Can someone help me understand enthelpy and free energy?

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SUMMARY

This discussion centers on the understanding of Helmholtz and Gibbs free energy in thermodynamics. The key equations discussed include Gibbs free energy defined as G = H - TS and Helmholtz free energy as F = U - TS, with ΔG = ΔH - TΔS and ΔF = ΔU - TΔS respectively. Participants clarify that the TS term accounts for the energy associated with entropy changes at constant temperature and pressure. The introduction of these free energy concepts is necessary to analyze systems under specific constraints, such as constant temperature and volume, which are essential for understanding energy exchanges in thermodynamic processes.

PREREQUISITES
  • Understanding of thermodynamic state variables, specifically enthalpy (H), internal energy (U), and entropy (S).
  • Familiarity with the first and second laws of thermodynamics.
  • Knowledge of the Legendre Transform and its application in thermodynamics.
  • Basic concepts of closed and isolated systems in thermodynamics.
NEXT STEPS
  • Study the derivation and implications of the Legendre Transform in thermodynamics.
  • Learn about the conditions under which Gibbs and Helmholtz free energies are minimized.
  • Explore the relationship between entropy changes and energy exchanges in thermodynamic systems.
  • Investigate real-world applications of Gibbs and Helmholtz free energy in chemical reactions and phase transitions.
USEFUL FOR

Students and professionals in physics and chemistry, particularly those focusing on thermodynamics, energy systems, and chemical engineering. This discussion is beneficial for anyone seeking to deepen their understanding of thermodynamic potentials and their applications.

  • #31
Zeppos10 said:
Yes, I read the whole thread, but not all of it pertains to the interpretation of G=H-TS and this is what I emphasized.
I would like to know applications of G outside chemistry: is it used in mechanics ? In electrical systems ? I look for the domain of application, which might help us.
btw: If G=H-TS, then G only applies to systems for which H is defined: which cannot be more often then for systems for which H applies.
G and H are defined for _every_ thermodynamic system; you can go between the two by a standard Legendre transform. depending on the application (and on the tabulated values for your system of interest, you choose one of the two (or another potential, such as that by Helmholtz). All these descriptions are equivalent, but calculating with one description may be far simpler than with another one.
 
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  • #32
A. Neumaier said:
G and H are defined for _every_ thermodynamic system; you can go between the two by a standard Legendre transform. depending on the application (and on the tabulated values for your system of interest, you choose one of the two (or another potential, such as that by Helmholtz). All these descriptions are equivalent, but calculating with one description may be far simpler than with another one.

For the discussion on "Why (not) the Legendre Transform" see post #7 at
https://www.physicsforums.com/showthread.php?t=313535
 
  • #33
Zeppos10 said:
For the discussion on "Why (not) the Legendre Transform" see post #7 at
https://www.physicsforums.com/showthread.php?t=313535

Zeppos10 said:
Callen, one of the first to convert to the LT-approach of thermodynamics, writes in 1987 (Thermodynamics etc, p138): "the introduction of the transformed representations is purely a matter of convenience".
True. And in complicated problems, there is a BIG difference between which formulation one uses - in one a particular problem may be tractable, in another one not.
Zeppos10 said:
1. First of all: there is nothing convenient about the Legendre transform.
Others find it _very_ convenient; that's why it made it into all textbooks.
Zeppos10 said:
2. In general (for an arbitrary, but well defined system), both U(V,S) and H(p,S) are unknown (unspecified) functions:
But in general (for any particular specific system), both U(V,S) and H(p,S) are convex functions, and one of the two (or, more often the Gibbs or Helmholtz free energy) is usually approximately known, and can be used for predictions.
 
Last edited:
  • #34
I do believe that equations and conditions involving G are of particular use in multicomponent systems.

As such you will find G used in alloy metallurgy and flow processes such as combustion engines, where the chemical reaction is secondary to the mechanical considerations.

Whether you consider this Chemistry, Chemical Engineering or Mechanical Engineering is moot.
 

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