The pills that cause this problem are typically very porous. They have tiny spaces between kinda powdery stuff. These tiny spaces act like they would for soil or stone,and draw in any liquids that touch them (capillary action).
Since in this case, that liquid is the thin layer of moisture on your throat, drawing it in essentially creates a minor suction at each tiny space, which sticks the pill in your throat.
So often, it literally *does* stick.
Beyond that, though, the pill can also irritate the throat, especially after a while, which may mimic the feeling even after it starts to dissolve.
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