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Water at 100 C is a little bit cooler than steam at 100 C because there is still some heat in the water that has not been given up. This is called the heat of vaporization and is approximately equal to 2268 J. 

When water turns to steam, then steam takes on this additional heat energy and this is the reason why steam at 100 C is "hotter" than water at the same temperature.
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The next stage of boiling water is steam.....so basically steam is more hot.because of this steam causes severe burns.. 
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