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Our bodies cool us down by sweating because water requires a significant amount of energy to change state from liquid to gas, making it an ideal medium for carrying thermal energy away from our bodies.

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Additional insights we found via HowStuffWorks
The high amount of energy required to evaporate water, known as the heat of vaporization, comes from the energy needed to separate water molecules from one another, which are held together by hydrogen bonds.
Because temperature is related to the average kinetic energy of molecules, those with the highest energy in this distribution evaporate first, lowering the average and thus the object's temperature.
This process—evaporative cooling—is the reason why misting fans are used for cooling.
If the air is very humid, it is already saturated with water vapor and cannot hold much more, limiting sweating's effectiveness and making temperatures feel higher.
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