several reaction products. Under conditions of medium-low pressure (0.8–4 Torr) and long mean residence times (0.5 s) in the probe, the oxidations yielded mostly stable products. Hydrogen sulfide was oxidized to form SO, SO2, S2 and S2O whose relative intensities were studied as a function of temperature and reactant mixture composition. Methanethiol yielded CH3SNO, CH3SSCH3, CS2, SO2 and traces of SO3 and SO3H depending on the temperature and reactant mixture composition.