Ever since I started running, all I know is that I need to drink a sh*t ton of electrolytes. But I would like to understand why on a physiological level.
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Theres nothing thats magical about it (even if its got what the plants crave).
A general rule of the human body is that water follows salt. Your sweat glands excrete water to cool you down. In order to accomplish this, the glandular cells have molecular machinery for pumping out sodium and chloride. The water follows the salt.
If you sweat a lot, you can lose a significant amount of sodium and chloride. The body is good at adjusting for this (by controlling renal excretion of sodium and chloride into urine) but only to a point. If you rehydrate with just plain water after losing a lot through sweat, you can potentially have a dangerous condition called hyponatremia.
For a typical Western diet that is already quite high in salt, and assuming a reasonable amount of sweat, you can often safely rehydrate with just water. A very general and nonspecific guideline is to consider sports drink if your exercise lasts longer than an hour.
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