Nitric oxide (NO) spontaneously produces the dioxide when exposed to air:
2 NO + O2 --> NO2
It is also generated in various reactions by nitric acid, e.g. when metalls, such as Copper or Silver, are exposed to nitric acid.
It reacts, even at normal temperature&pressure, with water, where it disproportionates to nitric and nitrous acid[?]. That reaction is used in the Ostwald process.
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