[Thermo] - Maxwells Relations? Prove the Validity of the Equations

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Discussion Overview

The discussion revolves around proving the validity of Maxwell's relations in thermodynamics, specifically focusing on equations involving partial derivatives related to entropy, enthalpy, and internal energy. Participants are exploring the mathematical relationships and attempting to derive these equations, while addressing issues with units and notation.

Discussion Character

  • Homework-related
  • Mathematical reasoning
  • Technical explanation

Main Points Raised

  • One participant presents three equations involving second derivatives of thermodynamic potentials with respect to entropy and volume, expressing uncertainty about how to prove their validity using Maxwell's relations.
  • Another participant suggests differentiating temperature with respect to entropy at constant pressure to aid in proving the second equation.
  • A participant expresses a realization about the relationships between temperature, internal energy, and enthalpy, but remains uncertain about the third equation.
  • Two participants challenge the validity of the first equation based on unit discrepancies, indicating a need for correction.
  • A later post clarifies the first equation's form, correcting the variables involved and suggesting a method to derive the relationship using the differential form of Helmholtz free energy.

Areas of Agreement / Disagreement

Participants generally agree on the validity of the second and third equations but express disagreement regarding the first equation, with some participants identifying unit inconsistencies. The discussion remains unresolved as participants continue to seek clarity on the first equation.

Contextual Notes

There are limitations regarding the assumptions made about the relationships between thermodynamic variables, and the discussion highlights the need for careful attention to units and notation in thermodynamic equations.

tesla22
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Homework Statement

We are working on some problems for class and we are given statements which I accept as valid but don't know how to prove they are valid. I believe I have to utilize the maxwell relations but the terms seem unfamiliar to me.

Homework Equations



(1)
Partial
(d^2f / ds^2)_T = T / Kv

(2)
Partial
(d^2h / ds^2)_P = T / C_p

(3)
Partial
(d^2u / ds^2)_v = T / C_v

The Attempt at a Solution



For the first equation, I know that the isothermal compressibiity K = -1/v partial(dv/dP)_T

For the second equation I also know that C_p/T = partial(ds/dT)_P = 1/T * partial(dh/dT)_P and i need to take this knowledge to combine the equations but I don't see how I would be getting the square on the ds out of this. Obviously I'm missing something.

C_v/T should be the same proof with u in place of h holding v constant.

Thanks for any help.
 
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Thank You, I think the answers were staring me in the face but in a different format and i didn't put 2 and 2 together until your response. I now have a solution where T=du/ds with v constant and T=dh/ds with p constant (correct?) and plugging these into the equations cv=T(ds/dt)_v and cp=T(dt/ds)_p to get the desired proof. I think its right.

I'm still struggling with the third one however so any assistance would be appreciated. How do you make the proper symbols appear?
 
The first relation can't be true, the units don't match up.
 
Mapes said:
The first relation can't be true, the units don't match up.

Yes that's the one I'm struggling with sorry, the first one. The 2nd and 3rd I believe I have proven as said in the previous post.

I completely screwed up the first one, the actual problem is as follows:

(d^2f / dv^2)_T = 1 / Kv

This is the one I am struggling with at the moment. Sorry I was trying too hard to convey the format of the problem that i got the variables wrong somehow.
 
OK, that makes a lot more sense. Try writing out the differential form of the Helmholtz free energy dF and taking the derivative of that twice with respect to V at constant T. The first derivative equals a well-known parameter.
 

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