Why must the Gibbs Free Energy be proportional to N?

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Discussion Overview

The discussion centers on the relationship between Gibbs Free Energy (G) and the number of particles (N), specifically questioning why G must be proportional to N. Participants explore the definitions of extensive and intensive properties in thermodynamics and provide examples to illustrate their points.

Discussion Character

  • Debate/contested
  • Technical explanation

Main Points Raised

  • Some participants argue that if G is defined as \(G(T, P, N) = (TPN)^{1/3}\), then it can be extensive but not proportional to N, as shown by the transformation \(G(\lambda T, \lambda P, \lambda N) = \lambda G\).
  • Others contend that this example does not satisfy the definition of extensiveness, as \(G(T,P,\lambda N) \neq \lambda G(T,P,N)\), suggesting that G is not extensive in this case.
  • One participant emphasizes that the definition of an extensive property requires that scaling all extensive variables results in a scaled output, questioning the use of intensive variables like pressure and temperature in the argument.
  • Another participant clarifies that only extensive variables should be multiplied by \(\lambda\) when scaling the system size, reinforcing the distinction between extensive and intensive properties.

Areas of Agreement / Disagreement

Participants express disagreement regarding the interpretation of extensiveness in relation to Gibbs Free Energy, with no consensus reached on whether G must be proportional to N or the validity of the examples provided.

Contextual Notes

Participants highlight the importance of distinguishing between extensive and intensive variables, indicating that the definitions and examples used may depend on the context of the discussion.

aliens123
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In the textbook Thermal Physics by Daniel Schroeder he says the following:
5.35.PNG


However, I don't follow this argument. Let's say that G was the following:
$$G(T, P, N) = (TPN)^{1/3}$$
Then
$$G(\lambda T, \lambda P, \lambda N) = \lambda G$$
So $$G$$ is extensive, but $$G \not \propto N.$$
 
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aliens123 said:
Let's say that G was the following:
$$G(T, P, N) = (TPN)^{1/3}$$
Then
$$G(\lambda T, \lambda P, \lambda N) = \lambda G$$
So $$G$$ is extensive, but $$G \not \propto N.$$
In this example ##G## is not extensive since ##G(T,P,\lambda N)\ne \lambda G(T,P,N)##
 
Dale said:
In this example ##G## is not extensive since ##G(T,P,\lambda N)\ne \lambda G(T,P,N)##
Isn't the definition of extensive
$$Q(\lambda q_1, \lambda q_2, ..., \lambda q_n ) = \lambda Q(q_1, q_2, ..., q_n)?$$
 
aliens123 said:
Isn't the definition of extensive
$$Q(\lambda q_1, \lambda q_2, ..., \lambda q_n ) = \lambda Q(q_1, q_2, ..., q_n)?$$
The ##q_i## need to be extensive here. You are looking at ##P## and ##T## which are intensive. If you double the amount of stuff, temperature and pressure don't double. Have a look at the rabbits on the page before the excerpt you used in the OP.
 
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No, you have to multiply only the extensive variables with ##\lambda##. The intensive variables don't change when scaling the "system size". That's the definition of extensive vs. intensive variables.
 

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