Maxwell relations Thermodynamics

AI Thread Summary
The discussion centers on demonstrating the Maxwell relation in thermodynamics, specifically showing that the partial derivative of temperature with respect to volume at constant entropy and particle number equals the negative of the partial derivative of pressure with respect to entropy at constant volume and particle number. Participants explore the relationship between internal energy, temperature, and pressure, emphasizing the importance of continuity in these functions. One participant expresses concern about justifying the assumption of continuity for internal energy, while others suggest that experimental evidence could serve as a sufficient basis for this assumption. The conversation highlights the need for a solid theoretical foundation in thermodynamics, particularly regarding the validity of Schwartz's relation.
thonwer
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Homework Statement


Show that: (\frac{∂T} {∂V})_S,_n=-(\frac {∂P} {∂S})_V,_n

Homework Equations


dU=TdS-PdV+μdn

The Attempt at a Solution


\frac {∂} {∂S} (\frac{∂U} {∂V})_S,_n=-(\frac {∂P} {∂S})_V,_n

\frac {∂} {∂V} (\frac{∂U} {∂S})_V,_n=(\frac{∂T} {∂V})_S,_n

I tried to isolate T and P, but I get stuck:
TdS=dU+PdV

-PdV=dU-TdS

How can I demonstrate that they are equal?
 
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It looks like you already had it in your first two equations of Attempt at a Solution. You are aware that 2nd partial derivatives with respect to two variables are interchangeable (commutative), correct?

Chet
 
Yes I see that, but I ment to obtain −(\frac {∂P} {∂S})_V,_n from (\frac {∂T} {∂V})_S,_n or viceversa, demonstrating Schwartz relation in some way.
 
thonwer said:
Yes I see that, but I ment to obtain −(\frac {∂P} {∂S})_V,_n from (\frac {∂T} {∂V})_S,_n or viceversa.
Isn't that what your first two equations under Attempt demonstrate?

Chet
 
If I say they are equal, I am assuming that Schwartz relation is valid in this case, or that U is a continuos function. I want to demonstrate why Schwartz relation is valid.
 
thonwer said:
If I say they are equal, I am assuming that Schwartz relation is valid in this case, or that U is a continuos function. I want to demonstrate why Schwartz relation is valid.
What's wrong with assuming that U is a continuous function for a single-component single-phase material?

Chet
 
Nothing, but in an exam I would have to reason why I assume that U is continuous, so if I could go from -\left( {\frac{\partial P} {\partial S}}\right)_{V,n} to \left( {\frac{\partial T} {\partial V}}\right)_{S,n} by using derivatives and their properties, the problem would be solved I think.
 
Why would you think it's not continuous?

Chet
 
  • #10
I think it's continuous, I know from theory, but it's not a given in the problem, so if i use it, I have to say why. As I don't know how to justify that U is continuous, I think that, if I can demonstrate that Schwartz relation is valid, then, I can avoid justifying its continuity.
 
  • #11
thonwer said:
I think it's continuous, I know from theory, but it's not a given in the problem, so if i use it, I have to say why. As I don't know how to justify that U is continuous, I think that, if I can demonstrate that Schwartz relation is valid, then, I can avoid justifying its continuity.
I don't know what to say. Are you a mathematician or a physicist? If the latter, why would you think that internal energy is not a continuous function of entropy and volume?

Chet
 
  • #12
I'm studying Physics, and I know it is a continuous function of entropy and volume, but one thing is knowing and another is proving. I need to prove this knowledge.
 
  • #13
thonwer said:
I'm studying Physics, and I know it is a continuous function of entropy and volume, but one thing is knowing and another is proving. I need to prove this knowledge.
It's observed experimentally. Does that count as proof? Otherwise you need to start looking into statistical thermo.

Chet
 
  • #14
Mmm statiscal thermo is a subject I will study next year, so if there's no other proof I suppose experimental proof is what I need.Thank you.
 
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