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Basically, you have to understand that a phase change takes heat to reach the vaporization point and more heat to actually change the molecules into the desired phase. Once enough heat is added to water that it reaches the vaporization temp, any xtra heat added will cause some of the molecules to change into the vapor phase. Thus, at this point, there is a mix of water and vapor, all at the same temperature but with varying levels of heat added. Since pure vapor requires a lot more heat than water at the same temperature, vapor will burn you worse. When you think of the graph, the plateau between the water and the vapor is the extra heat being added to change water into vapor. The temperature, or y axis is the same, but the heat added is still increasing.
In the process of phase change (in this case vaporization) the temperature doesn't change (stays at 100C). However, when making steam, there is still heat and energy being added to break the bonds, which is why steam causes severe burns.
It takes more energy; in the form of heat; to go from water to steam than it does to go from water to boiling water. Since it takes more energy to go through that phase change you would get a worse burn.
Essentially, boiling water at 100 degrees celcius, becomes steam at 100 degrees celcius when it overcomes the latent heat of vaporization. Hence, when skin is exposed to steam, it absorbs more heat from steam as it fist needs to lose the heat of vaporization and convert back to water at 100 degrees. Thus, steam causes more severe burns.
Steam is at a higher energy level than boiling water is so even though they are existing at the same temperature, the extra energy and thus burning ability is transferred to a burn victim when the steam condenses and lowers temperature after contact with skin.
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