In a detailed and well documented article http://www.snopes.com/science/microwave.asp, Snopes confirms that water boiled in a microwave oven can suddenly “explode.” The incident cited in this article involved a 26 year-old who heated a cup of water to make instant coffee. The water became super-heated and erupted from the cup as he was looking into the cup. He is reported to have experienced 1st and 2nd degree burns and partial loss of vision in one eye.
Superheated water blowing up is a rare occurrence, but one that can be completely prevented if you leave a non-metallic object such as a wooden spoon in the cup.
-Pete Burns
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