Maxwell relations with heat capacity

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Discussion Overview

The discussion revolves around using Maxwell relations and the Euler chain relation to express the partial derivative of entropy with respect to temperature at constant pressure, in terms of heat capacity, expansion coefficient, and isothermal compressibility. The context is primarily homework-related, focusing on theoretical concepts in thermodynamics.

Discussion Character

  • Homework-related
  • Technical explanation
  • Mathematical reasoning

Main Points Raised

  • One participant attempts to express the change in entropy with respect to pressure and volume, suggesting that they are unsure how the expansion coefficient and thermal compressibility relate to the problem.
  • Another participant proposes differentiating entropy as a function of temperature and volume, leading to a method for comparing derivatives under different conditions.
  • A later reply indicates that the original poster successfully solved the problem using the suggested method, expressing gratitude for the assistance.
  • Another participant elaborates on their successful derivation of a relation between the partial derivative of entropy with respect to temperature at constant pressure and other thermodynamic quantities, referencing the Maxwell relations and Euler's chain rule.
  • This participant also discusses the connection between specific heat and entropy, providing a detailed mathematical formulation.

Areas of Agreement / Disagreement

There appears to be no consensus on the initial approach to the problem, as participants express different methods and reasoning. However, one participant confirms they solved the problem, while another elaborates on their derivation, indicating multiple perspectives on the topic.

Contextual Notes

Some participants express uncertainty about the relevance of certain thermodynamic concepts, such as the expansion coefficient and thermal compressibility, which may indicate limitations in their understanding of the broader implications of the problem.

fraggedmemory
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Homework Statement


Use the Maxwell relations and the Euler chain relation to express (ds/dt)p in terms of the heat capacity Cv = (du/dt)v. The expansion coefficient alpha = 1/v (dv/dt)p, and the isothermal compressibility Kt = -1/v (dV/dp)T. Hint. Assume that S= S(p,V)

Homework Equations


dQ(rev) = Tds
The maxwell relations
Euler Chain relation

The Attempt at a Solution



Alright, my attempts at this involved trying find common partial derivatives from the information already given. I couldn't find anything. But then looking at the hint I thought that there might be a way to express the change in entropy with respect to pressure and volume. I get this ds = (dU + PdV)/T assuming constant pressure. I am really not sure what I am suppose to do. I especially don't get what the expansion coefficient and thermal compressibility has to do with anything, but that might be because I can't see the big picture with this problem.

A step by step explanation would be greatly appreciated.
 
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I'd rather consider S to be a function of T and V. Then I could differentiate S as

dS=\left(\frac{dS}{dT}\right)_V\,dT+\left(\frac{dS}{dV}\right)_T\,dV

Then I'd differentiate with respect to T at constant p:

\left(\frac{dS}{dT}\right)_p=\left(\frac{dS}{dT}\right)_V+\left(\frac{dS}{dV}\right)_T\left(\frac{dV}{dT}\right)_p

You should be able to figure out the rest. This is a useful trick for when you want to compare derivatives taken under different conditions.
 
I am very thankful for your reply. However, I managed to solve the problem several hours after my post. Your method though is something that I didn't think of, so I do appreciate it.
 
fraggedmemory said:

Homework Statement


I'm not sure about the sentence "all variables and given/known data".

fraggedmemory said:
Use the Maxwell relations and the Euler chain relation to express (ds/dt)p in terms of the heat capacity Cv = (du/dt)v. The expansion coefficient alpha = 1/v (dv/dt)p, and the isothermal compressibility Kt = -1/v (dV/dp)T. Hint. Assume that S= S(p,V)

Homework Equations


dQ(rev) = Tds
The maxwell relations
Euler Chain relation

In fact I succeed in order to obtain a relation between:
\left(\frac{\partial s}{\partial T}\right)_p
and c_v, \alpha, k_T, T, v just following the mapes's hint to consider S as a function of T and V. Where minuscle letter for extensive quantity means: "this quantity is molar", and all transformation are intended to involve a costant number of molecules.

In fact:

\left(\frac{\partial s}{\partial T}\right)_p = \left(\frac{\partial s}{\partial T}\right)_v + \left(\frac{\partial s}{\partial v}\right)_T \left(\frac{\partial v}{\partial T}\right)_T

The Maxwell's relation following from d(-p dv - sdT)=0 tell us:
\left(\frac{\partial s}{\partial v}\right)_p= \left(\frac{\partial p}{\partial T}\right)_v
Now the Euler's chain rule give us the link between the first derivative in second addend, the compressibility and the thermal expansion coefficient. In fact:

\left(\frac{\partial p}{\partial T}\right)_v \left(\frac{\partial T}{\partial v}\right)_p\left(\frac{\partial v}{\partial p}\right)_T = -1

and:

\left(\frac{\partial T}{\partial v}\right)_p = 1/\left(\frac{\partial v}{\partial T}\right)_p

so that:

\left(\frac{\partial p}{\partial T}\right)_v = \frac{\alpha}{k_T}

In order to complete the derivation we need to use the given alternative definition of specific heat:

c_v = T \left(\frac{\partial s}{\partial T}\right)_v = \left(\frac{\partial u}{\partial T}\right)_v

Which follow from:

T dS = dU + p dV

So obtaining:

\left(\frac{\partial s}{\partial T}\right)_p = \frac{c_v}{T} + \frac{\alpha^2 v}{k_T}

is this what was required?


fraggedmemory said:

The Attempt at a Solution



Alright, my attempts at this involved trying find common partial derivatives from the information already given. I couldn't find anything. But then looking at the hint I thought that there might be a way to express the change in entropy with respect to pressure and volume. I get this ds = (dU + PdV)/T assuming constant pressure. I am really not sure what I am suppose to do. I especially don't get what the expansion coefficient and thermal compressibility has to do with anything, but that might be because I can't see the big picture with this problem.

A step by step explanation would be greatly appreciated.
 

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