physical chemistry10.2.pptVIP

* * 10.2 Ensemble method 10.2.1 Statistical method Bulk properties(p,V,T,…) Macroscopic Properties of individual particle(εi,ψi, gi) Microscopic Pi=const. Microscopic state partition function Review: equilibrium state 10.2.2 Fundamental hypothesis Time-average observables of system N : number of microscopic state in the system of interest t E E3 E2 E1 E2 E4 E5 ? ? ? ? ? ? Ni : number of microscopic state of Ei Ensemble-average observables of system Gibbs hypothesis： Macroscopic ：N,V,E specified … E1 E2 E3 E4 E1 1 N,V,E E1 3 N,V,E E3 2 N,V,E E2 … Ensemble : hypothetical collection of a number