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Steam at 100C causes a worse burn than water at 100C because steam at 100C has a lot more energy than boiling water at the same temperature. If you recall the phase change graph, a lot of energy is put into vaporizing water into a gas. During a phase change, the temperature remains constant, but the amount of heat supplied continues to increase. Therefore, since steam has a lot more heat (energy) than boiling water at the same temperature, the burn from a steam is much worse.
Steam is not hotter than boiling water at 100 C but will be carrying more energy because of the energy input required to change the phase. As a result, there is a large enthalpy for condensation and when the energy is released on skin, there is a more severe burn.
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