The mechanism of formation of the ions H3O+H2O and H3O+(H2O)2 in ionized oxygen, starting from O2+/O4+ has been investigated with a selected ion‐drift chamber mass spectrometer, using lower water vapor pressures than previous studies. With these conditions, the H3O+ ion was not observed indicating that the reaction O2+H2O+H2O→H3O++OH+O2 is endothermic; the ion H3O+(H2O)2 was found to arise mainly from the sequence O2+H2O→O2(H2O)2+→(H2O)3+→H3O+ (H2O)2 rather than by attachment of H2O to H3O+H2O. For the intermediate ion O2(H2O)2+ one must consider the possibility that two different structures exist whose reactions with water vapor give different products.

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