The real key is the difference between evaporation and vaporization. Evaporation (mostly) happens at the surface of a liquid whereas vaporization (boiling) happens within the liquid. The difference is in the energy of those molecules. All water molecules are attracted to other water molecules because water molecules are like little magnets. All the molecules within the liquid have molecules surrounding them holding them in place, meaning it takes a lot of energy to get them to boil. Molecules on the surface have air above rather than more water, so they have less molecules to escape from and need less energy to escape to a gaseous state, so it can happen at much lower temperatures.
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