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Related Concept Videos

Phase Transitions: Melting and Freezing02:39

Phase Transitions: Melting and Freezing

Heating a crystalline solid increases the average energy of its atoms, molecules, or ions, and the solid gets hotter. At some point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their fixed positions, and the solid begins the process of transitioning to the liquid state or melting. At this point, the temperature of the solid stops rising, despite the continual input of heat, and it remains constant until all of the solid is...
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Solid–Solid Solutions

The temperature-composition phase diagram of two solids, A and B, which are immiscible in the solid phase but form miscible liquids, shows that when the temperature is low, these two exist as separate, pure solids (A and B). As the temperature increases, they transition into a single-phase liquid solution where A and B coexist. Moving from point a1 to a2 in the phase diagram, the composition changes such that solid B begins to separate from the solution, enriching the remaining liquid with A.
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States of Water

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The physical form of a substance changes on changing its temperature. For example, raising the temperature of a liquid causes the liquid to vaporize (convert into vapor). The process is called vaporization—a surface phenomenon. Vaporization occurs when the thermal motion of the molecules overcome the intermolecular forces, and the molecules (at the surface) escape into the gaseous state. When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase molecules...
Phase Transitions: Sublimation and Deposition02:33

Phase Transitions: Sublimation and Deposition

Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming any liquid. Snow and ice sublimate at temperatures below the melting point of water, a slow process that may be accelerated by winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes...
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Sublimation is the direct transformation of a solid to a gaseous state. For instance, at standard pressure and room temperature, solid carbon dioxide sublimes to gaseous carbon dioxide. The phase diagram depicts the conditions required for sublimation. This process occurs at the solid-gas phase boundary and is not observed above the triple point of the substance. The reverse of sublimation is called deposition, where a gaseous substance condenses directly into a solid. Sublimation and...

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Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures
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Do supercooled liquids freeze by spinodal decomposition?

Lawrence S Bartell1, David T Wu

  • 1Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, USA.

The Journal of Chemical Physics
|November 13, 2007
PubMed
Summary

Spinodals are unlikely to occur during the freezing of one-component liquids at moderate supercooling. Ramified solidlike fluctuations in supercooled liquids do not signal spinodal decomposition but influence liquid properties.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Thermodynamics

Background:

  • Spinodal decomposition is a theoretical phase transition relevant to liquid-solid phase changes.
  • Previous studies suggested spinodals might occur in freezing at moderate supercooling (T/T_melt=0.6).
  • Ramified solidlike fluctuations are observed in simulations of supercooled liquids.

Purpose of the Study:

  • To investigate the likelihood of spinodal occurrence in one-component liquid freezing.
  • To determine if ramified solidlike fluctuations are precursors to spinodal decomposition.

Main Methods:

  • Analysis of heuristic evidence from molecular dynamics simulations of selenium hexafluoride.
  • Theoretical arguments based on nucleation kinetics.

Main Results:

  • Evidence suggests spinodals do not occur even at significant supercooling (deeper than T/T_melt=0.6).
  • Ramified fluctuations do not act as true freezing nuclei but impact liquid properties.
  • Supercooled liquids exhibiting these fluctuations do not show spinodal behavior.

Conclusions:

  • Spinodal decomposition is unlikely in one-component liquid freezing at moderate supercooling.
  • Ramified solidlike fluctuations influence supercooled liquid properties but are not harbingers of spinodal decomposition.