Gibbs-Maxwell Relation: A Derivation Explained

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Homework Help Overview

The discussion revolves around the Gibbs-Maxwell relation and its derivation, specifically focusing on the relationship between chemical potential, pressure, and volume in the context of thermodynamics. Participants are exploring the implications of the Gibbs free energy and the Gibbs-Duhem equation.

Discussion Character

  • Conceptual clarification, Mathematical reasoning, Assumption checking

Approaches and Questions Raised

  • The original poster attempts to understand the derivation of the relationship \(\partial\mu / \partial P = V/N\) and questions whether it can be derived solely from Gibbs free energy. Other participants discuss the Gibbs-Duhem equation and its role in this derivation, with some seeking clarification on how it connects to the original problem.

Discussion Status

Participants are actively engaging with the concepts, with some providing insights into the derivation process. There is an ongoing exploration of how the Gibbs-Duhem equation relates to the original poster's question, and while some clarity has been offered, no consensus has been reached on the necessity of the Gibbs-Duhem relation for deriving the desired expression.

Contextual Notes

There is a mention of the constraint of constant temperature being necessary for the derivation, and some participants express uncertainty about the completeness of their understanding regarding the derivation steps involved.

astropi
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So, this is not a homework problem. Merely for my own understanding.
This is (or should be) relatively simple I believe. Anyway, start of with Gibbs free energy and take the derivate, we arrive at:

dG = -SdT + VdP + \mu dN

take the partials we can see that with respect to dP we get V, with respect to dT we get -S, and with respect to dN we get mu. So far so good. Now, I know that if you take

\partial\mu / \partial P = V/N

but I'm just not seeing it? Is this not simply taking the derivative of G once more with respect to N? I think I'm missing something simple, so any help is appreciated. Thanks.
 
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You can get to

\left(\frac{\partial\mu }{ \partial P}\right)_T = \frac{V}{N}

from the http://en.wikipedia.org/wiki/Gibbs%E2%80%93Duhem_equation" . The constraint of constant temperature is required.
 
Last edited by a moderator:
Mapes said:
You can get to

\left(\frac{\partial\mu }{ \partial P}\right)_T = \frac{V}{N}

from the http://en.wikipedia.org/wiki/Gibbs%E2%80%93Duhem_equation" . The constraint of constant temperature is required.

Hi, could you please explain how the Gibbs-Duhem equation leads to V/N? I understand how to derive the Gibbs-Duhem equation, but fail to see how it helps us in this case. Sorry if it should be obvious and I just can't see it.
 
Last edited by a moderator:
Start with S\,dT-V\,dP+N\,d\mu=0, so that d\mu/dP=V/N-S/N(dT/dP). At constant temperature, the expression simplifies to V/N. Does this make sense?
 
Mapes said:
Start with S\,dT-V\,dP+N\,d\mu=0, so that d\mu/dP=V/N-S/N(dT/dP). At constant temperature, the expression simplifies to V/N. Does this make sense?

It certainly does. In one of my stat-mech books it "showed" the derivation, but only said use -SdT + VdP +\mu dN which is clearly using the Gibbs free energy. I wonder if they just glossed over the part that you need to use the Gibbs-Duhem relation, or can you actually get V/N using Gibbs and not the Gibbs-Duhem relation? Thanks again!
 

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