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Sublimation (physics)

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Sublimation (physics)


Sublimation is the transition of a substance directly from the solid to the gas phase without passing through an intermediate liquid phase. Sublimation is an endothermic phase transition that occurs at temperatures and pressures below a substance's triple point in its phase diagram. The reverse process of sublimation is desublimation, or deposition.

At normal pressures, most chemical compounds and elements possess three different states at different temperatures. In these cases, the transition from the solid to the gaseous state requires an intermediate liquid state. Note, however, that the pressure referred to here is the partial pressure of the substance, not the total (e.g., atmospheric) pressure of the entire system. So, all solids that possess an appreciable vapor pressure at a certain temperature usually can sublimate in air (e.g., water ice just below 0 °C). For some substances, such as carbon and arsenic, sublimation is much easier than evaporation from the melt, because the pressure of their triple point is very high, and it is difficult to obtain them as liquids.

Sublimation requires additional energy and is an endothermic change. The enthalpy of sublimation (also called heat of sublimation) can be calculated as the enthalpy of fusion plus the enthalpy of vaporization.

Examples

Carbon dioxide

Solid carbon dioxide (dry ice) sublimates readily at atmospheric pressure at −78.5 °C (194.65 K, −104.2 °F), whereas liquid CO2 can be obtained at pressures and temperatures above the triple point (5.2 atm, −56.4 °C).

Water

Snow and ice sublimate, although more slowly, below the melting point temperature.[1] In freeze-drying, the material to be dehydrated is frozen and its water is allowed to sublimate under reduced pressure or vacuum. The loss of snow from a snowfield during a cold spell is often caused by sunshine acting directly on the upper layers of the snow. Ablation is a process that includes sublimation and erosive wear of glacier ice.

Other compounds

Iodine produces fumes on gentle heating. It is possible to obtain liquid iodine at atmospheric pressure by controlling the temperature at just above the melting point of iodine. In forensic science, iodine vapor can reveal latent fingerprints on paper.[2]

Naphthalene, a common ingredient in mothballs, also sublimates easily. Arsenic can also sublimate at high temperatures.

Various substances appear to sublimate because of undergoing chemical reactions or decomposition; for example, ammonium chloride when heated decomposes into hydrogen chloride and ammonia.

Sublimation purification

Sublimation is a technique used by chemists to purify compounds. A solid is typically placed in a sublimation apparatus and heated under vacuum. Under this reduced pressure, the solid volatilizes and condenses as a purified compound on a cooled surface (cold finger), leaving a non-volatile residue of impurities behind. Once heating ceases and the vacuum is removed, the purified compound may be collected from the cooling surface.[3][4]

Historical usage

In the pseudoscience of alchemy, sublimation was used to refer to the process in which a substance is heated to a vapor, then immediately collects as sediment on the upper portion and neck of the heating medium (typically a retort or alembic), but can also be used to describe other similar non-laboratory transitions. It is mentioned by alchemical authors such as Basil Valentine and George Ripley, and in the Rosarium philosophorum, as a process necessary for the completion of the magnum opus. Here, the word sublimation is used to describe an exchange of "bodies" and "spirits" similar to laboratory phase transition between solids and gases. Valentine, in his Triumphal Chariot of Antimony (published 1678) makes a comparison to spagyrics in which a vegetable sublimation can be used to separate the spirits in wine and beer.[5] Ripley uses language more indicative of the mystical implications of sublimation, indicating that the process has a double aspect in the spiritualization of the body and the corporalizing of the spirit.[6] He writes:

And Sublimations we make for three causes,
The first cause is to make the body spiritual.
The second is that the spirit may be corporeal,
And become fixed with it and consubstantial.
The third cause is that from its filthy original.
It may be cleansed, and its saltiness sulphurious
May be diminished in it, which is infectious.[7]

See also

To
Solid Liquid Gas Plasma
From Solid Solid-solid transformation Melting / fusion Sublimation
Liquid Freezing Boiling / evaporation
Gas Deposition Condensation Ionization
Plasma Recombination / deionization

References

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