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Phase transitions commonly refer to when a substance transforms between one of the four states of matter to another. At the phase transition point for a substance, for instance the boiling point, the two phases involved - liquid and vapor, have identical free energies and therefore are equally likely to exist.
Melting is therefore classified as a first-order phase transition. Melting occurs when the Gibbs free energy of the liquid becomes lower than the solid for that material. The temperature at which this occurs is dependent on the ambient pressure. Low-temperature helium is the only known exception to the general rule. [2]
The latent internal energy of a system is the internal energy a system requires to undergo a phase transition. Its value is specific to the substance or mix of substances in question. The value can also vary with temperature and pressure. Generally speaking the value is different for the type of phase change being accomplished.
The energy released/absorbed by phase transition from solid to liquid, or vice versa, the heat of fusion is generally much higher than the sensible heat. Ice, for example, requires 333.55 J/g to melt, but then water will rise one degree further with the addition of just 4.18 J/g.
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 the slow removal of heat when in contact with air, which is a poor heat conductor.
A typical phase diagram for a single-component material, exhibiting solid, liquid and gaseous phases. The solid green line shows the usual shape of the liquid–solid phase line. The dotted green line shows the anomalous behavior of water when the pressure increases. The triple point and the critical point are shown as red dots.
The heat of solidification (when a substance changes from liquid to solid) is equal and opposite. This energy includes the contribution required to make room for any associated change in volume by displacing its environment against ambient pressure. The temperature at which the phase transition occurs is the melting point or the freezing point ...
The solid–liquid phase boundary can only end in a critical point if the solid and liquid phases have the same symmetry group. [5] For most substances, the solid–liquid phase boundary (or fusion curve) in the phase diagram has a positive slope so that the melting point increases with pressure.