Can the Second Law of Thermodynamics Explain Freezing Water at -5°C?

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Discussion Overview

The discussion revolves around the application of the second law of thermodynamics to predict the spontaneous freezing of liquid water at -5°C under constant pressure. Participants explore theoretical aspects related to phase transitions, thermodynamic potentials, and entropy calculations.

Discussion Character

  • Homework-related
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant presents a homework problem regarding the prediction of freezing water using the second law of thermodynamics, expressing difficulty in deriving the result.
  • Another participant prompts the original poster to consider which thermodynamic potential remains constant during phase changes at constant temperature and pressure, suggesting this could aid in finding the entropy of freezing.
  • A participant notes that the enthalpy of freezing is the opposite of the enthalpy of fusion, seeking clarification on this relationship.
  • Further clarification is provided regarding the use of Gibbs free energy in determining phase transitions and the relationship between enthalpy and entropy during these processes.

Areas of Agreement / Disagreement

Participants express varying levels of understanding and seek clarification on specific thermodynamic concepts. There is no consensus on the original problem's solution, and multiple viewpoints regarding the relationships between enthalpy, entropy, and Gibbs free energy are presented.

Contextual Notes

Participants discuss the assumptions related to the constancy of Cp and the interpretation of thermodynamic equations. The discussion does not resolve the mathematical steps required to predict the freezing of water.

Aeon
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Homework Statement


Show that the second law of thermodynamics predicts the spontaneous freezing of liquid water at -5[tex]^{o}[/tex]C under 1 bar of constant pressure. Assume that Cp is temperature independent.

Standard water fusion enthalpy = 6.008 kJ/mol @ 273.15 K

[tex]\geq[/tex] has to be interpreted as greater than, not greater or equal, in this example.

Homework Equations



A: [tex]dS[/tex] [tex]\geq[/tex] [tex]\frac{\partial q}{T}[/tex]

B: [tex]\Delta[/tex][tex]S_{transition}[/tex] = [tex]\frac{\Delta H_{transition}}{T_{transition}}[/tex]

C: [tex]\Delta S = \int \frac{Cp}{T} dT[/tex]

D: [tex]\Delta H = q[/tex] in an isobaric process

The Attempt at a Solution



After having wasted an hour or so on this presumably easy problem, I cannot get the second law to predict the freezing.

[tex]Cp\ ln(T) \geq \frac{\Delta H_{transition}}{T_{transition}}[/tex] ?

Some advice would be appreciated. I know the proof is simple. I'm having some brain fog atm though.

Thanks!
 
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Hi Aeon, welcome to PF. What thermodynamic potential stays constant for phase changes at constant temperature and pressure? And using this, can you find the entropy of freezing from the enthalpy of freezing?
 
I have been reading on the forums for some time. I never had to ask a question yet though.
Thanks!

On a phase transition diagram, Gibbs free energy of one phase is equal to G of another phase when you follow the phase transition curves.

Is the enthalpy of freezing opposite of the enthalpy of fusion?
 
Aeon said:
On a phase transition diagram, Gibbs free energy of one phase is equal to G of another phase when you follow the phase transition curves.

Exactly. So by using the definition of G, the entropy of fusion can be determined. Now you can calculate the difference in G between the phases - and a spontaneous process will tend to minimize G.

Aeon said:
Is the enthalpy of freezing opposite of the enthalpy of fusion?

Yes, and that was a typo; I meant fusion! Enthalpy and entropy of freezing would have the opposite signs.
 

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