[Physics] Why is the Gibbs Free Energy $F-HM$

energystatistical mechanicsthermodynamics

With magnetism, the Gibbs Free Energy is $F-HM$, where $F$ is the Helmholtz Free Energy, $H$ is the auxiliary magnetic field, and $M$ is magnetization.

Why is this? Normally, in thermodynamics, we Legendre Transform the various free energies into each other to maximize the global entropy. In these cases, we subtract $TS$ when we are imagining a system exchanging heat with a thermal reservoir (i.e. heat bath at constant temperature $T$), add $PV$ when we exchange volume $V$ with a constant pressure reservoir at pressure $P$, and subtract $\mu N$ when we exchange particles with a chemical reservoir at constant chemical potential $\mu$.

In every other case, we exchange heat, volume, and particles with the reservoir. How do we justify writing $G=F-HM$. Though it is true that $H$ is maintained constant, we don't exchange magnetization with a "magnetic reservoir".

Best Answer

According to the first law of thermodynamics

\begin{align}U=TS+YX+\sum_j\mu_jN_j.\end{align}

Where $Y$ is the generalized force, $dX$ is the generalized displacement.

Helmholtz Free Energy

\begin{align}F=U-TS=YX+\sum_j\mu_jN_j. \end{align}

Gibbs Free Energy

\begin{align}G=U-TS-YX=\sum_j\mu_jN_j.\end{align}

Therefore that

\begin{align}G=F-YX.\end{align}

In your case, $Y=H$, $X=M$, so we get

\begin{align}G=F-HM.\end{align}

You can see the textbook:

A Modern Course in Statistical Physics by L. E. Reichl, 2nd, ed (1997), p23, 42, 45.

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