Sublimation (phase transition): Difference between revisions

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{{Short description|Transition of a substance directly from the solid to thegas gaswithout statemelting}}

{{Redirect|Sublimates||Sublimation (disambiguation){{!}}Sublimation}}

{{distinguish|subliminal stimuli}}

{{pp|small=yes}}

<!--

<!-- READ BEFORE EDIT, sublimation refers to ALL THREE CASES:

1. the transition below triple point and below boiling point

1. Sublime gradually: below triple point and left of solid-gas boundary

(similar to evaporation)

(bottom left of solid in phase diagram)

2. theSublime transitionrapidly: below triple point and at boilingsolid-gas pointboundary

(similar to boiling)

3. theSublime transitiongradually: above triple point and belowleft meltingof pointsolid-liquid boundary (yes, solid sublimes above triple point)

(also similar to evaporation, just higher pressure)

(top left of solid in phase diagram)

These three cases jointly exhaust the solid space in the phrase diagram. This makes sense, after all, technically, all solids sublime (depending mostly on vapour pressure, which is very situational).

One may notice there is a fourth case in the solid space, that is, at the solid-liquid boundary. It is uncertain if the solid is still defined as subliming WHILE melting, and in case it is, it would be subliming rapidly.

- the definition is simply the transition of a substance directly from the solid to the gas state, without passing through the liquid state

-->

- technically, all solids sublime (depending mostly on vapour pressure) --><!-- checking some online English dictionaries:

<!--

checking some online English dictionaries:

1. sublime and sublimate are both valid, and both have some other meanings

(https://www.merriam-webster.com/dictionary/sublime#did-you-know)

(also almost every dictionary)

2. sublimate may mean the product

(https://www.merriam-webster.com/dictionary/sublimate#dictionary-entry-2)

(https://www.collinsdictionary.com/dictionary/english/sublimate)

(https://www.dictionary.com/browse/sublimate)

(https://chambers.co.uk/search/?query=sublimate&title=21st)

(https://www.wordreference.com/definition/sublimate)

3. sublimation may also mean itself followed by deposition

(https://www.collinsdictionary.com/dictionary/english/sublime)

(https://www.dictionary.com/browse/sublime)

4. sublimation seems used to mean deposition alone but this meaning is now completely obsolete, few if any online dictionary has such meaning as of 2023, the archaic use is likely phased out

-->

[[File:Nickelocen an einem Kühlfinger.jpg|thumb|right|Dark green [[crystals]] of [[nickelocene]], sublimed and freshly deposited on a [[cold finger]]]]

yes, this is very confusing -->

[[File:Sublimation of iodine.webm|thumb|Sublimation of [[iodine]]]]

'''Sublimation''' is the [[Phase transition|transition of a substance]] directly from the [[solid]] to the [[gas]] state, without passing through the [[liquid]] state.<ref>{{cite book |last1=Whitten |first1=Kenneth W. |last2=Gailey |first2=Kenneth D. |last3=Davis |first3=Raymond E. |title=General chemistry |url=https://archive.org/details/generalchemistry00whit_0 |url-access=registration |date=1992 |publisher=Saunders College Publishing |isbn=0-03-072373-6 |page=[https://archive.org/details/generalchemistry00whit_0/page/475 475] |edition=4th}}</ref> The verb form of sublimation is ''sublime'', or less preferably, ''sublimate''.<ref name=":0">{{cite Merriam-Webster|Sublimate}}</ref> ''Sublimate'' also refers to the product obtained by sublimation.<ref name=":0" /><ref>[https://www.collinsdictionary.com/dictionary/english/sublimate "Sublimate"]. [[Collins English Dictionary#CollinsDictionary.com|CollinsDictionary.com Dictionary]].</ref> The point at which sublimation occurs rapidly (for further details, see [[#False correspondence with vaporization|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.

[[File:Nickelocen an einem Kühlfinger.jpg|thumb|right|Dark green [[crystals]] of [[nickelocene]], sublimed and freshly deposited on a [[cold finger]]]]

'''Sublimation''' is the [[Phase transition|transition of a substance]] directly from the [[solid]] to the [[gas]] state, without passing through the [[liquid]] state.<ref>{{cite book |last1=Whitten |first1=Kenneth W. |last2=Gailey |first2=Kenneth D. |last3=Davis |first3=Raymond E. |title=General chemistry |url=https://archive.org/details/generalchemistry00whit_0 |url-access=registration |date=1992 |publisher=Saunders College Publishing |isbn=0-03-072373-6 |page=[https://archive.org/details/generalchemistry00whit_0/page/475 475] |edition=4th}}</ref> The verb form of sublimation is ''sublime'', or less preferably, ''sublimate''<ref name=":0">{{cite Merriam-Webster|Sublimate}}</ref>. The product obtained by sublimation is also called the ''sublimate''<ref name=":0" />. The reverse process of sublimation is [[deposition (phase transition)|''deposition'']] or(also called ''desublimation''), in which a substance passes directly from a gas to a solid phase, without passing through the liquid state.<ref name="DepositionDef">{{cite journal |title=Controlling condensation and frost growth with chemical micropatterns |first1=Jonathan B. |last1=Boreyko |first2=Ryan R. |last2=Hansen |first3=Kevin R. |last3=Murphy |first4=Saurabh |last4=Nath |first5=Scott T. |last5=Retterer |first6=C. Patrick |last6=Collier |journal=Scientific Reports |year=2016 |volume=6 |pages=19131 |doi=10.1038/srep19131 |pmid=26796663 |pmc=4726256 |bibcode=2016NatSR...619131B}}</ref>

AllTechnically, all solids may sublime, though most sublime at extremely low rates that are hardly detectable under usual conditions. At [[standard conditions for temperature and pressure|normal pressures]], most [[chemical compound]]s and [[chemical element|elements]] possess three different states at different [[temperature]]s. 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]]|''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, sublimessublimation occurs at an appreciable rate (e.g. water ice just below 0&nbsp;°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 [[intermolecular force|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, itthere is often confusedconfusion as to what counts as a sublimation.

=== False correspondence with vaporization ===

While [[vaporizationVaporization]] (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., Solid-to-gas transitionwhich 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.{{cn|date=April 2024}}<!-- This distinction is used only on this page and nowhere else, to minimize confusion. If there is a better distinction, change it along with the examples. If this violates the policy of Wikipedia, please delete this paragraph, and if possible, also provide a better solution. -->

=== Misuse for chemical reaction ===

The term ''sublimation'' refers specifically to a [[physical change]] of [[state of matter|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.

=== UncommonHistorical definition ===

Sublimation is sometimeshistorically 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 (phase transition)|deposition]]).<ref>{{Dictionary.com|Sublime}}</ref><ref>[[Filehttps:Comparison//www.collinsdictionary.com/dictionary/english/sublime carbon"Sublime"]. dioxide[[Collins waterEnglish phase diagramsDictionary#CollinsDictionary.svgcom|thumb|upright=2|Comparison of phase diagrams of carbon dioxide (red) and water (blue) showing the carbon dioxide sublimation point (middle-left) at 1 atmosphereCollinsDictionary.com As dry ice is heated, it crosses this point along the bold horizontal line from the solid phase directly into the gaseous phaseDictionary]].</ref> Water,(See on[[#Historical the other hand, passes through a liquid phase at 1 atmosphere.usage|below]])

==Examples==

[[File:Comparison carbon dioxide water phase diagrams.svg|thumb|upright=2|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.]]

The examples shown are substances that noticeably sublime under certain conditions.

===Carbon dioxide===

[[File:Dry Ice Vapor (17490553041).jpg|thumb|[[Dry ice]] subliming in air]]

Solid [[carbon dioxide]] ([[dry ice]]) sublimes everywhererapidly along the linesolid-gas boundary (sublimation point) below the triple point (e.g., at the temperature of −78.5&nbsp;°C (194.65 K, {{convert|194.65|K|F|disp=output only}}) at [[atmospheric pressure]]), whereas its melting into liquid CO₂ can occur along the solid-liquid lineboundary ([[melting point]]) at pressures and temperatures above the triple point (i.e., 5.1 atm, −56.6&nbsp;°C).

===Water===

[[Snow]] and [[ice]] sublime, although more slowly,gradually at temperatures below the freezing/[[solid-liquid boundary (melting point]]) temperature line at(generally 0&nbsp;°C), forand at partial pressures below the triple point pressure of {{convert|612|Pa|atm|abbr=on}}, at a low rate.<ref>{{cite journal |last=Fassnacht |first=S. R. |year=2004 |title=Estimating Alter-shielded gauge snowfall undercatch, snowpack sublimation, and blowing snow transport at six sites in the coterminous USA |journal=Hydrol. Process. |doi=10.1002/hyp.5806 |bibcode=2004HyPr...18.3481F |volume=18 |issue=18 |pages=3481–3492|s2cid=129927018 }}</ref> 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. [[Ablation]]Sublimation of ice is a processfactor thatto includes sublimation andthe erosive wear of [[glacier ice]], known as [[ablation]] in [[glaciology]].<ref>{{citationCite web needed|url=http://amsglossary.allenpress.com/glossary/search?p=1&query=ablation&submit=Search |title=''Glossary of Meteorology'' |access-date=October2010-07-05 |archive-url=https://web.archive.org/web/20110917232831/http://amsglossary.allenpress.com/glossary/search?p=1&query=ablation&submit=Search |archive-date=2011-09-17 |url-status=dead 2021}}</ref>

===Naphthalene===

[[File:Sublimation reaction of naphthalene.jpg|thumb|Experimental set up for the sublimation reaction of [[naphthalene]], Solidsolid naphthalene sublimes and form the crystal-like structure at the bottom of the [[watch glass]]]]

[[Naphthalene]], an organic compound commonly found in pesticides such as [[mothball]]s, sublimes easily because it is made of non-polar molecules that are held together only by [[Van der Waals force|van der Waals]] intermolecular forces. Naphthalene is a solid that sublimes readily at [[standard conditions for temperature and pressure|standard atmospheric temperature]]<ref>

[[File:Crystal-like sublimated naphthalene.jpg|thumb|Solid compound of [[naphthalene]] sublimed to form a crystal-like structure on the cool surface.]]

[[Naphthalene]], an organic compound commonly found in pesticides such as [[mothball]]s, sublimes easily because it is made of non-polar molecules that are held together only by [[Van der Waals force|van der Waals]] intermolecular forces. Naphthalene is a solid that sublimes readilygradually at [[standard conditions for temperature and pressure|standard atmospheric temperature]],<ref>

{{cite book

|last=Caroll |first=J.

Line 71 ⟶ 83:

|isbn=9780128005750

|page=16

|publisher=Gulf Professional

}}</ref> at a high rate, with the boilingcritical point (sublimation point) at around 80{{nbsp}}°convert|80|C or 176{{nbsp|F}}°F.<ref>

{{cite web

|author=Staff writer(s)

|date=2015

|title=what solidsolids go through sublimation?

|publisher=National Science Foundation and UCSB School-University partnership

|url=http://scienceline.ucsb.edu/getkey.php?key=4306

Line 86 ⟶ 99:

|isbn=978-0534408336

|pages=781–782

|publisher=Thomson Brooks/Cole

}}</ref> to make the solid form of naphthalene evaporate into gas. On cool surfaces, the naphthalene vapours will solidify to form needle-like crystals.

[[File:Sublimation reaction of naphthalene.jpg|thumb|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]]]]

[[File:Crystal-like sublimated naphthalene.jpg|thumb|Solid compound of [[naphthalene]] sublimed to form a crystal-like structure on the cool surface.]]

===Iodine===

[[Iodine]] sublimes gradually and produces visible fumes on gentle heating at [[standard conditions for temperature and pressure|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 [[fingerprint]]s on paper.<ref>{{cite book

[[File:Camphor sublimation 1.jpg|thumb|upright|[[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]] sublimes and produces visible fumes on gentle heating at [[standard conditions for temperature and pressure|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 [[fingerprint]]s on paper.<ref>{{cite book

|last=Girard |first=James

|year= 2011

Line 104 ⟶ 113:

=== Other substances ===

[[File:Camphor sublimation 1.jpg|thumb|upright|[[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.]]

[[Arsenic]] can sublime readily at high temperatures.

At [[atmospheric pressure]], [[arsenic]] sublimes gradually upon heating, and sublimes rapidly at {{convert|887|K|C}}.<ref name="Holl3">{{cite book |last=Holleman |first=Arnold F. |title=Lehrbuch der Anorganischen Chemie |author2=Wiberg, Egon |author3=Wiberg, Nils |date=1985 |publisher=Walter de Gruyter |isbn=978-3-11-007511-3 |edition=91–100 |pages=675–681 |language=de |chapter=Arsen}}</ref>

[[Cadmium]] and [[zinc]] sublime much more than other common materials, so they are not suitable [[materials for use in vacuum]] because they sublime much more than other common materials.{{citation needed|date=May 2019}}

==Purification by sublimation==

Line 155 ⟶ 166:

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|date=October 2021}}

==Table of phase transitions of matter==

{{Table of phase transitions}}

==See also==

Line 163 ⟶ 177:

*[[Phase diagram]]

*[[Phase transition|Phase transitions]]

==Table of phase transitions of matter==

{{Table of phase transitions}}

{{Clear}}

==References==