Statistical Thermodynamics of Incompletely Specified Systems

Publisher Website
Google Scholar
Abstract
A formal theory of incompletely specified systems based on reasonable physical assumptions is presented. It is shown that the free energy for such systems involves the average of the logarithm of the partition function, rather than the average of the partition function itself. It is further shown that one cannot always replace the logarithm of the partition function by its average in all of the equations of statistical thermodynamics. The method differs from that of Mazo. We do not obtain a term corresponding to an entropy of mixing due to random elements. Finally, fluctuations as calculated here differ from those implied by Mazo's method. Due to the formal nature of the problem, a strict right—wrong distinction between the two methods cannot be made.

This publication has 6 references indexed in Scilit: