A new point of view on freezing point.

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    Freezing Point
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Discussion Overview

The discussion revolves around the concept of the freezing point of water, particularly in relation to nucleation processes and the influence of impurities. Participants explore the definitions and conditions under which freezing occurs, including the roles of homogeneous and heterogeneous nucleation, as well as the relationship between freezing and melting points.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant suggests that pure water will not freeze above -40°C without impurities, proposing a definition of freezing point based on the inability of impurities to further raise the freezing temperature.
  • Another participant states that the freezing point is defined as the temperature where the Gibbs free energy of the liquid and solid phases are equal, indicating a connection to kinetic theory.
  • A follow-up question is raised regarding why the melting point coincides with the "maximum" freezing point.
  • Another participant explains that melting and freezing are phase transitions and that supercooling occurs due to energy barriers in nucleation, contrasting this with the relatively constant melting point due to easier nucleation processes.
  • This participant concludes that the freezing and melting points are the same under conditions of sufficient nucleation sites, emphasizing the role of Gibbs free energy in defining these points.

Areas of Agreement / Disagreement

Participants express differing views on the definition of the freezing point and the relationship between freezing and melting points. While some agree on the Gibbs free energy perspective, others challenge or seek clarification on the implications of nucleation and impurities.

Contextual Notes

The discussion includes assumptions about the conditions under which freezing occurs, such as the presence of impurities and nucleation sites. There is also a dependence on the definitions of phase transitions and Gibbs free energy, which may not be universally accepted or understood in the same way by all participants.

kelvin490
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It is very hard to have homogeneous nucleation in common situation. Pure water with no nuclei at all will not freeze above -40oC. The presence of impurity particles allow the so-called heterogeneous nucleation to occur so that we can see water freeze at 0oC. It may be reasonable to guess at what temperature between -40oC and 0oC will water freeze depends on the amount of impurities in water. But we never see water freeze above 0oC at atmospheric pressure. Can the freezing point be defined in the following way? Freezing point is the temperature at which further increase of impurities cannot increase the temperature for the substance to freeze.
 
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This point (which also corresponds to the melting point) is already defined as the temperature at which the Gibbs free energy of each phase, liquid and solid, is equal. Your definition is a byproduct of this and kinetic theory.
 
Mapes said:
This point (which also corresponds to the melting point) is already defined as the temperature at which the Gibbs free energy of each phase, liquid and solid, is equal. Your definition is a byproduct of this and kinetic theory.

Thanks.But why the melting point coincides with the "maximum" freezing point?
 
Melting and freezing are, of course, two sides of the same coin: a phase transition. Liquids can be supercooled because of the energy barrier associated with nucleating the first bit of solid, as you know; sometimes cooling is necessary to provide the driving force for nucleation.

In contrast, the melting point is relatively constant because there's little or no activation energy involved with melting; nucleation occurs with ease. (An equivalent way of saying this is that for all or nearly all materials, the liquid phase wets the solid phase, so it's not necessary to nucleate a tiny droplet.)

So the melting point and the freezing point are the same, given that there are plenty of nucleation sites for the freezing case, and both values are set by the equivalence of energies for the two phases. Since we're assuming constant temperature and pressure, the energy is specifically the Gibbs free energy.
 

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