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When we look at the heating curve for water, we see that there is more heat being supplied to turn the liquid into vapor. The enthalpy of vaporization is considerably large for water, which means that the enthalpy on condensation (when steam touches a cold surface/skin) will be a large, exothermic reaction and release a lot more energy (40.7 kJ/mol) then when liquid water touches the skin.
The process of water becoming a gas (vaporization) takes much longer than the process of ice becoming water (melting). Since this process is longer, more heat is supplied throughout and the enthalpy is greater, meaning that the steam will release much more energy/heat as opposed to the liquid
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