Your digestive system for solid food is basically just a tube, so the spicy bits that don’t get digested fully or still retain some of the spicy chemicals make it all the way to your butthole and burn.
Urine is different though. Fluid gets absorbed from your digestive system, getting filtered through membranes and such, then goes into your bloodstream to circulate through your cells, before finally getting the extra water and contaminants filtered out by your kidneys and dumping into your bladder. Those layers of filter stop the spicy chemicals from making it into your pee.
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