Two reasons that humid air makes you hot:
1) water transfers heat much faster than air (thermal conductivity). So moist hot air makes you hotter faster than dry hot air (same for moist cold air making you cold faster)
2) when you sweat, it’s the evaporation of the sweat that cools you down. When the air is humid, it is already holding a lot of water (humidity) so sweat takes longer to evaporate because the air is slower to absorb more water.
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