Internal Energy/Helmholtz Free Energy Proof

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SUMMARY

The discussion focuses on proving the relationship (∂(βA)/∂β)N,V = E, where A represents the Helmholtz Free Energy defined as A = E - TS, and E is the Internal Energy. The initial attempt incorrectly assumed S (entropy) to be constant, leading to the erroneous conclusion that (∂(βE)/∂β) equals E. The correct approach involves applying the first law of thermodynamics and recognizing that both S and E are not constant under the given conditions.

PREREQUISITES
  • Understanding of Helmholtz Free Energy (A = E - TS)
  • Familiarity with the first law of thermodynamics (dE = TdS - pdV + ΣUidni)
  • Knowledge of statistical mechanics, specifically the concept of β = 1/(kBT)
  • Basic calculus, particularly partial derivatives and chain rule applications
NEXT STEPS
  • Study the derivation of the first law of thermodynamics in detail
  • Learn about the implications of variable entropy in thermodynamic processes
  • Explore advanced topics in statistical mechanics, focusing on the role of temperature and entropy
  • Investigate the relationship between Helmholtz Free Energy and other thermodynamic potentials
USEFUL FOR

Students and professionals in thermodynamics, physicists, and anyone studying statistical mechanics or thermodynamic potentials will benefit from this discussion.

mobwars
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Homework Statement



Show that (∂(βA)/∂β)N,V = E, where A = E - TS is the Helmholtz Free Energy and E is the Internal Energy.

Homework Equations


A = E - TS
dE = TdS - pdV + ΣUidni
β = 1 / (kBT)

The Attempt at a Solution


(∂(βA)/∂β)N,V = (∂/∂β) * (βE - βTS)
(∂(βA)/∂β)N,V = (∂/∂β) * (βE - TS/(kBT))
(∂(βA)/∂β)N,V = (∂/∂β) * (βE - S/(kB))
(∂(βA)/∂β)N,V = (∂(βE)/∂β) [S/(kB) goes away because S is constant for Helmholtz Free Energy]
(∂(βA)/∂β)N,V = E

This solution just feels entirely too easy and simplified. I think you're supposed to do something with the fact that T and S are actual variables in the equation and some chain rule is needed, but that didn't seem to get me anywhere either. Anyone know what's really going on here?
 
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mobwars said:
(∂(βA)/∂β)N,V = (∂(βE)/∂β) [S/(kB) goes away because S is constant for Helmholtz Free Energy]
(∂(βA)/∂β)N,V = E

The two lines above are incorrect. As you suspected, S is not generally constant for a process in which N and V are kept constant.
Also, ∂(βE)/∂β ≠ E because E is not generally constant either.

It might help to make use of the first law as written in your second relevant equation.
 
Start with your first two relevant equations by taking dA and then eliminating dE.

Chet
 

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