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Concept
Melting
Summary
Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid. This occurs when the internal energy of the solid increases, typically by the application of heat or pressure, which increases the substance's temperature to the melting point. At the melting point, the ordering of ions or molecules in the solid breaks down to a less ordered state, and the solid melts to become a liquid.
Substances in the molten state generally have reduced viscosity as the temperature increases. An exception to this principle is the element sulfur, whose viscosity increases in the range of 160 °C to 180 °C due to polymerization.
Some organic compounds melt through mesophases, states of partial order between solid and liquid.
From a thermodynamics point of view, at the melting point the change in Gibbs free energy ∆G of the substances is zero, but there are non-zero changes in the enthalpy (H) and the entropy (S), known respectively as the enthalpy of fusion (or latent heat of fusion) and the entropy of fusion. 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. Helium-3 has a negative enthalpy of fusion at temperatures below 0.3 K. Helium-4 also has a very slightly negative enthalpy of fusion below 0.8 K. This means that, at appropriate constant pressures, heat must be removed from these substances in order to melt them.
Melting point#Predicting the melting point of substances (Lindemann's criterion) and Lindemann index
Among the theoretical criteria for melting, the Lindemann and Born criteria are those most frequently used as a basis to analyse the melting conditions.
The Lindemann criterion states that melting occurs because of "vibrational instability", e.g.
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