When we say temperature, it’s only the average temperature of a substance. Individual molecules may be much hotter or colder. In the case of water, the molecules closest to the surface are a lot more exposed to heat and therefore can just evaporate away without the rest of the water boiling.
One of the sources of your confusion is the conflation of evaporation and boiling – evaporation occurs at all temperatures, and always from the surface. Boiling happens at 100°C (at sea level), and happens throughout the liquid, not just the surface.
Latest Answers