You’ve got receptors in your skin that say “hey, there’s too much heat here and it is damaging me!” when the temperature gets beyond a certain threshold, and send the signal to your brain.
Alcohol, interestingly enough, causes those receptors to lower that threshold. Suddenly they sense a lower temperature as ‘burning’ and now, with their lower threshold, they suddenly go “holy crap, I’m on fire” and send your brain a signal.
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