Sublimation (phase transition)

<h2 id="confusions">Confusions</h2>
<p>While the definition of sublimation is simple, there is often confusion as to what counts as a sublimation.
</p>
<h3>False correspondence with vaporization</h3>
<p><a href="/facts/Vaporization/0Uxpy1WQ">Vaporization</a> (from liquid to gas) is divided into two types: vaporization on the surface of the liquid is called <a href="/facts/Evaporation/tgvIlJys">evaporation</a>, and vaporization at the boiling point with formation of bubbles in the interior of the liquid is called <a href="/facts/Boiling/BHxWzT2k">boiling</a>. However there is <i>no</i> such distinction for the solid-to-gas transition, which is always called sublimation in both corresponding cases.
</p>
<h4>Potential distinction</h4>
<p>For clarification, a distinction between the two corresponding cases is needed. With reference to a <a href="/facts/Phase_diagram/rcemFgW0">phase diagram</a>, 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 <i>gradual sublimation</i>; and the substance <i>sublimes gradually</i>, regardless of rate. The sublimation that occurs at the solid-gas boundary (critical sublimation point) (corresponding to boiling in vaporization) may be called <i>rapid sublimation</i>, and the substance <i>sublimes rapidly</i>. The words "gradual" and "rapid" have acquired special meanings in this context and no longer describe the rate of sublimation.
</p>
<h3>Misuse for chemical reaction</h3>
<p>The term <i>sublimation</i> refers specifically to a <a href="/facts/Physical_change/kfzhe7M3">physical change</a> of <a href="/facts/State_of_matter/ojlIA1UF">state</a> 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 <a href="/facts/Ammonium_chloride/SfXdntlv">ammonium chloride</a> into hydrogen chloride and ammonia is <i>not</i> sublimation but a chemical reaction. Similarly the combustion of candles, containing <a href="/facts/Paraffin_wax/11Dyraqg">paraffin wax</a>, to <a href="/facts/Carbon_dioxide/xGzpppEp">carbon dioxide</a> and <a href="/facts/Water_vapor/DX5IUFG0">water vapor</a> is <i>not</i> sublimation but a chemical reaction with oxygen.
</p>
<h3>Historical definition</h3>
<p>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 (<a href="/facts/Deposition_(phase_transition)/JweT4Eqs">deposition</a>).<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a><a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> (See below)
</p>
<h2 id="examples">Examples</h2>

<p>The examples shown are substances that noticeably sublime under certain conditions.
</p>
<h3>Carbon dioxide</h3>

<p>Solid <a href="/facts/Carbon_dioxide/xGzpppEp">carbon dioxide</a> (<a href="/facts/Dry_ice/BvW99HtH">dry ice</a>) sublimes rapidly along the solid-gas boundary (sublimation point) below the triple point (e.g., at the temperature of −78.5 °C, at <a href="/facts/Atmospheric_pressure/wJLMSaVG">atmospheric pressure</a>), whereas its melting into liquid CO2 can occur along the solid-liquid boundary (<a href="/facts/Melting_point/MY0w0h0k">melting point</a>) at pressures and temperatures above the triple point (i.e., 5.1 atm, −56.6 °C).
</p>
<h3>Water</h3>
<p><a href="/facts/Snow/HEFKcgIB">Snow</a> and <a href="/facts/Ice/BGvkKFjD">ice</a> 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.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> In <a href="/facts/Freeze-drying/aURqwbrQ">freeze-drying</a>, 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 <a href="/facts/Snowfield/cS3877el">snowfield</a> 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 <a href="/facts/Glacier_ice/BGvkKFjD">glacier ice</a>, known as <a href="/facts/Ablation/tTSHH09G">ablation</a> in <a href="/facts/Glaciology/dSElvpIj">glaciology</a>.<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a>
</p>
<h3>Naphthalene</h3>

<p><a href="/facts/Naphthalene/RU2sV8mN">Naphthalene</a>, an organic compound commonly found in pesticides such as <a href="/facts/Mothball/sbepfL5r">mothballs</a>, sublimes easily because it is made of non-polar molecules that are held together only by <a href="/facts/Van_der_Waals_force/jyGU8Vh9">van der Waals</a> intermolecular forces. Naphthalene is a solid that sublimes gradually at <a href="/facts/Standard_temperature_and_pressure/JhJv9KFJ">standard temperature and pressure</a>,<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> at a high rate, with the critical sublimation point at around 80 °C (176 °F).<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> At low temperature, its vapour pressure is high enough, 1 mmHg at 53 °C,<a class="footnote-ref" id="fnref:12" href="#fn:12"><sup>12</sup></a> to make the solid form of naphthalene evaporate into gas. On cool surfaces, the naphthalene vapours will solidify to form needle-like crystals.
</p>
<h3>Iodine</h3>
<p><a href="/facts/Iodine/JlfMecMf">Iodine</a> sublimes gradually and produces visible fumes on gentle heating at <a href="/facts/Standard_conditions_for_temperature_and_pressure/JhJv9KFJ">standard atmospheric temperature</a>. 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 <a href="/facts/Forensic_science/4upVa2vB">forensic science</a>, iodine vapor can reveal latent <a href="/facts/Fingerprint/5WLcd20T">fingerprints</a> on paper.<a class="footnote-ref" id="fnref:13" href="#fn:13"><sup>13</sup></a>
</p>
<h3>Other substances</h3>

<p>At <a href="/facts/Atmospheric_pressure/wJLMSaVG">atmospheric pressure</a>, <a href="/facts/Arsenic/k1c4f44D">arsenic</a> sublimes gradually upon heating, and sublimes rapidly at 887 K (614 °C).<a class="footnote-ref" id="fnref:14" href="#fn:14"><sup>14</sup></a>
</p><p><a href="/facts/Cadmium/wXkV2eIX">Cadmium</a> and <a href="/facts/Zinc/80b1qgk3">zinc</a> sublime much more than other common materials, so they are not suitable <a href="/facts/Materials_for_use_in_vacuum/pooN9Tny">materials for use in vacuum</a>.
</p>
<h2 id="purification-by-sublimation">Purification by sublimation</h2>

<p>Sublimation is a technique used by <a href="/facts/Chemist/N09K7Bdm">chemists</a> to purify <a href="/facts/Chemical_compound/37FXqqtv">compounds</a>. A solid is typically placed in a <a href="/facts/Sublimation_apparatus/ghhp0Hjn">sublimation apparatus</a> and heated under <a href="/facts/Vacuum/BTk3goyV">vacuum</a>. Under this reduced <a href="/facts/Pressure/eyc37GRG">pressure</a>, the solid <a href="/facts/Volatility_(chemistry)/90r3ep6w">volatilizes</a> and condenses as a purified compound on a cooled surface (<a href="/facts/Cold_finger/Nvot1raj">cold finger</a>), leaving a non-volatile residue of <a href="/facts/Impurities/FfPvIRoB">impurities</a> behind. Once heating ceases and the vacuum is removed, the purified compound may be collected from the cooling surface.<a class="footnote-ref" id="fnref:15" href="#fn:15"><sup>15</sup></a><a class="footnote-ref" id="fnref:16" href="#fn:16"><sup>16</sup></a>
For even higher purification efficiencies, a <a href="/facts/Temperature_gradient/YhWj21zy">temperature gradient</a> 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 <a href="/facts/Cold_trap/hqutpKYR">cold trap</a>), 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 <a href="/facts/Organic_electronics/FCPAEwx3">organic electronics industry</a>, where very high purities (often > 99.99%) are needed to satisfy the standards for consumer electronics and other applications.
</p>
<h2 id="historical-usage">Historical usage</h2>
<p>In ancient <a href="/facts/Alchemy/CEx0U1Em">alchemy</a>, a <a href="/facts/Protoscience/aNyCaQQq">protoscience</a> that contributed to the development of modern chemistry and medicine, alchemists developed a structure of basic laboratory techniques, theory, terminology, and experimental methods. <i>Sublimation</i> 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 <a href="/facts/Retort/lwrgFkIC">retort</a> or <a href="/facts/Alembic/Fzhdute7">alembic</a>), but can also be used to describe other similar non-laboratory transitions. It was mentioned by alchemical authors such as <a href="/facts/Basil_Valentine/6BVlJQNj">Basil Valentine</a> and <a href="/facts/George_Ripley_(alchemist)/m9CzsFjv">George Ripley</a>, and in the <i><a href="/facts/Rosarium_philosophorum/FjsDhPGu">Rosarium philosophorum</a></i>, as a process necessary for the completion of the <a href="/facts/Magnum_opus_(alchemy)/x8HvNu7R">magnum opus</a>. Here, the word <i>sublimation</i> was used to describe an exchange of "bodies" and "spirits" similar to laboratory phase transition between solids and gases. Valentine, in his <i><a href="/facts/Basil_Valentine/6BVlJQNj">Le char triomphal de l'antimoine</a></i> (Triumphal Chariot of Antimony, published 1646) made a comparison to <a href="/facts/Spagyrics/rGuyyCk2">spagyrics</a> in which a vegetable sublimation can be used to separate the spirits in wine and beer.<a class="footnote-ref" id="fnref:17" href="#fn:17"><sup>17</sup></a> 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.<a class="footnote-ref" id="fnref:18" href="#fn:18"><sup>18</sup></a> He writes:<a class="footnote-ref" id="fnref:19" href="#fn:19"><sup>19</sup></a>
</p>
<blockquote>
<p>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.
</p>
</blockquote>
<h2 id="sublimation-predictions">Sublimation predictions</h2>
<p>The <a href="/facts/Enthalpy/bBou8lCE">enthalpy</a> of sublimation has commonly been predicted using the <a href="/facts/Equipartition_theorem/EJfmTK6W">equipartition theorem</a>. If the <a href="/facts/Lattice_energy/MRVJpWfk">lattice energy</a> is assumed to be approximately half the packing energy, then the following thermodynamic corrections can be applied to predict the enthalpy of sublimation. Assuming a 1 <a href="/facts/Molar_concentration/P2WL5b9q">molar</a> <a href="/facts/Ideal_gas/80EfYGFj">ideal gas</a> gives a correction for the thermodynamic environment (pressure and volume) in which pV = RT, hence a correction of 1RT. Additional corrections for the <a href="/facts/Molecular_vibration/Y0ovRukI">vibrations</a>, <a href="/facts/Rigid_rotor/Ue8nrySx">rotations</a> and translation then need to be applied. From the <a href="/facts/Equipartition_theorem/EJfmTK6W">equipartition theorem</a> 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.<a class="footnote-ref" id="fnref:20" href="#fn:20"><sup>20</sup></a> This leads to the following approximate sublimation enthalpy. A similar approximation can be found for the <a href="/facts/Entropy/s52IXeFz">entropy</a> term if rigid bodies are assumed.<a class="footnote-ref" id="fnref:21" href="#fn:21"><sup>21</sup></a><a class="footnote-ref" id="fnref:22" href="#fn:22"><sup>22</sup></a>

Δ
        
          H
          
            sublimation
          
        
        =
        −
        
          U
          
            lattice energy
          
        
        −
        2
        R
        T
      
    
    {\displaystyle \Delta H_{\text{sublimation}}=-U_{\text{lattice energy}}-2RT}

</p>
<h2 id="dye-sublimation-printing">Dye-sublimation printing</h2>
<p class="note">Main article: <a href="/facts/Dye-sublimation_printer/rWlGmy1l">Dye-sublimation printer</a></p>
<p>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.
</p><p>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.
</p><p>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.
</p><p>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.
</p>
<h2 id="table-of-phase-transitions-of-matter">Table of phase transitions of matter</h2>
<a href="/facts/Phase_transition/eLP2BY8R">Phase transitions</a> of matter (<ul><li>v</li><li>t</li><li>e</li></ul>)<table><tbody><tr><th>ToFrom</th><th><a href="/facts/Solid/hj5UsXno">Solid</a></th><th><a href="/facts/Liquid/t9GkLWzt">Liquid</a></th><th><a href="/facts/Gas/hVVAoodV">Gas</a></th><th><a href="/facts/Plasma_(physics)/1d3btMVU">Plasma</a></th></tr><tr><th>Solid</th><td></td><td><a href="/facts/Melting/zhhDBo5V">Melting</a></td><td>Sublimation</td><td></td></tr><tr><th>Liquid</th><td><a href="/facts/Freezing/0kNr25SF">Freezing</a></td><td></td><td><a href="/facts/Vaporization/0Uxpy1WQ">Vaporization</a></td><td></td></tr><tr><th>Gas</th><td><a href="/facts/Deposition_(phase_transition)/JweT4Eqs">Deposition</a></td><td><a href="/facts/Condensation/yvmkI08A">Condensation</a></td><td></td><td><a href="/facts/Ionization/W13Ceavd">Ionization</a></td></tr><tr><th>Plasma</th><td></td><td></td><td><a href="/facts/Plasma_recombination/M7MR8XDx">Recombination</a></td><td></td></tr></tbody></table>
<h2 id="see-also">See also</h2>
<ul><li><a href="/facts/Ablation/tTSHH09G">Ablation</a></li>
<li><a href="/facts/Enthalpy_of_sublimation/fAsEUnh5">Enthalpy of sublimation</a></li>
<li><a href="/facts/Freeze-drying/aURqwbrQ">Freeze-drying</a></li>
<li><a href="/facts/Freezer_burn/us7mqees">Freezer burn</a> – common process involving sublimation</li>
<li><a href="/facts/Phase_diagram/rcemFgW0">Phase diagram</a></li>
<li><a href="/facts/Phase_transition/eLP2BY8R">Phase transitions</a></li></ul>

<h2 id="external-links">External links</h2>
<ul><li> Media related to Sublimation at Wikimedia Commons</li></ul>

<h2 id="references">References</h2>

<ol>
<li id="fn:1"><p>Whitten, Kenneth W.; Gailey, Kenneth D.; Davis, Raymond E. (1992). General chemistry (4th ed.). Saunders College Publishing. p. 475. ISBN 0-03-072373-6. <a href="0-03-072373-6" target="_blank">0-03-072373-6</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li>
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<li id="fn:3"><p>"Sublimate". Merriam-Webster.com Dictionary. Merriam-Webster. <a href="https://www.merriam-webster.com/dictionary/Sublimate" target="_blank">https://www.merriam-webster.com/dictionary/Sublimate</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li>
<li id="fn:4"><p>"Sublimate". CollinsDictionary.com Dictionary. <a href="https://www.collinsdictionary.com/dictionary/english/sublimate" target="_blank">https://www.collinsdictionary.com/dictionary/english/sublimate</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li>
<li id="fn:5"><p>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. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4726256" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4726256</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li>
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<li id="fn:8"><p>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. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li>
<li id="fn:9"><p>"Glossary of Meteorology". Archived from the original on 2011-09-17. Retrieved 2010-07-05. <a href="https://web.archive.org/web/20110917232831/http://amsglossary.allenpress.com/glossary/search?p=1&query=ablation&submit=Search" target="_blank">https://web.archive.org/web/20110917232831/http://amsglossary.allenpress.com/glossary/search?p=1&query=ablation&submit=Search</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li>
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<li id="fn:11"><p>Staff writer(s) (2015). "what solids go through sublimation?". National Science Foundation and UCSB School-University partnership. Retrieved 13 November 2015. <a href="http://scienceline.ucsb.edu/getkey.php?key=4306" target="_blank">http://scienceline.ucsb.edu/getkey.php?key=4306</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li>
<li id="fn:12"><p>Pavia, D. (2005). Introduction to organic laboratory technique. Thomson Brooks/Cole. pp. 781–782. ISBN 978-0534408336. <a href="978-0534408336" target="_blank">978-0534408336</a> <a href="#fnref:12" class="footnote-back-ref">↩</a></p></li>
<li id="fn:13"><p>Girard, James (2011). Criminalistics: Forensic Science, Crime and Terrorism. Jones & Bartlett Learning. pp. 143–144. ISBN 978-0-7637-7731-9. <a href="978-0-7637-7731-9" target="_blank">978-0-7637-7731-9</a> <a href="#fnref:13" class="footnote-back-ref">↩</a></p></li>
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<li id="fn:21"><p>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 Solubility of Crystalline Druglike Molecules". Journal of Chemical Information and Modeling. 54 (3): 844–56. doi:10.1021/ci4005805. PMC 3965570. PMID 24564264. <a href="https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3965570" target="_blank">https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3965570</a> <a href="#fnref:21" class="footnote-back-ref">↩</a></p></li>
<li id="fn:22"><p>McDonagh, James; Palmer, David S.; Van Mourik, Tanja; Mitchell, John B. O. (17 October 2016). "Are The Sublimation Thermodynamics of organic molecules predictable?" (PDF). Journal of Chemical Information and Modeling. 56 (11): 2162–2179. doi:10.1021/acs.jcim.6b00033. hdl:10023/11874. ISSN 1549-9596. PMID 27749062. <a href="https://strathprints.strath.ac.uk/58416/1/McDonagh_etal_JCIM_2016_Are_the_sublimation_thermodynamics_of_organic.pdf" target="_blank">https://strathprints.strath.ac.uk/58416/1/McDonagh_etal_JCIM_2016_Are_the_sublimation_thermodynamics_of_organic.pdf</a> <a href="#fnref:22" class="footnote-back-ref">↩</a></p></li>
</ol>

Sublimation (phase transition) open-in-new

Sublimation (phase transition)