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A monotectic reaction consists of change from a liquid and to a combination of a solid and a second liquid, where the two liquids display a miscibility gap. [1] Separation into multiple phases can occur via spinodal decomposition, in which a single phase is cooled and separates into two different compositions.
However, only solid→liquid and liquid→solid phase changes are practical for PCMs. Although liquid–gas transitions have a higher heat of transformation than solid–liquid transitions, liquid→gas phase changes are impractical for thermal storage because large volumes or high pressures are required to store the materials in their gas phase.
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.
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 state or phase of a given set of matter can change depending on pressure and temperature conditions, transitioning to other phases as these conditions change to favor their existence; for example, solid transitions to liquid with an increase in temperature.
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.
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.
The enthalpy of fusion is the amount of energy required to convert one mole of solid into liquid. For example, when melting 1 kg of ice (at 0 °C under a wide range of pressures), 333.55 kJ of energy is absorbed with no temperature change. The heat of solidification (when a substance changes from liquid to solid) is equal and opposite.