How Can Maxwell's Relations Be Applied to Thermodynamic Equations?

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SUMMARY

This discussion focuses on the application of Maxwell's Relations to derive specific thermodynamic equations from "Introductory Statistical Mechanics" by Bowley and Sanchez. The key equations demonstrated include $$T dS = C_v dT + T (\frac{\partial P}{\partial T})_V dV$$ and $$TdS = C_p dT - T( \frac{\partial V}{\partial T})_P dP$$. The user successfully proved the first equation by manipulating the internal energy expression $$dU = TdS - PdV$$ and applying Maxwell's Relations to relate entropy, volume, and pressure derivatives. The discussion concludes with a confirmation of the derived equations and the relationships between the variables involved.

PREREQUISITES
  • Understanding of Maxwell's Relations in thermodynamics
  • Familiarity with the concepts of internal energy and entropy
  • Knowledge of partial derivatives in multivariable calculus
  • Basic principles of thermodynamic equations and state functions
NEXT STEPS
  • Study the derivation and applications of the four common Maxwell's Relations
  • Explore the relationship between internal energy and entropy in thermodynamics
  • Learn about the implications of the Clausius-Clapeyron equation on phase transitions
  • Investigate the role of specific heat capacities, C_v and C_p, in thermodynamic processes
USEFUL FOR

This discussion is beneficial for students and professionals in physics and engineering, particularly those focusing on thermodynamics, statistical mechanics, and related fields. It is especially useful for anyone looking to deepen their understanding of thermodynamic equations and their derivations using Maxwell's Relations.

Dewgale
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Homework Statement


This is question 2.18 from Bowley and Sanchez, "Introductory Statistical Mechanics" .

Show with the help of Maxwell's Relations that
$$T dS = C_v dT + T (\frac{\partial P}{\partial T})_V dV$$
and
$$TdS = C_p dT - T( \frac{\partial V}{\partial T})_P dP.$$

Then, prove that
$$(\frac{\partial U}{\partial V})_T = T (\frac{\partial P}{\partial T})_V - P$$

Homework Equations


The four common Maxwell's Relations. They can be found here: https://en.wikipedia.org/wiki/Maxwell_relations.

The Attempt at a Solution


The issue for me is the first part. I have managed to prove that the second is true.
My attempt thus far:
Using the fact that ##dU = TdS - PdV##, we can rewrite the equation as $$TdS = dU + PdV.$$
We can then multiply and divide dU by dT to get $$TdS = (\frac{\partial U}{\partial T})_V dT + PdV.$$ However, ##\frac{\partial U}{\partial T}_V = C_v##, and so we have $$TdS = C_v dT + PdV.$$
This then leaves me with the issue of how to convert the term PdV ##\to T (\frac{\partial P}{\partial T})_V dV##. I was considering using the relation ##\frac{\partial P}{\partial T} = \frac{\partial S}{\partial V}##, but I'm not sure how to get that to work. I'll keep working at it, but any help is appreciated!
 
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Dewgale said:
We can then multiply and divide dU by dT to get $$TdS = (\frac{\partial U}{\partial T})_V dT + PdV.$$
Well, this is certainly not true! Recall that given a multivariable function ##f(x,y)##, we have
df(x,y) = \left(\frac{\partial f}{\partial x}\right)_{y} dx + \left(\frac{\partial f}{\partial y}\right)_{x} dy
 
Fightfish said:
Well, this is certainly not true! Recall that given a multivariable function ##f(x,y)##, we have
df(x,y) = \left(\frac{\partial f}{\partial x}\right)_{y} dx + \left(\frac{\partial f}{\partial y}\right)_{x} dy

I solved it!
Consider the fact that $$ dU = (\frac{\partial U}{\partial S}) dS + (\frac{\partial U}P\partial V}) dV.$$ Then since ##dU = TdS - PdV##, we can see that ##\frac{\partial U}{\partial S} = T##, or ##\frac{\partial S}{\partial U} = \frac{1}{T}##. Now, consider a function ##S=S(U,V)##.
$$dS = (\frac{\partial S}{\partial U}) dU_V + (\frac{\partial S}{\partial V}) dV$$
Using one of the Maxwell relations, we know that ##\frac{\partial S}{\partial V} = \frac{\partial P}{\partial T}##. We also know that ##dU_V = C_V dT##. Therefore, we have
$$dS = \frac{1}{T} C_V dT + (\frac{\partial P}{\partial T}) dV$$
and multiplying through by T gives
$$TdS = C_V dT + T(\frac{\partial P}{\partial T}) dV$$

A similar process using S(U,P) will give the other. Thank you!
 

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