Gibbs Energy: Understanding A=G+hM

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SUMMARY

The discussion clarifies the relationship between Helmholtz energy (A), Gibbs energy (G), external magnetic field (h), and magnetization (M) in magnetic systems. The equation A = G + hM is examined, emphasizing that hM does not equate to -PV. The conversation highlights the importance of using the Legendre transform to derive relevant potentials when considering systems with constant temperature and magnetic field. The discussion also warns against the inconsistent terminology used by various authors regarding thermodynamic potentials.

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  • Understanding of Helmholtz energy and Gibbs energy in thermodynamics
  • Familiarity with magnetization and external magnetic fields
  • Knowledge of Legendre transforms in thermodynamic contexts
  • Basic principles of statistical mechanics
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KFC
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In a book about stat. mech., I read the following relaiton for magnetic system

A = G + hM

where A is the Helmholtz energy, G is the Gibbs energy and h is the external magnetic field, M is the magetization. I know from thermodynamic, we have

A = U - TS

or

A = G - PV

so, hM = -PV ?

I don't understand what is hM. If I know magnetization, external field and Gibbs energy, how to get Helmholtz energy?
 
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This goes back to that issue I believe you mentioned earlier: magnetization is usually ignored in thermodynamics, so authors can be inconsistent when adding the relevant terms. When we're including magnetization in an open system, energy is

U=TS-PV+\mu N+hM

The relevant potential when temperature, pressure, and field are kept constant is acquired by the Legendre transform

\Phi=U-TS+PV-hM

Some authors may call \Phi the Gibbs energy, which risks great confusion. (I'm using the symbol \Phi as a dummy variable here.)

To figure out the potentials, just remember that you need to remove (by Legendre transform) any conjugate pairs associated with constant variables. Don't rely on the consistency of names like Helmholtz, Gibbs, etc. If someone's working with a system at constant temperature and field, for example, you know you need to consider the potential

\Lambda=U-TS-mH

whatever it might be called. (Again, \Lambda is just a dummy variable.) I hope it's helpful to see the method to constructing these potentials. Does this make sense?

(To reiterate, it's definitely not true that hM=-PV.)
 

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