When
ice melts, all of the hydrogen bonds do not collapse at once. The
cagelike framework disintegrates piecemeal, and even in liquid water
at room temperature there are clusters of several hundred water molecules
hydrogen-bonded together in ways similar to that of ice. As the temperature
is raised, these icelike domains break up more and more, and the same
quantity of water takes up less room. At the same time, the bulk solution
is expanding as the temperature rises. These two effects are in competition.
When ice first melts, the breaking up of the cage structure predominates,
and water contracts. It continues to contract as the temperature increases
from 0C to 4C, and more of the icelike structures are broken up. Not
until the temperature rises above 4C does the normal thermal expansion
become more important than the breakup of the hydrogen-bonded cages.
Water has its minimum volume and maximum density at 4C, and only above
this temperature does it begin to expand as it is heated, as does
any other liquid.
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