The fire dousing effect does definitely trigger before the fire would have a chance to spread from liquid nature, and the potion splash applies to burning terrain and characters. Potion splashes only douse the exact tile that they're thrown on though, so if there's more fire nearby the grass will help it spread.
Pixel Dungeon
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Gotcha, I observed wrongly. Then I have to say "very hard" instead of "almost impossible". My suggestion still stand tho, that is to activate only on drinking.
IMO it's almost never worth it to spend a potion to douse flames anyway.
Thing is, I love me some frozen carpaccio