Sublimation (phase

transition)
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From Wikipedia, the free encyclopedia

"Sublimates" redirects here. For other uses, see Sublimation (disambiguation).

Not to be confused with subliminal stimuli.

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

Sublimation of iodine
Sublimation is the transition of a substance directly from the solid to the gas
state, without passing through the liquid state.[1] The verb form of sublimation is
sublime, or less preferably, sublimate.[2] Sublimate also refers to the product
obtained by sublimation.[2][3] The point at which sublimation occurs rapidly (for
further details, see below) is called critical sublimation point, or simply
sublimation point. Notable examples include sublimation of dry ice at room
temperature and atmospheric pressure, and that of solid iodine with heating.

The reverse process of sublimation is deposition (also called desublimation), in

which a substance passes directly from a gas to a solid phase, without passing
through the liquid state.[4]

All solids sublime, though most sublime at extremely low rates that are hardly
detectable. 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 gas 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 sublime if its
vapour pressure is higher than the surrounding partial pressure of the same
substance, and in some cases, sublimes at an appreciable rate (e.g. water ice just
below 0 °C).

For some substances, such as carbon and arsenic, sublimation from solid state
is much more achievable than evaporation from liquid state and it is difficult to
obtain them as liquids. This is because the pressure of their triple point in its
phase diagram (which corresponds to the lowest pressure at which the
substance can exist as a liquid) is very high.

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,
sublimation 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.

Confusions

While the definition of sublimation is simple, there is often confusion as to what

counts as a sublimation.

False correspondence with vaporization

Vaporization (from liquid to gas) is divided into two types: vaporization on the
surface of the liquid is called evaporation, and vaporization at the boiling point
with formation of bubbles in the interior of the liquid is called boiling. However
there is no such distinction for the solid-to-gas transition, which is always called
sublimation in both corresponding cases.

Potential distinction

For clarification, a distinction between the two corresponding cases is needed.

With reference to a phase diagram, the sublimation that occurs left of the solid-
gas boundary, the triple point or the solid-liquid boundary (corresponding to
evaporation in vaporization) may be called gradual sublimation; and the
substance sublimes gradually, regardless of rate. The sublimation that occurs at
the solid-gas boundary (critical sublimation point) (corresponding to boiling in
vaporization) may be called rapid sublimation, and the substance sublimes
rapidly. The words "gradual" and "rapid" have acquired special meanings in this
context and no longer describe the rate of sublimation. [citation needed]

Misuse for chemical reaction

The term sublimation refers specifically 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.

Historical definition

Sublimation is historically used as a generic term to describe a two-step phase

transition ― a solid-to-gas transition (sublimation in a more precise definition)
followed by a gas-to-solid transition (deposition).[5][6] (See below)

Examples
 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.

Carbon dioxide

Dry ice subliming in air

Solid carbon dioxide (dry ice) sublimes rapidly along the solid-gas boundary
(sublimation point) below the triple point (e.g., at the temperature of −78.5 °C, at
atmospheric pressure), whereas its melting into liquid CO2 can occur along the
solid-liquid boundary (melting point) at pressures and temperatures above the triple
point (i.e., 5.1 atm, −56.6 °C).

Water

Snow and ice sublime gradually at temperatures below the solid-liquid boundary
(melting point) (generally 0 °C), and at partial pressures below the triple point
pressure of 612 Pa (0.00604 atm), at a low rate.[7] 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 a snowfield during a cold spell is
often caused by sunshine acting directly on the upper layers of the snow.
Sublimation of ice is a factor to the erosive wear of glacier ice, also called
ablation in glaciology.[citation needed]

Naphthalene

Naphthalene, an organic compound commonly found in pesticides such as

mothballs, sublimes easily because it is made of non-polar molecules that are
held together only by van der Waals intermolecular forces. Naphthalene is a solid
that sublimes gradually at standard temperature and pressure,[8] at a high rate,
with the critical sublimation point at around 80 °C or 176 °F. [9] At low temperature,
its vapour pressure is high enough, 1 mmHg at 53 °C, [10] to make the solid form of
naphthalene evaporate into gas. On cool surfaces, the naphthalene vapours will
solidify to form needle-like crystals.

Experimental set up for the sublimation reaction of naphthalene Solid naphthalene sublimes and
form the crystal-like structure at the bottom of the watch glass

Solid compound of naphthalene sublimed to form a crystal-like structure on the cool surface.

Iodine
 Camphor subliming in a cold finger. The crude product in the bottom is dark brown; the white
purified product on the bottom of the cold finger above is hard to see against the light background.

Iodine gradually sublimes and produces visible fumes on gentle heating at

standard atmospheric temperature. It is possible to obtain liquid iodine at
atmospheric pressure by controlling the temperature at just between the melting
point and the boiling point of iodine. In forensic science, iodine vapor can reveal
latent fingerprints on paper.[11]

Other substances

Arsenic can sublime readily at high temperatures.

Cadmium and zinc sublime much more than other common materials, so they are
not suitable materials for use in vacuum.[citation needed]

Purification by sublimation
 Crystals of ferrocene after purification by vacuum sublimation

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.[12][13] For even higher purification efficiencies,
a temperature gradient is applied, which also allows for the separation of different
fractions. Typical setups use an evacuated glass tube that is heated gradually in
a controlled manner. The material flow is from the hot end, where the initial
material is placed, to the cold end that is connected to a pump stand. By
controlling temperatures along the length of the tube, the operator can control
the zones of re-condensation, with very volatile compounds being pumped out of
the system completely (or caught by a separate cold trap), moderately volatile
compounds re-condensing along the tube according to their different volatilities,
and non-volatile compounds remaining in the hot end. Vacuum sublimation of
this type is also the method of choice for purification of organic compounds for
use in the organic electronics industry, where very high purities (often > 99.99%)
are needed to satisfy the standards for consumer electronics and other
applications.[citation needed]

Historical usage

In ancient alchemy, a protoscience that contributed to the development of

modern chemistry and medicine, alchemists developed a structure of basic
laboratory techniques, theory, terminology, and experimental methods.
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 was 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 was used to describe an exchange of "bodies" and
"spirits" similar to laboratory phase transition between solids and gases.
Valentine, in his Le char triomphal de l'antimoine (Triumphal Chariot of Antimony,
published 1646) made a comparison to spagyrics in which a vegetable
sublimation can be used to separate the spirits in wine and beer. [14] Ripley used
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.[15] He writes:[16]

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.

Sublimation predictions

The enthalpy of sublimation has commonly been predicted using the

equipartition theorem. If the lattice energy is assumed to be approximately half
the packing energy,[clarification needed] then the following thermodynamic corrections
can be applied to predict the enthalpy of sublimation. Assuming a 1 molar ideal
gas gives a correction for the thermodynamic environment (pressure and volume)
in which pV = RT, hence a correction of 1RT. Additional corrections for the
vibrations, rotations and translation then need to be applied. From the
equipartition theorem gaseous rotation and translation contribute 1.5RT each to the final
state, therefore a +3RT correction. Crystalline vibrations and rotations contribute 3RT
each to the initial state, hence −6RT. Summing the RT corrections; −6RT + 3RT + RT =
−2RT.[17] This leads to the following approximate sublimation enthalpy. A similar
approximation can be found for the entropy term if rigid bodies are assumed.[18]
[19]

Δ𝐻sublimation=−𝑈lattice energy−2𝑅𝑇
Dye-sublimation printing

Main article: Dye-sublimation printer

Dye-sub printing is a digital printing technology using full color artwork that
works with polyester and polymer-coated substrates. Also referred to as digital
sublimation, the process is commonly used for decorating apparel, signs and
banners, as well as novelty items such as cell phone covers, plaques, coffee
mugs, and other items with sublimation-friendly surfaces. The process uses the
science of sublimation, in which heat and pressure are applied to a solid, turning
it into a gas through an endothermic reaction without passing through the liquid
phase.[citation needed]

In sublimation printing, unique sublimation dyes are transferred to sheets of

“transfer” paper via liquid gel ink through a piezoelectric print head. The ink is
deposited on these high-release inkjet papers, which are used for the next step of
the sublimation printing process. After the digital design is printed onto
sublimation transfer sheets, it is placed on a heat press along with the substrate
to be sublimated.[citation needed]

In order to transfer the image from the paper to the substrate, it requires a heat
press process that is a combination of time, temperature and pressure. The heat
press applies this special combination, which can change depending on the
substrate, to “transfer” the sublimation dyes at the molecular level into the
substrate. The most common dyes used for sublimation activate at 350 degrees
Fahrenheit. However, a range of 380 to 420 degrees Fahrenheit is normally
recommended for optimal color.[citation needed]

The result of the sublimation process is a nearly permanent, high resolution, full
color print. Because the dyes are infused into the substrate at the molecular level,
rather than applied at a topical level (such as with screen printing and direct to
garment printing), the prints will not crack, fade or peel from the substrate under
normal conditions.[citation needed]

See also

● Ablation
● Enthalpy of sublimation
● Freeze-drying
● Freezer burn – common process involving sublimation
 ● Phase diagram
● Phase transitions

Table of phase transitions of matter

To Solid Liquid Gas Plasma

From

Solid Melting Sublimation

Liquid Freezing Vaporization

Gas Depositio Condensatio Ionizatio

n n n

Plasma Recombinatio
n

References

● ^ Whitten, Kenneth W.; Gailey, Kenneth D.; Davis, Raymond E. (1992). General chemistry
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● ^
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● "Sublimate". Merriam-Webster.com Dictionary.
● ^ "Sublimate". CollinsDictionary.com Dictionary.
● ^ Boreyko, Jonathan B.; Hansen, Ryan R.; Murphy, Kevin R.; Nath, Saurabh; Retterer,
Scott T.; Collier, C. Patrick (2016). "Controlling condensation and frost growth with
chemical micropatterns". Scientific Reports. 6: 19131. Bibcode:2016NatSR...619131B.
doi:10.1038/srep19131. PMC 4726256. PMID 26796663.
● ^ "Sublime". Dictionary.com Unabridged (Online). n.d.
● ^ "Sublime". CollinsDictionary.com Dictionary.
● ^ Fassnacht, S. R. (2004). "Estimating Alter-shielded gauge snowfall undercatch,
snowpack sublimation, and blowing snow transport at six sites in the coterminous
 USA". Hydrol. Process. 18 (18): 3481–3492. Bibcode:2004HyPr...18.3481F.
doi:10.1002/hyp.5806. S2CID 129927018.
● ^ Caroll, J. (2014). Natural Gas Hydrates. Gulf Professional. p. 16. ISBN 9780128005750.
● ^ Staff writer(s) (2015). "what solids go through sublimation?". National Science
Foundation and UCSB School-University partnership. Retrieved 13 November 2015.
● ^ Pavia, D. (2005). Introduction to organic laboratory technique. Thomson Brooks/Cole.
pp. 781–782. ISBN 978-0534408336.
● ^ Girard, James (2011). Criminalistics: Forensic Science, Crime and Terrorism. Jones &
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● ^ R. B. King Organometallic Syntheses. Volume 1 Transition-Metal Compounds;
Academic Press: New York, 1965. ISBN 0-444-42607-8.
● ^ Harwood, Laurence M.; Moody, Christopher J. (1989). Experimental organic chemistry:
Principles and Practice (Illustrated ed.). WileyBlackwell. pp. 154–155. ISBN 978-0-632-
02017-1.
● ^ Barrett, Francis (1815). The lives of alchemystical philosophers: with a critical
catalogue of books in occult chemistry, and a selection of the most celebrated treatises
on the theory and practice of the hermetic art. Macdonald and Son for Lackington, Allen,
& Co. p. 233.
● ^ DiBernard, Barbara (1980). Alchemy and Finnegans wake. SUNY Press. p. 57. ISBN
978-0873953887.
● ^ Ripley, George (1591). Compound of Alchemy.
● ^ Gavezzotti, A. (1997). Theoretical Aspects and Computer Modeling of the Molecular
Solid State. Chichester: Wiley and Sons.
● ^ McDonagh, J. L.; Nath; De Ferrari, Luna; Van Mourik, Tanja; Mitchell, John B. O. (2014).
"Uniting Cheminformatics and Chemical Theory To Predict the Intrinsic Aqueous
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● ^ McDonagh, James; Palmer, David S.; Van Mourik, Tanja; Mitchell, John B. O. (17
October 2016). "Are The Sublimation Thermodynamics of organic molecules
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External links

● Media related to Sublimation at Wikimedia Commons

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