Extremum of thermodynamic potentials: confusion

Join the discussion
Registration is free. Start your own thread to ask a follow-up.
2 replies · 1K views
Dazed&Confused
Messages
190
Reaction score
3
An alternative formulation of the second law is that the energy of the system [itex]U[/itex] is minimised if the temperature and entropy of the system are held constant.
However, [tex]dU= TdS -pdV[/tex]
which means that [itex]U[/itex] is presumably constant if the volume [itex]V[/itex] and the entropy [itex]S[/itex] are kept constant. How then can [itex]U[/itex] change so that it is minimised?
 
Physics news on Phys.org
Thanks for replying. I have seen two versions. One is in Steven Blundell's book where he derives the availability which satisfies
[itex]dA= dU + p_0dV -T_0dS \leq 0[/itex] where the subscripted variables are the reservoir ones. He then states that if [itex]V, S[/itex] are constant then [itex]dA = dU \leq 0[/itex] so that [itex]U[/itex] is minimised.

The other version uses a completely different approach but crucially no mention is made of [itex]V[/itex] being constant as you say.