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It is well known that H2O spontaneously autoionizes to H+ and OH- when it is in liquid phase. I was wondering whether it does the same in gas phase, either to the same extent as in liquid phase or at all.

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Yes, water is ionized to some extent in all phases. One study even extends to 1,000 K!

A concise discussion of the change in ionization with temperature at Chemguide also explains the variation of pH of neutral water with temperature. [The concept of pH 7 being neutral is based on Kw (in mol2 dm-6) of ~10-14 at ~300 K.]

In general, the higher the temperature, the more a compound is ionized.

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  • $\begingroup$ Thing is, in actual vapour and low temp. auto-ionisation is as good as non-existent. $\endgroup$
    – Mithoron
    Commented Dec 23, 2019 at 14:03
  • $\begingroup$ @Mithoron, read the answer: "water is ionized to some extent". "as good as non-existent," is not none. $\endgroup$ Commented Jul 3, 2022 at 3:09
  • $\begingroup$ OP asked to what extent. Later you talk about liquid water. While it's true that raising temp. raised deg. of autoionization, vaporisation lowers it extremely. $\endgroup$
    – Mithoron
    Commented Jul 3, 2022 at 13:35

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