Meaning of thermodynamical potentials (F,H,G,E)

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Discussion Overview

The discussion revolves around the intuitive meanings and connections of thermodynamic potentials: internal energy (E), Helmholtz free energy (F), enthalpy (H), and Gibbs free energy (G). Participants explore the conceptual understanding of these potentials and their implications in thermodynamic processes.

Discussion Character

  • Exploratory
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant expresses difficulty in defining thermodynamic potentials and suggests that, similar to energy, these concepts may lack a straightforward definition.
  • The same participant attempts to understand Gibbs free energy (G) through quasistatic processes and questions its connection to entropy changes.
  • Another participant clarifies the formula for G and suggests that thermodynamic potentials can be viewed as indicators of spontaneity for processes under varying conditions.
  • There is a correction regarding the interpretation of G, emphasizing that it is the change in G that must be negative for spontaneous processes at constant temperature and pressure.
  • A comparison is made between the behavior of G in thermodynamic processes and potential energy in mechanical processes, illustrating the concept of spontaneity.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the intuitive meanings of the thermodynamic potentials, and multiple interpretations and clarifications are presented throughout the discussion.

Contextual Notes

There are unresolved aspects regarding the definitions and intuitive understandings of the thermodynamic potentials, as well as the implications of entropy changes in relation to these quantities.

sisife
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Hello!

I'm trying to grasp the "intuitive" meaning of the thermodynamical potetials E,F,H and G, or at least of their connections.

As in other threads before mentioned, I learned that you can't real.y give an meaningful definition of energy , so I assume for the other potentials this is also true.
As for what energy 'is', you could just as easily as "What is 'red'? The fact that a simple answer doesn;t exist does not make the concept any less useful.

But at least I have a kind of intuition what energy is, in contrary to the other quantities.

I tried to understand G by considering a quasistatic process. Then Q=TS and W=PV. So G=E-TS-PV is the energychange in a system in a non-quasi-static process (e.g. due to friction etc., or due to a difference in the entropy change (but here I am confused about, how this is connected)). Is this correct?

Are there nice ways to illustrate the other ones? Or is this simply a waste of time? (if I don't have an ituition for what I am doing I always find it difficult to find solutions for a problem).


thanks for your help
 
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Hi sisife, welcome to PF. First, G is E-TS+PV. Second, it may be easiest to think of the potentials as "barometers" for spontaneity for processes occurring under different conditions. For processes at constant temperature and pressure, G must be negative for any spontaneous process. At constant temperature and volume, the Helmholtz energy (A or F) must be negative, and so on.

These relationships can all be derived from the required entropy increase during any spontaneous process in a closed system.
 
Mapes said:
For processes at constant temperature and pressure, G must be negative for any spontaneous process.

You mean to write: For processes at constant temperature and pressure, *the change in* G must be negative for any spontaneous process.

I.e., G decreases...

To the OP, you can compare the above statement to what happens to the energy in mechanical processes--E.g., a ball rolls *down* a hill--a spontaneous process decreases the potential energy.
 
That's a good picture, that will help.
Thank you!
 

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