Water Expands On Frezing

Most liquids have a quite simple behavior when they are cooled (at a fixed pressure): they shrink. The liquid contracts as it is cooled; because the molecules are moving slower they are less able to overcome the attractive intermolecular forces drawing them closer to each other. Then the freezing temperature is reached, and the substance solidifies, which causes it to contract some more because crystalline solids are usually tightly packed. Water is one of the few exceptions to this behavior. When liquid water is cooled, it contracts like one would expect until a temperature of approximately 4 degrees Celsius is reached. After that, it expands slightly until it reaches the freezing point, and then when it freezes it expands by approximately 9%. This unusual behavior has its origin in the structure of the water molecule. There is a strong tendency to form a network of hydrogen bonds, where each hydrogen atom is in a line between two oxygen atoms. This hydrogen bonding tendency gets stronger as the temperature gets lower (because there is less thermal energy to shake the hydrogen bonds out of position). The ice structure is completely hydrogen bonded, and these bonds force the crystalline structure to be very "open", as shown in the following picture:

Picture credits In the following two pictures, the first shows a typical structure of liquid water, while the second is an ice structure; note the extra open space in the ice.

It is this open solid structure that causes ice to be less dense than liquid water. That is why ice floats on water, for which we should all be thankful because if water behaved "normally" many bodies of water would freeze solid in the winter, killing all the life within them. Water's "density maximum" is a product of the same phenomenon. Close to the freezing point, the water molecules start to arrange locally into ice-like structures. This creates some "openness" in the liquid water, which tends to decrease its density. This is opposed by the normal tendency for cooling to increase the density; it is at approximately 4 degrees Celsius that these opposing tendencies are balanced, producing the density maximum.

A water molecule consists of two hydrogen atoms and one oxygen atom. The three atoms make an angle; the H-O-H angle is approximately 104.5 degrees. The center of each hydrogen atom is approximately 0.0957 nm from the center of the oxygen atom. The structure of a single water molecule is shown below:

Picture credits Because oxygen is more electronegative than hydrogen (in other words, electrons tend to be in the neighborhood of the oxygen), the hydrogen atoms end up with a partial positive charge and the oxygen atom with a partial negative charge. This separation of charge produces a net dipole moment on the molecule; for the isolated water molecule this dipole moment is approximately 1.85 Debye units. This molecular structure leads to hydrogen bonding, which is a stabilized structure in which a hydrogen atom is in a line between the oxygen atom on its own molecule and the oxygen on another molecule. This picture shows a hydrogen-bonded structure between two water molecules:

These hydrogen bonds, with their extra attractive energy, are the cause of many of the unusual properties of water, including its large heat of vaporization and its expansion upon freezing.