Microscopic Foundations of Thermodynamics and Generalized Statistical Ensembles Page: 6
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equal to that of the initial state. For every umkehrbar process in
a thermally isolated system the entropy of the final state is equal
to that of the initial state
The expressions nicht umkehrbar and umkehrbar could be translated into the cur-
rent scientific English as non-quasi-static and quasi-static respectively.2 It must be
stressed that the entropy principle refers to transformations caused by the variation
of some external parameter, and is not at all a statement about the spontaneous ten-
dencies of physical systems. If the variation of the external parameter acts in such a
way as to drive the system out of equilibrium (non-quasi-static process) the entropy
will increase. If it acts in such a way that the system remains arbitrarily close to
equilibrium (quasi-static process) then the entropy will not change.
A few commentators have expressed the idea that the second law might not entail
any time-asymmetry [16]. According to them the time asymmetry stems from another
phenomenological fact that is often confused with the second law itself, namely
THE EQUILIBRIUM PRINCIPLE: An isolated system in an ar-
bitrary initial state within a finite fixed volume will spontaneously
attain a unique state of equilibrium.
The authors of Ref. [16] refer to this basic principle as the minus first law of thermo-
dynamics to stress the fact that it is more fundamental than all the other thermody-
namic laws. In fact the Zeroth, First and Second laws all make use of the concept of
equilibrium.
In this part of the thesis we will address the second law as expressed by the
entropy principle enunciated above. For the sake of completeness and simplicity we
shall re-express it as the following three statements:
2Often the expressions irreversible and reversible are used as synonymous of non-quasi-static
and quasi-static
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Campisi, Michele. Microscopic Foundations of Thermodynamics and Generalized Statistical Ensembles, dissertation, May 2008; Denton, Texas. (https://digital.library.unt.edu/ark:/67531/metadc6128/m1/16/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; .