Wednesday, January 4, 2017

Why Warm Water Freezes Faster Than Cold

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 firstMany explanations for the “Mpemba effect” have been proposed, including ones based on evaporation, temperature gradients, impurities, and dissolved gases.


In warm water, weak hydrogen bonds break (top, red squiggles), leaving fragments
that easily reorganize into an ice lattice (bottom), a new study says.

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.

Apart from learning what the name of this effect is and why it occurs, you can now answer two unit 1 past paper questions with the knowledge that:

1. Hydrogen bonds are largely electrostatic in nature.


2. Each water molecule forms four hydrogen bonds (from diagram).