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Materials

Why warm water freezes faster than cold water

Fewer hydrogen bonds in warm water make it easier to form ice lattice

by Jyllian Kemsley
January 2, 2017 | A version of this story appeared in Volume 95, Issue 1

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Credit: J. Chem. Theory Comput.
In warm water, weak hydrogen bonds break (top, red squiggles), leaving fragments that easily reorganize into an ice lattice (bottom), a new study says.
This reaction scheme shows how hydrogen bonding phenomena are involved in water freezing.
Credit: J. Chem. Theory Comput.
In warm water, weak hydrogen bonds break (top, red squiggles), leaving fragments that easily reorganize into an ice lattice (bottom), a new study says.

Nearly 50 years ago, Erasto B. Mpemba and Denis G. Osborne reported that if samples of water at 90 °C and 25 °C are cooled, the one starting at 90 °C begins freezing first. Many explanations for the “Mpemba effect” have been proposed, including ones based on evaporation, temperature gradients, impurities, and dissolved gases. A new computational study suggests that the effect arises from the liquid’s hydrogen bond network (J. Chem. Theory Comput. 2016, DOI: 10.1021/acs.jctc.6b00735). Southern Methodist University’s Dieter Cremer and colleagues investigated clusters of 50 and 1,000 water molecules, characterizing the types and strengths of the clusters’ 350 and more than 1 million hydrogen bonds, respectively. In (H2O)1,000, raising the temperature from 10 °C to 90 °C led to fewer hydrogen bonds, as weaker, predominately electrostatic bonds broke. That left behind cluster fragments with strong hydrogen bonds with more covalent character and proportionately more “dangling” or terminal hydrogen bonds. That hydrogen bond combination enables the fragments to easily reorganize and form the hexagonal lattice of ice.

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