Conditions of equilibrium and stability

This month Peter Mander’s CarnotCycle blog talks about the interesting world of statistical equilibriums. And particularly it talks about stable equilibriums. A system’s in equilibrium if it isn’t going to change over time. It’s in a stable equilibrium if being pushed a little bit out of equilibrium isn’t going to make the system unpredictable.

For simple physical problems these are easy to understand. For example, a marble resting at the bottom of a spherical bowl is in a stable equilibrium. At the exact bottom of the bowl, the marble won’t roll away. If you give the marble a little nudge, it’ll roll around, but it’ll stay near where it started. A marble sitting on the top of a sphere is in an equilibrium — if it’s perfectly balanced it’ll stay where it is — but it’s not a stable one. Give the marble a nudge and it’ll roll away, never to come back.

In statistical mechanics we look at complicated physical systems, ones with thousands or millions or even really huge numbers of particles interacting. But there are still equilibriums, some stable, some not. In these, stuff will still happen, but the kind of behavior doesn’t change. Think of a steadily-flowing river: none of the water is staying still, or close to it, but the river isn’t changing.

CarnotCycle describes how to tell, from properties like temperature and pressure and entropy, when systems are in a stable equilibrium. These are properties that don’t tell us a lot about what any particular particle is doing, but they can describe the whole system well. The essay is higher-level than usual for my blog. But if you’re taking a statistical mechanics or thermodynamics course this is just the sort of essay you’ll find useful.



In terms of simplicity, purely mechanical systems have an advantage over thermodynamic systems in that stability and instability can be defined solely in terms of potential energy. For example the center of mass of the tower at Pisa, in its present state, must be higher than in some infinitely near positions, so we can conclude that the structure is not in stable equilibrium. This will only be the case if the tower attains the condition of metastability by returning to a vertical position or absolute stability by exceeding the tipping point and falling over.


Thermodynamic systems lack this simplicity, but in common with purely mechanical systems, thermodynamic equilibria are always metastable or stable, and never unstable. This is equivalent to saying that every spontaneous (observable) process proceeds towards an equilibrium state, never away from it.

If we restrict our attention to a thermodynamic system of unchanging composition and apply…

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