Abstract
We report that gaseous isoprene ISO(g) is oxidized into soluble species on the surface of aqueous acidic FeCl2 solutions simultaneously exposed to H2O2(g). In our experiments, ISO(g) and/or H2O2(g) streams intersect aqueous pH ∼ 2 FeCl2 microjets for ∼10 μs. The products formed in these reactive encounters are identified in situ via online electrospray ionization mass spectrometry. We found that the (ISO)nH+ oligomers generated from ISO(g) on the surface of pH < 4 water are oxidized into myriad products whose combined yields exceed 5%. MS2 analysis reveals that the positive ions derived from the protonation of neutral products split H2O and O neutrals, whereas the less abundant negative carboxylate ion products undergo CO, H2O, and CO2 losses. Significantly, all products are fully quenched by ·OH scavenger tert-butyl alcohol. These results are consistent with an oxidation process initiated by the addition of ·OH from (Fe2+(aq) + H2O2(g)) to (ISO)nH+, followed by fast reactions involving dissolved H2O2, HO...
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