I deriving this Maxwell relation

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Homework Help Overview

The discussion revolves around deriving a specific Maxwell relation using enthalpy and its associated equations. The original poster attempts to manipulate the differential form of enthalpy and related thermodynamic identities to arrive at the desired relation.

Discussion Character

  • Exploratory, Conceptual clarification, Mathematical reasoning

Approaches and Questions Raised

  • Participants discuss the manipulation of the differential form of enthalpy and the application of the chain rule in thermodynamic equations. There is a focus on understanding why certain terms appear in the expressions and how to correctly apply the definitions of thermodynamic potentials.

Discussion Status

Some participants provide guidance on using the appropriate thermodynamic potential for the variables in question, while others express uncertainty about the original poster's approach and the specific requirements of the problem. Multiple interpretations of how to proceed are being explored.

Contextual Notes

The original poster is constrained by the requirement to use enthalpy in their derivation, despite suggestions to consider other thermodynamic potentials. There is also a noted confusion regarding the relationship between the variables and the equations involved.

Yekonaip
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Homework Statement


By considering small changes in enthalpy,
and using the central equation, derive the Maxwell relation

\left (\frac{\partial S}{\partial V} \right )_{T}= \left (\frac{\partial p}{\partial T} \right )_{V}


Homework Equations


H=U+pV
dU=TdS-pdV


The Attempt at a Solution


So the way I attempted this was to get an expression for dH,
dH=dU+pdV+Vdp
dH=TdS+Vdp

Honestly I don't know the reason that pV splits up into pdV and Vdp but just know that it does that so I'd appreciate it if someone could input on that?

Then I used the fact that,
dH=\left ( \frac{\partial H}{\partial S} \right )_{p}dS+\left ( \frac{\partial H}{\partial p} \right )_{S}dp
and that
\frac{\partial^{2} H}{\partial S\partial p}=\frac{\partial^{2} H}{\partial p\partial S}

This basically yields me with the relation,

\left (\frac{\partial T}{\partial p} \right )_{S}= \left (\frac{\partial V}{\partial S} \right )_{p}


So I know this is a correct relation, however it isn't the relation that the question requires. I'm not really sure where to go from here, is there a way to rearrange the equation I ended up with? Or was this a Red Herring and I should have gone about it a different way?

Thank you for your time. I really appreciate it!
 
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Since, as independent variables in the partial derivatives you have T and [/itex]V[/itex], you should use the corresponding thermodynamic potential, for which these variables are "natural". This is the free energy rather than the enthalpy, i.e.,
F(T,V)=U-TS.
Write down the first Law, i.e., evaluate \mathrm{d} F=\ldots and use the commutativity of the 2nd derivatives as in your example with the enthalpy.
 
Sorry I may have been a little vague. I understand what you're saying but the question specifically asks to consider Enthalpy and use the equation,
H=U+pV
 
Yekonaip said:
Sorry I may have been a little vague. I understand what you're saying but the question specifically asks to consider Enthalpy and use the equation,
H=U+pV
From the central equation and the definition of F, it follows that dF = -SdT-PdV. This should give you the required maxwell relation. The equation for the enthalpy is consistent with all this too. So, who knows what the question means.

Chet
 
Yekonaip said:
Honestly I don't know the reason that pV splits up into pdV and Vdp but just know that it does that so I'd appreciate it if someone could input on that?

That is just the chain rule from simple calculus. d(pV) = pdV+VdpFor the rest of it, you did indeed prove one of the Maxwell relations, although I am not sure, how to do it for the one you had to find, using the enthalpy. An idea would be to try using:

U = -T^2 (∂(F/T)/∂T)V

in the equation for the enthalpy, or some other way of expressing U, that allows you to introduce F
 

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