Sublimation (phase transition)

Transition of a substance directly from the solid to the gas state / From Wikipedia, the free encyclopedia

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Sublimation is the transition of a substance directly from the solid to the gas state,[1] without passing through the liquid state.[2] Sublimation is an endothermic process that occurs at temperatures and pressures below a substance's triple point in its phase diagram, which corresponds to the lowest pressure at which the substance can exist as a liquid. The reverse process of sublimation is deposition or desublimation, in which a substance passes directly from a gas to a solid phase.[3] Sublimation has also been used as a generic term to describe a solid-to-gas transition (sublimation) followed by a gas-to-solid transition (deposition).[4] While vaporization from liquid to gas occurs as evaporation from the surface if it occurs below the boiling point of the liquid, and as boiling with formation of bubbles in the interior of the liquid if it occurs at the boiling point, there is no such distinction for the solid-to-gas transition which always occurs as sublimation from the surface.

Dark green crystals of nickelocene, sublimed and freshly deposited on a cold finger

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. The pressure referred to is the partial pressure of the substance, not the total (e.g. atmospheric) pressure of the entire system. Thus, any solid can sublimate if its vapour pressure is higher than the surrounding partial pressure of the same substance, and in some cases sublimates at an appreciable rate (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.

The term sublimation refers to a physical change of state and is not used to describe the transformation of a solid to a gas in a chemical reaction. For example, the dissociation on heating of solid ammonium chloride into hydrogen chloride and ammonia is not sublimation but a chemical reaction. Similarly the combustion of candles, containing paraffin wax, to carbon dioxide and water vapor is not sublimation but a chemical reaction with oxygen.

Sublimation is caused by the absorption of heat which provides enough energy for some molecules to overcome the attractive forces of their neighbors and escape into the vapor phase. Since the process requires additional energy, it is an endothermic change. The enthalpy of sublimation (also called heat of sublimation) can be calculated by adding the enthalpy of fusion and the enthalpy of vaporization.

Comparison of phase diagrams of carbon dioxide (red) and water (blue) showing the carbon dioxide sublimation point (middle-left) at 1 atmosphere. As dry ice is heated, it crosses this point along the bold horizontal line from the solid phase directly into the gaseous phase. Water, on the other hand, passes through a liquid phase at 1 atmosphere.