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There were several theories trying to explain the Mpemba effect. One of them is that a frost layer on top insulates the water below and slows freezing; another is that hot water evaporates faster which lowers the volume available for freezing.
Also a theory including different substances dissolved into water was proposed, but none of them offered satisfying explanation of the phenomenon. - See more at:
http://interestingengineering.com/why-hot-water-freezes-faster-than-cold-water/
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