Gibbs-Maxwell Relation: A Derivation Explained

In summary, the conversation discusses the derivation of the equation \left(\frac{\partial\mu }{ \partial P}\right)_T = \frac{V}{N} from the Gibbs-Duhem equation. The constraint of constant temperature is required for this derivation. The conversation also mentions confusion regarding the use of the Gibbs-Duhem relation and the Gibbs free energy in obtaining this equation.
  • #1
astropi
47
0
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:

[tex] dG = -SdT + VdP + \mu dN[/tex]

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

[tex] \partial\mu / \partial P = V/N [/tex]

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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  • #2
You can get to

[tex] \left(\frac{\partial\mu }{ \partial P}\right)_T = \frac{V}{N} [/tex]

from the http://en.wikipedia.org/wiki/Gibbs%E2%80%93Duhem_equation" . The constraint of constant temperature is required.
 
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  • #3
Mapes said:
You can get to

[tex] \left(\frac{\partial\mu }{ \partial P}\right)_T = \frac{V}{N} [/tex]

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.
 
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  • #4
Start with [itex]S\,dT-V\,dP+N\,d\mu=0[/itex], so that [itex]d\mu/dP=V/N-S/N(dT/dP)[/itex]. At constant temperature, the expression simplifies to [itex]V/N[/itex]. Does this make sense?
 
  • #5
Mapes said:
Start with [itex]S\,dT-V\,dP+N\,d\mu=0[/itex], so that [itex]d\mu/dP=V/N-S/N(dT/dP)[/itex]. At constant temperature, the expression simplifies to [itex]V/N[/itex]. Does this make sense?

It certainly does. In one of my stat-mech books it "showed" the derivation, but only said use [tex]-SdT + VdP +\mu dN[/tex] 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!
 

1. What is the Gibbs-Maxwell Relation?

The Gibbs-Maxwell Relation is a mathematical equation that relates the thermodynamic properties of a system, such as temperature, pressure, and volume, to each other. It is derived from the laws of thermodynamics and is used to analyze and understand the behavior of complex systems.

2. Who discovered the Gibbs-Maxwell Relation?

The Gibbs-Maxwell Relation was independently derived by two scientists, American physicist Josiah Willard Gibbs and Scottish physicist James Clerk Maxwell, in the late 19th century. Both scientists made significant contributions to the field of thermodynamics and their equations are still used today in many applications.

3. How is the Gibbs-Maxwell Relation derived?

The Gibbs-Maxwell Relation is derived from the fundamental laws of thermodynamics, specifically the first and second laws. It involves manipulating and combining equations for entropy, enthalpy, and other thermodynamic properties to arrive at the final relation. The derivation can be complex and requires a strong understanding of thermodynamics and calculus.

4. What are the applications of the Gibbs-Maxwell Relation?

The Gibbs-Maxwell Relation has many applications in various fields such as chemistry, physics, and engineering. It is used to analyze and predict the behavior of complex systems, such as chemical reactions, phase transitions, and heat engines. It is also used in the development of equations of state and in the study of thermodynamic processes.

5. Are there any limitations to the Gibbs-Maxwell Relation?

While the Gibbs-Maxwell Relation is a powerful tool in thermodynamics, it does have some limitations. It is only valid for systems in equilibrium and does not apply to non-equilibrium processes. Additionally, it may not be applicable to systems with high pressures or temperatures, or systems with non-ideal behavior. Therefore, it is important to consider these limitations when using the relation in practical applications.

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