Entropy Boltzmann-Gibbs

In modem physics, there exist alternative theories for the equilibrium statistical mechanics [1, 2] based on the generalized statistical entropy [3-12]. They are compatible with the second part of the second law of thermodynamics, i.e., the maximum entropy principle [13-14], which leads to uncertainty in the definition of the statistical entropy and consequently the equilibrium probability density functions. This means that the equilibrium statistical mechanics is in a crisis. Thus, the requirements of the equilibrium thermodynamics shall have an exclusive role in selection of the right theory for the equilibrium statistical mechanics. The main difficulty in foundation of the statistical mechanics based on the generalized statistical entropy, i.e., the deformed Boltzmann-Gibbs entropy, is the problem of its connection with the equilibrium thermodynamics. The proof of the zero law of thermodynamics and the principle of additivity... 

For the Boltzmann-Gibbs entropy S p] = —/p In pdx, thermodynamic force becomes... 

We have called this average the Boltzmann-Gibbs entropy, where Sbg is the entropy per molecule and n is the molecular number density. For s = 1, we recover Boltzmann s definition... 

Nonequilibrium Steady State (NESS). The system is driven by external forces (either time dependent or nonconservative) in a stationary nonequilibrium state, where its properties do not change with time. The steady state is an irreversible nonequilibrium process that cannot be described by the Boltzmann-Gibbs distribution, where the average heat that is dissipated by the system (equal to the entropy production of the bath) is positive. 

The general mathematical formulation of the equilibrium statistical mechanics based on the generalized statistical entropy for the first and second thermodynamic potentials was given. The Tsallis and Boltzmann-Gibbs statistical entropies in the canonical and microcanonical ensembles were investigated as an example. It was shown that the statistical mechanics based on the Tsallis statistical entropy satisfies the requirements of equilibrium thermodynamics in the thermodynamic limit if the entropic index z=l/(q-l) is an extensive variable of state of the system. 

The thermodynamic potential of the canonical ensemble, the Helmholtz free energy, is the first thermodynamic potential g=F, which is a function of the variables of state u 1 = T, x2=V, x3=N, and x4=z. It is obtained from the fundamental thermodynamic potential / =E (the energy) by the Legendre transform (Eq. (7)), exchanging the variable of state x1 =S of the fundamental thermodynamic potential with its conjugate variable u 1 = / . In the canonical ensemble, the first partial derivatives (Eq. (1)) of the fundamental thermodynamic potential are defined asu2=-p, u3=p, and u 4 = - S. The entropy (Eq. (46)) for the Tsallis and Boltzmann-Gibbs statistics in the canonical ensemble can be rewritten as... 

The entropy S for the Tsallis and Boltzmann-Gibbs statistics in the microcanonical ensemble can be written as... 

We note that for systems at equilibrium, is independent of the locator vector r and Eq. (5.80) reduces to Gibbs entropy for equilibrium systems, Eq. (4.39).l Also, note that the introduction of Planck s constant in the logarithm term of Boltzmann s entropy, Eq. (5.79), is necessary on account of dimensional arguments, albeit it is often incorrectly left out. 

Nearly ten years ago, Tsallis proposed a possible generalization of Gibbs-Boltzmann statistical mechanics. [1] He built his intriguing theory on a reexpression of the Gibbs-Shannon entropy S = —k Jp r) np r)dr written... 

When g = 1 the extensivity of the entropy can be used to derive the Boltzmann entropy equation 5 = fc In W in the microcanonical ensemble. When g 1, it is the odd property that the generalization of the entropy Sq is not extensive that leads to the peculiar form of the probability distribution. The non-extensivity of Sq has led to speculation that Tsallis statistics may be applicable to gravitational systems where interaction length scales comparable to the system size violate the assumptions underlying Gibbs-Boltzmann statistics. [4]... 

In the 19th century the variational principles of mechanics that allow one to determine the extreme equilibrium (passing through the continuous sequence of equilibrium states) trajectories, as was noted in the introduction, were extended to the description of nonconservative systems (Polak, 1960), i.e., the systems in which irreversibility of the processes occurs. However, the analysis of interrelations between the notions of "equilibrium" and "reversibility," "equilibrium processes" and "reversible processes" started only during the period when the classical equilibrium thermodynamics was created by Clausius, Helmholtz, Maxwell, Boltzmann, and Gibbs. Boltzmann (1878) and Gibbs (1876, 1878, 1902) started to use the terms of equilibria to describe the processes that satisfy the entropy increase principle and follow the "time arrow."... 

At constant external pressure the enthalpy is the relevant thermodynamic potential for the Boltzmann distribution. A large area A implies that the distribution of the thicknesses is confined near the minimum of the enthalpy, while a small value of A corresponds to large thickness fluctuations. The first case corresponds to a low enthalpy, but a large entropy, whereas the second to a large enthalpy, but a low entropy. The real distribution is provided by the minimization of the Gibbs free energy with respect to A at constant external pressure II. 

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