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Is the Hessian matrix of thermodynamic potentials regarding extensive variables positive definite?

Physics Asked on May 31, 2021

We learned that the Hessian matrix of thermodynamic potentials regarding extensive variables is positive definite (as a stability condition).

If we take the grand potential in its natural variables,
$$Omega(T,V,mu),qquad dOmega=-SdT-pdV-Ndmu$$
the only extensive variable is $V$, so it should follow that
$$left(frac{partial^2Omega}{partial V^2}right)_{T,mu}>0impliesleft(frac{-partial p}{partial V}right)_{T,mu}>0impliesleft(frac{partial p}{partial V}right)_{T,mu}<0$$

However, with help of the Gibbs-Duhem equation, one can also follow that
$$left(frac{partial p}{partial V}right)_{T,mu}=0,$$
which apparently is a contradiction. So is the Hessian matrix really only semidefinite?


The derivation with the Gibbs-Duhem equation works as follows:
$$0=U-TS+pV-mu N=Omega+pViffOmega(T,V,mu)=-p(T,V,mu)V$$
As $dOmega=-SdT-pdV-Ndmu$ one gets:
$$left(frac{partialOmega}{partial V}right)_{T,mu}=-poverset{!}{=}left(frac{partial(-pV)}{partial V}right)_{T,mu}=-p-Vleft(frac{partial p}{partial V}right)_{T,mu}$$
Which implies
$$left(frac{partial p}{partial V}right)_{T,mu}=0$$

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