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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.
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.
A vapor can exist in equilibrium with a liquid (or solid), in which case the gas pressure equals the vapor pressure of the liquid (or solid). A supercritical fluid (SCF) is a gas whose temperature and pressure are above the critical temperature and critical pressure respectively. In this state, the distinction between liquid and gas disappears.
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.
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.
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 melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends on pressure and is usually specified at a standard pressure such as 1 atmosphere or 100 kPa. When ...