Thermodynamics – How to Understand System in Mechanical but not Thermal Equilibrium

statistical mechanicsthermodynamics

Let's say there are two systems which can interact by a moving wall but cannot exchange heat. Then the system will be in mechanical, but not necessarily in thermal equilibrium.

The maximality of entropy in mechanical equilibrium requires only the ratio p/T to be equal. So there is a possible equilibrium state where one system has double pressure and double temperature…

Where is my mistake?

Best Answer

This is a classic conundrum and it is called the "problem of the adiabatic piston". You can find it discussed in books on thermodynamics by Landau & Lifhsitz and by Callen. Another very thorough analysis is by Gruber "Thermodynamics of systems with internal adiabatic constraints: time evolution of the adiabatic piston". (You can find Gruber's article here free http://citeseerx.ist.psu.edu/viewdoc/summary?doi=10.1.1.55.995 )

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