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Statistical mechanics of the isoenthalpic-isobaric ensemble

1981; Springer Science+Business Media; Volume: 64; Issue: 2 Linguagem: Inglês

10.1007/bf02903282

2037-4895

J. R. Ray, H. W. Graben, J. M. Haile,

Advanced Thermodynamics and Statistical Mechanics

A detailed analysis is given for the isoenthalpic-isobaric ensemble in classical statistical mechanics. The properties of the phase space for the ensemble are defined and the connection with thermo-dynamics is established. The general expression for the average properties in the ensemble is presented and mean square fluctuation properties are related to thermodynamics. In particular, previous results that relate the mean square volume fluctuations to the isobaric heat capacity are confirmed. In addition, new results are obtained in which cross-fluctuations are related to the volume expansivity. The technique for deriving fluctuation formulae is new and represents the first time fluctuation formulae have been derived directly within a shell ensemble.