Is \( c_P \) Pressure Independent if \( \alpha = \frac{1}{T} \)?

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SUMMARY

The discussion revolves around the proof that the specific heat at constant pressure, \( c_P \), is independent of pressure when the thermal expansion coefficient \( \alpha \) is defined as \( \alpha = \frac{1}{T} \). The key equation derived is \( \left ( \frac{\partial c_P }{\partial P} \right ) _T=0 \), which is established through the use of Maxwell relations and the properties of molar volume \( v \). The proof is completed by demonstrating that the partial derivative \( \frac{\partial }{\partial T} \left [ \left ( \frac{v(T,P)}{T} \right ) \right ] _P \) equals zero, confirming the pressure independence of \( c_P \).

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  • Understanding of thermodynamic concepts, particularly specific heat and thermal expansion.
  • Familiarity with Maxwell relations in thermodynamics.
  • Knowledge of partial derivatives and their application in thermodynamic equations.
  • Basic understanding of the relationship between molar volume, temperature, and pressure.
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  • Study the derivation and implications of Maxwell relations in thermodynamics.
  • Learn about the properties and applications of specific heat at constant pressure, \( c_P \).
  • Explore the concept of thermal expansion coefficients and their significance in thermodynamic systems.
  • Investigate the relationship between enthalpy changes and specific heat in various thermodynamic processes.
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Homework Statement


I'm stuck on a relatively simple exercise which can be found in Callen's book: Show that if ##\alpha = \frac{1}{T}## then ##c_P## is pressure independent.

Homework Equations


What they ask me to show is: If ##\frac{1}{v} \left ( \frac{\partial v }{\partial T} \right ) _P=\frac{1}{T} \Rightarrow \left ( \frac{\partial c_P }{\partial P} \right ) _T=0##.
Where the lower case v is the molar volume and for what will follow the lower case letters are molar quantities.

The Attempt at a Solution


##c_P=T \left ( \frac{\partial s }{\partial T} \right ) _P##. Since both alpha and the specific heat at constant pressure are given in terms of T and P, I will think about v and ##c_p## as functions of T and P.
So ##\left ( \frac{\partial c_P }{\partial P} \right ) _T=T \frac{\partial }{\partial P} \left [\left ( \frac{\partial s }{\partial T} \right ) _P \right ] _T=T \frac{\partial }{\partial T} \left [ \left ( \frac{\partial s }{\partial P} \right ) _T \right ] _P##. Now I use a Maxwell relation, namely that ##\left ( \frac{\partial s }{\partial P} \right ) _T=- \left ( \frac{\partial v }{\partial T} \right ) _P##.
So I get that ##\left ( \frac{\partial c_P }{\partial P} \right ) _T=-T\frac{\partial }{\partial T} \left [ \left ( \frac{\partial v }{\partial T} \right ) _P \right ] _P=-T \frac{\partial }{\partial T} \left [ \left ( \frac{v(T,P)}{T} \right ) \right ] _P##.
So if I can show that ##\frac{\partial }{\partial T} \left [ \left ( \frac{v(T,P)}{T} \right ) \right ] _P=0## then the job would be done. However I'm stuck here, I haven't been able to find a way to show that... Am I going the wrong way? Or simply missing a simple thing?

Edit: Nevermind, problem solved. lol, I was missing a simple thing. I had to perform the partial derivative and I indeed reach that it's worth 0 and hence the proof is completed.
 
Last edited:
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The equation for the enthalpy change expressed in terms of dT and dP is given by
dH=C_pdT+V(1-\alpha T)dP

The form of this equation is
dH=\frac{\partial H}{\partial T}dT+\frac{\partial H}{\partial P}dP

Therefore,

\frac{\partial H}{\partial T}=C_p
\frac{\partial H}{\partial P}=V(1-\alpha T)
So,\frac{\partial^2 H}{\partial T \partial P}=\frac{\partial C_p}{\partial P}=\frac{\partial (V(1-\alpha T))}{\partial T}
 

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