Gibbs Free Energy and Equation of State

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Discussion Overview

The discussion revolves around the relationship between Gibbs free energy and the equation of state, particularly focusing on the expression for volume in terms of Gibbs function. Participants explore the definitions and implications of state functions and equations of state in thermodynamics.

Discussion Character

  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant questions the relationship between Gibbs function and the equation of state, seeking a deeper understanding of the expression V=(∂G/∂P)_T.
  • Another participant provides a derivation of the relationship, starting from the definition of Gibbs free energy (G = U - TS + PV) and showing how it leads to the expression for volume.
  • A participant expresses gratitude for the explanation and seeks clarification on the nature of state functions, suggesting that they relate two or more extensive variables.
  • Further elaboration is provided on the concept of state functions and equations of state, with an example of the ideal gas equation and the assertion that knowing three independent thermodynamic variables can determine a fourth.

Areas of Agreement / Disagreement

Participants appear to agree on the mathematical relationship between Gibbs free energy and volume, but there is no consensus on the broader implications or definitions of state functions and equations of state, as some points remain exploratory.

Contextual Notes

Some assumptions about the definitions of state functions and the conditions under which the equations of state apply are not fully explored, leaving room for further discussion.

electricspit
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I'm wondering why the Gibbs function is related to the equation of state as follows (supposedly):

V=(\frac{∂G}{∂P})_T

I found a thread on here that mentions this relationship, but doesn't explain it at all. Any help understanding this would be appreciated, this is my first introduction to the Gibbs and Helmholtz functions and I'm trying to understand as fully as I can.
 
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It is a consequence of the definition G:

$$
G = U - TS + PV.
$$

Since

$$
dU = TdS - PdV,
$$

it follows that

$$
dG = -SdT + VdP
$$

and thus the volume V is given by

$$
V = \left(\frac{\partial G}{\partial P}\right)_T.
$$
 
Awesome thank you, just what I was looking for!

So then a state function itself is just any relation that relates 2 or more extensive variables?
 
electricspit said:
So then a state function itself is just any relation that relates 2 or more extensive variables?

If you have a simple system ("simple" here means that the system can do work only by volume expansion) that consists of one pure substance, giving the values of three independent thermodynamic variables fixes the values of all other variables. An equation of state is an equation that can be used to solve a fourth variable when three are known. A familiar example is the ideal gas equation PV=nRT, but other variables like entropy or free energy can also appear in an equation of state.
 

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