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Chemistry LibreTexts

Statistical Mechanical Ensembles

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  • The central application of statistical mechanics rests on the assumption that the average of a property over a large number of systems will give the same value as the thermodynamic quantity of interest. We can distinguish between mechanical properties such as pressure, energy, volume etc. and non-mechanical properties such as entropy. Although there are a large number of particles and an extremely large number of quantum states accessible to even a small system, the state of the system can be characterized by just a few thermodynamic variables.

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