Solidification

Freezing, or solidification, is a phase transition in which a liquid turns into a solid when its temperature is lowered below its freezing point.

For most substances, the melting and freezing points are the same temperature; however, certain substances possess differing solid–liquid transition temperatures. For example, agar displays a hysteresis in its melting point and freezing point. It melts at 85 °C (185 °F) and solidifies from 32 °C to 40 °C (89.6 °F to 104 °F).

Most liquids freeze by crystallization, formation of crystalline solid from the uniform liquid. This is a first-order thermodynamic phase transition, which means that, as long as solid and liquid coexist, the temperature of the whole system remains very nearly equal to the melting point due to slow removal of heat when in contact with air, which is a poor heat conductor. Because of the latent heat of fusion, the freezing is greatly slowed down and the temperature will not drop anymore once the freezing starts but will continue dropping once it finishes. Crystallization consists of two major events, nucleation and crystal growth. Nucleation is the step wherein the molecules start to gather into clusters, on the nanometer scale, arranging in a defined and periodic manner that defines the crystal structure. The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size.

In spite of the second law of thermodynamics, crystallization of pure liquids usually begins at a lower temperature than the melting point, due to high activation energy of homogeneous nucleation. The creation of a nucleus implies the formation of an interface at the boundaries of the new phase. Some energy is expended to form this interface, based on the surface energy of each phase. If a hypothetical nucleus is too small, the energy that would be released by forming its volume is not enough to create its surface, and nucleation does not proceed. Freezing does not start until the temperature is low enough to provide enough energy to form stable nuclei. In presence of irregularities on the surface of the containing vessel, solid or gaseous impurities, pre-formed solid crystals, or other nucleators, heterogeneous nucleation may occur, where some energy is released by the partial destruction of the previous interface, raising the supercooling point to be near or equal to the melting point. The melting point of water at 1 atmosphere of pressure is very close to 0 °C (32 °F, 273.15 K), and in the presence of nucleating substances the freezing point of water is close to the melting point, but in the absence of nucleators water can super cool to −40 °C (−40 °F, 233 K) before freezing. Under high pressure (2,000 atmospheres) water will super cool to as low as −70 °C (−94 °F, 203 K) before freezing.

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