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Kammerling Onnes in 1908, brought about an advancement of the problem of classifying those transitional phenomena that are not ordinary changes of state. 19 K. In particular, at this temperature discontinuities were observed of the thermal dilatation coeﬃcient, of the dielectric constant, and of the constant-volume speciﬁc heat. The two forms of liquid helium were denoted by He I and He II. 19 K, He I was stable, whereas He II was stable below this temperature. This was called the λ-transition because of the shape of the graph of speciﬁc heat as a function of T .
Instead of sketching here this standard presentation of the bases of ensemble theory of statistical mechanics, we propose an equivalent conceptual construction, which we could deﬁne as a “top-down” approach, based on an old and almost forgotten work by L. ” In other words, the second law of thermodynamics is the founding physical principle of ensemble statistical mechanics. 7 Let us now recall Szilard’s work, which surprised many, including Einstein and von Laue, in which the author showed that the second law of thermodynamics provides information not only about the mean values of macroscopic observables but also about their ﬂuctuation properties.
49) where F (N, V, T ) is the Helmholtz free energy computed in the canonical ensemble. 50) where v = V/N is the speciﬁc volume (inverse density), and where we have used P (v) = −(1/N )(∂F/∂v) for the pressure of the system. It is an experimental fact that (∂P/∂v) ≤ 0 holds always true. 50) we have σN /N → ∞ as N → ∞. 48), we ﬁnally obtain the Helmholtz free energy, from which all the other thermodynamic functions can be derived. 6 Phase Transitions Phase transitions involve abrupt major changes of the physical properties of macroscopic objects when a thermodynamic parameter is even slightly varied across a critical value.