How Does Gibbs Free Energy Relate to Phase Changes?

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Discussion Overview

The discussion revolves around the relationship between Gibbs free energy and phase changes, specifically during transitions such as melting and freezing. Participants explore the implications of Gibbs free energy, enthalpy, and entropy during these processes, addressing both theoretical and conceptual aspects.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant states that during phase changes, the temperature remains constant while energy is used for the phase transition, questioning how this relates to Gibbs free energy.
  • Another participant asserts that Gibbs free energy is not constant during phase changes, referencing the equation ΔG = ΔH - TΔS and noting that entropy also changes.
  • A different participant explains that during a reversible phase change, Gibbs free energy does not change, providing a mathematical expression to support this claim.
  • Some participants discuss the conditions under which ΔG equals zero during first-order and second-order phase transitions, indicating that ΔG = 0 for both types of transitions.
  • There is mention of the spontaneity of processes as indicated by the sign of ΔG, with ΔG < 0 suggesting a spontaneous process.

Areas of Agreement / Disagreement

Participants express differing views on the constancy of Gibbs free energy during phase changes, with some asserting it remains constant while others argue it does not. The discussion includes competing interpretations of the implications of ΔG in relation to phase transitions.

Contextual Notes

Participants reference specific conditions and mathematical expressions related to Gibbs free energy, enthalpy, and entropy, but do not resolve the underlying assumptions or definitions that may affect their claims.

Who May Find This Useful

This discussion may be of interest to students and professionals in physics and chemistry, particularly those studying thermodynamics and phase transitions.

AbsoluteZer0
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Hi,

As I understand, during the process of phase change from a liquid to solid (or any phase change for that matter,) the temperature of the substance remains constant as the energy being applied to the substance is used in changing phase.

How does this relate to Gibbs free energy? I read that \Delta G during melting is zero. Enthalpy and entropy, however, increase. Does this have any relation to the uniformity of the temperature of the substance during the change of phase?

I'm led to believe that \Delta G &gt; 0 when phase change isn't taking place because of the changing temperature. (For example, when the temperature of water is raised from 30°C to 50°C.) How accurate is this assumption?

Thanks,
 
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AbsoluteZer0 said:
Hi,

As I understand, during the process of phase change from a liquid to solid (or any phase change for that matter,) the temperature of the substance remains constant as the energy being applied to the substance is used in changing phase.

How does this relate to Gibbs free energy? I read that \Delta G during melting is zero. Enthalpy and entropy, however, increase. Does this have any relation to the uniformity of the temperature of the substance during the change of phase?

I'm led to believe that \Delta G &gt; 0 when phase change isn't taking place because of the changing temperature. (For example, when the temperature of water is raised from 30°C to 50°C.) How accurate is this assumption?

Thanks,

Gibbs free energy is not constant during phase change! Who told you this ?

Clearly ΔG=ΔH-TΔS

Entropy factor also changes though...
 
sankalpmittal said:
Gibbs free energy is not constant during phase change! Who told you this ?

During a reversible phase change, e.g. slow melting of ice, G does not change.
##dG=VdP-SdT+\mu_l dN_l +\mu_s dN_S.##
P and T are constant and ##dN_l=-dN_s##. ##\mu_l=\mu_s## is the condition for equilibrium of the two phases, so dG=0.
ΔH is positive for melting (endothemal process), ΔS, too, as the entropy of the liquid is higher than that of the solid.
 
AbsoluteZer0 said:
<snip>

How does this relate to Gibbs free energy? I read that \Delta G during melting is zero. Enthalpy and entropy, however, increase. Does this have any relation to the uniformity of the temperature of the substance during the change of phase?
<snip>

The sign of ΔG tells you if the process is spontaneous (ΔG < 0) or not. As for phase transitions, there are at least 2 kinds: a 'first order phase transition' is accompanied by a discontinuous change in the derivative of the free energy and are associated with freezing/melting/etc. ΔG = 0 for a first order phase transition (ΔH = TΔS).

Second-order phase transitions are associated with discontinuous changes to the second derivative of the free energy. IIRC, ΔG = 0 for a second order phase transition as well.

http://www.helsinki.fi/~serimaa/soft-luento/soft-2-phase.html
 
Andy Resnick said:
The sign of ΔG tells you if the process is spontaneous (ΔG < 0) or not. As for phase transitions, there are at least 2 kinds: a 'first order phase transition' is accompanied by a discontinuous change in the derivative of the free energy and are associated with freezing/melting/etc. ΔG = 0 for a first order phase transition (ΔH = TΔS).

Second-order phase transitions are associated with discontinuous changes to the second derivative of the free energy. IIRC, ΔG = 0 for a second order phase transition as well.

http://www.helsinki.fi/~serimaa/soft-luento/soft-2-phase.html

Thanks
 

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