Sublimation (phase transition) 1

Sublimation (phase transition)

Sublimation refers to the process of transition of a substance from
the solid phase 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.
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 which
possess an appreciable vapor pressure at a certain temperature
usually can sublime in air (e.g. ice just below 0ÄC). For some Dark green crystals of nickelocene, freshly sublimed
substances, such as carbon and arsenic, sublimation is much easier on a cold finger.
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. The reverse process of sublimation is
deposition. The formation of frost is an example of meteorological
deposition.

Examples Water sublimation occurring on ice covered powerline

poles in strong sunlight at just above freezing.

Carbon dioxide
Solid carbon dioxide (dry ice) sublimes readily at atmospheric
pressure at -78.5ÄC (197.5 K, Ä104.2ÅÄF), while liquid CO2 can be
obtained at pressures and temperatures above the triple point (5.2
atm, -56.4ÄC).

Water
Snow and ice sublime, although more slowly, below the melting
point temperature. This allows wet cloth to be hung outdoors in
freezing weather and retrieved later in a dry state. In freeze-drying
the material to be dehydrated is frozen and its water is allowed to
sublime under reduced pressure or vacuum. The loss of snow from Small pellets of dry ice subliming in air.
a snowfield during a cold spell is often caused by sunshine acting
directly on the upper layers of the snow. Ablation is a process which includes sublimation and erosive wear of
glacier ice.
Sublimation (phase transition) 2

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.
Naphthalene, a common ingredient in mothballs, also sublimes
easily. Arsenic can also sublime at high temperatures.
Various substances appear to sublime because of undergoing
chemical reactions or decomposition; for example, ammonium
chloride when heated decomposes into hydrogen chloride and
ammonia.

Camphor subliming. Note the white purified camphor

on the cold finger, and the dark-brown crude product.

Sublimation purification
Sublimation is a technique used by chemists to purify compounds.
Typically a solid is 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.[1] [2]

Historical usage
Crystals of ferrocene after purification by vacuum
In alchemy, sublimation typically referred to the process by which
sublimation
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). It is one of the 12 core alchemical processes.
Sublimation (phase transition) 3

References
[1] King, R. B. Organometallic Syntheses. Volume 1 Transition-Metal Compounds; Academic Press: New York, 1965. ISBN 0-444-42607-8.
[2] Laurence M. Harwood, Christopher J. Moody. Experimental organic chemistry: Principles and Practice (Illustrated edition ed.).
pp.Å154Å155.
Article Sources and Contributors 4

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Image:Cp2NiSublimate.jpg ÅSource: http://en.wikipedia.org/w/index.php?title=File:Cp2NiSublimate.jpg ÅLicense: Public Domain ÅContributors: Smokefoot
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