[Physics] Thermodynamic Equilibrium vs Thermal Equilibrium

terminologythermodynamics

I am trying to understand the difference between thermodynamic and thermal equilibriums. According to wikipedia, they really are distinct; you can have one without the other. However, I am having trouble visualizing a somewhat less abstract and more physically realizable system where you can have one without the other. Is there some "non-pathological" system where we can see that it is in thermodynamic but not thermal equilibrium and another where we have thermal but not thermodynamic equilibrium?

I'm motivated by this question by a statement I heard regarding local and global temperature. In some system which can be partitioned into subsystems where local temperature is a well-defined quantity, the claim was made that the system can be in thermodynamic equilibrium and hence have a well-defined global temperature, yet the local temperature can fluctuate and differ from the global temperature. This seems quite paradoxical to me and hard to wrap my mind around, though in principle it seems possible.

Best Answer

This is a question of meaning of words - semantics. I did not make any research into how the terms are used in the classic physics literature, but I think the following view is quite reasonable:

  • system is in thermal equilibrium when any two parts of it are in direct or indirect thermal contact (capable of exchanging heat) but no appreciable heat is exchanged from one to another even after a long time (concern with heat flow)

  • system is in thermodynamic equilibrium when all macroscopic processes in it subsided(concern with any macroscopic flow, not only heat).

Is there some "non-pathological" system where:

  • we can see that it is in thermodynamic but not thermal equilibrium:

Yes, for example two gases of different temperature trapped in a cylindrical vessel separated by movable but thermally insulating piston. If the pressure of the gas is the same in both compartments, the system will remain without change indefinitely, so it is in thermodynamic equilibrium (under given constraint of perfect insulation). However, it is clearly not in thermal equilibrium, because there is no possibility of thermal exchange between the two parts.

Admittedly, this is an idealized situation, as there are no perfect thermal insulators in the real world. In practice such a system would not be in thermodynamic equilibrium either, as some heat would flow from the hotter to the colder gas. But it is possible to make walls that would maintain the state of different temperatures for a very long time without appreciable change in the macroscopic state, so this would be a system in thermodynamic equilibrium for all practical purposes.

  • another where we have thermal but not thermodynamic equilibrium:

Yes, for example a gas that is being compressed by a moving wall. The temperature and pressure increases everywhere as work is being performed on the gas elements; but there is no heat flux anywhere. The system is in thermal equilibrium, but not in thermodynamic equilibrium, as macroscopic changes are happening.

Of course, in practice the compression would not occur uniformly in the whole space, but there would be compression waves and heat exchange between elements of the gas. The system is thus not even in thermal equilibrium. But if the compression is done slowly enough, heat exchanges will be negligible and most energy transfer will be via work. Thus the system would be in thermal equilibrium for all practical purposes.

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