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Thermo_4_Lhandout - Thermodynamics 4 Thermodynamic...

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1 Thermodynamics 4. Thermodynamic Ensembles and Ergodicity; Thermodynamics and Living Systems BIOL 7110 / CHEM 8901 / BIOL 4105 / CHEM 4804 February 1, 2011 9. Thermodynamic Ensembles Thermodynamic ensemble: a virtual collection of a very large number of systems, each of which is an exact replica of the system of interest Experiments can be done at fixed volume (V), or at fixed pressure (P) or at fixed temperature (T). Experimentally, we can hold any two of these constant, but not all three! Consider an ideal gas, for example. The universal gas law, PV = NRT requires PV/T = NR = constant Why only two?
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2 9. Thermodynamic Ensembles Thermodynamic ensemble: a virtual collection of a very large number of systems, each of which is an exact replica of the system of interest Microcanonical (NVE) ensemble: Equilibrium state has maximum entropy Canonical (NVT) ensemble: Equilibrium state has minimum Helmholtz free energy A = E - TS Isothermal-isobaric (NPT) ensemble: Equilibrium state has minimum Gibbs free energy G = H – TS H = E + PV 9. Thermodynamic Ensembles
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