The Gibbs paradox of the first kind (GP1) refers to the false increase in entropy which, in statistical mechanics, is calculated from the process of combining two gas systems S1 and S2 consisting of distinguishable particles. Presented in a somewhat modified form, the GP1 manifests as a contradiction to the second law of thermodynamics. Contrary to popular belief, this contradiction affects not only classical but also quantum statistical mechanics. The present paper resolves the GP1 by considering two effects: 1. The uncertainty about which particles are located in S1 and which in S2 contributes to the entropies of S1 and S2. 2. S1 and S2 are correlated by the fact that if a certain particle is located in one system, it cannot be located in the other. As a consequence, the entropy of the total system consisting of S1 and S2 is not the sum of the entropies of S1 and S2.
The inclusion of the factor $\ln (1/N!)$ in the thermodynamic entropy proposed by Gibbs is shown to be equivalent to the validity of the fluctuation theorem with absolute irreversibility for gas mixing.
We study the propagation of entanglement after quantum quenches in the non-integrable para-magnetic quantum Ising spin chain. Tuning the parameters of the system, we observe a sudden increase in the entanglement production rate, which we show to be related to the appearance of new quasi-particle excitations in the post-quench spectrum. We argue that the phenomenon is the non-equilibrium version of the well-known Gibbs paradox related to mixing entropy and demonstrate that its characteristics fit the expectations derived from the quantum resolution of the paradox in systems with a non-trivial q…
We prove that information-theoretic maximum entropy (MaxEnt) approach to canonical ensemble is mathematically equivalent to the classic approach of Boltzmann, Gibbs and Darwin-Fowler. The two approaches, however, "interpret" a same mathematical theorem differently; most notably observing mean-energy in the former and energy conservation in the latter. However, applying the same MaxEnt method to grand canonical ensemble fails; while carefully following the classic approach based on Boltzmann's microcanonical {\em equal probability a priori} produces the correct statistics: One does not need to …
The Gibbs Mixing Paradox is a conceptual touchstone for understanding mixtures in statistical mechanics. While debates over the theoretical subtleties of particle distinguishability continue to this day, we seek to extend the discussion in another direction by considering devices which can only distinguish particles with limited accuracy. We introduce two illustrative models of sorting devices which are designed to separate a binary mixture, but which sometimes make mistakes. In the first model, discrimination between particle types is passive and sorting is driven, while the second model is b…
Identical classical particles are distinguishable. This distinguishability affects the number of ways W a macrostate can be realized on the micro-level, and from the relation S = k ln W leads to a non-extensive expression for the entropy. This result is usually considered incorrect because of its inconsistency with thermodynamics. It is sometimes concluded from this inconsistency that identical particles are fundamentally indistinguishable after all; and even that quantum mechanics is indispensable for making sense of this. In contrast, we argue that the classical statistics of distinguishable…
This paper introduces the basic concepts of information theory. Based on these concepts, we regard the states in the state space and the types of ideal gases as the symbols in a symbol set to calculate the mixing entropy of ideal gas involved in Gibbs Paradox. The discussion above reveals that the non-need for distinguishing can resolve the contradiction of Gibbs Paradox, implying the introduction of indistinguishability is not necessary. Further analysis shows that the information entropy of gas molecular types does not directly correlate to the energy of a gas system, so it should not be use…
Based on a reconsideration of the Gibbs paradox, we show that a residual, non-extensive term in entropy turns up upon mixing identical particles, whether they are indistinguishable or not. The positive contribution from this residual entropy leads to a decrease in free energy, and we suggest that this entropic mechanism may serve as a source of like-charge attractions between a pair of colloidal particles or other macroions. For a system of two colloidal particles along with their neutralizing counterions, such decrease in free energy is of a few thermal energies and therefore crucial to the e…
Gibbs paradox in the context of statistical mechanics addresses the issue of additivity of entropy of mixing gases. The usual discussion attributes the paradoxical situation to classical distinguishability of identical particles and credits quantum theory for enabling indistinguishability of identical particles to solve the problem. We argue that indistinguishability of identical particles is already a feature in classical mechanics and this is clearly brought out when the problem is treated in the language of information and associated entropy. We pinpoint the physical criteria for indistingu…
This article presents the results of research into the causes of the Gibbs paradox in the formulation discussed by J. W. Gibbs himself. In this formulation, we are talking about an inexplicable (paradoxical) jump in the entropy of mixing of two ideal gases during the transition from mixing different to mixing identical gases. It is shown that the entropy of mixing of different ideal gases and the entropy of mixing of identical ideal gases are different (non-identical) functions of the same gas parameters. That, called a paradoxical jump in the entropy of mixing, is not a jump in the value of s…
We present a fully quantum solution to the Gibbs paradox (GP) with an illustration based on a gedanken experiment with two particles trapped in an infinite potential well. The well is divided into two cells by a solid wall, which could be removed for mixing the particles. For the initial thermal state with correct two-particle wavefunction according to their quantum statistics, the exact calculations shows the entropy changes are the same for boson, fermion and non-identical particles. With the observation that the initial unmixed state of identical particles in the conventional presentations …
The classical Gibbs paradox concerns the entropy change upon mixing two gases. Whether an observer assigns an entropy increase to the process depends on their ability to distinguish the gases. A resolution is that an "ignorant" observer, who cannot distinguish the gases, has no way of extracting work by mixing them. Moving the thought experiment into the quantum realm, we reveal new and surprising behaviour: the ignorant observer can extract work from mixing different gases, even if the gases cannot be directly distinguished. Moreover, in the macroscopic limit, the quantum case diverges from t…
The ``Gibbs Paradox'' refers to several related questions concerning entropy in thermodynamics and statistical mechanics: whether it is an extensive quantity or not, how it changes when identical particles are mixed, and the proper way to count states in systems of identical particles. Several authors have recognized that the paradox is resolved once it is realized that there is no such thing as the entropy of a system, that there are many entropies, and that the choice between treating particles as being distinguishable or not depends on the resolution of the experiment. The purpose of this n…
Molecular collision within an ideal gas originates from an intrinsic short-range repulsive interaction. The collision reduces the average accessible physical space for a single molecule and this has a direct consequence on the entropy of the gas. The accessibility of a molecule to a spatial coordinate (x, y, z) inside the system depends on the local molecular density. By considering mechanical equilibrium between a system and a reservoir, the probability of the system in state i with volume vi is shown to be proportional to exp(-vi/v0) where v0 is the average volume per molecule. Incorporating…
The issue of the Gibbs paradox is that when considering mixing of two gases within classical thermodynamics, the entropy of mixing appears to be a discontinuous function of the difference between the gases: it is finite for whatever small difference, but vanishes for identical gases. The resolution offered in the literature, with help of quantum mixing entropy, was later shown to be unsatisfactory precisely where it sought to resolve the paradox. Macroscopic thermodynamics, classical or quantum, is unsuitable for explaining the paradox, since it does not deal explicitly with the difference bet…
This is an analysis of the additivity of the entropy of thermodynamical systems with finite heat baths. It is presented an expression for the physical entropy of weakly interacting ergodic systems, and it is shown that it is valid for both the microcanonical (constant energy), the Boltzmann-Gibbs canonical (infinite heat bath) and the Tsallis (finite heat bath) ensembles. This physical entropy may be written as a variant of Tsallis entropy. It becomes an additive function after a suitable choice of additive constants, in a procedure reminiscent to the solution presented by Gibbs to the paradox…
Defining the entropy of classical particles raises a number of paradoxes and ambiguities, some of which have been known for over a century. Several, such as Gibbs' paradox, involve the fact that classical particles are distinguishable, and in textbooks these are often `resolved' by appeal to the quantum-mechanical indistinguishability of atoms or molecules of the same type. However, questions then remain of how to correctly define the entropy of large poly-atomic particles such as colloids in suspension, of which no two are exactly alike. By performing experiments on such colloids, one can est…
The entropy of Boltzmann-Gibbs, as proved by Shannon and Khinchin, is based on four axioms, where the fourth one concerns additivity. The group theoretic entropies make use of formal group theory to replace this axiom with a more general composability axiom. As has been pointed out before, generalised entropies crucially depend on the number of allowed number degrees of freedom $N$. The functional form of group entropies is restricted (though not uniquely determined) by assuming extensivity on the equal probability ensemble, which leads to classes of functionals corresponding to sub-exponentia…
Dunkel and Hilbert, "Consistent thermostatistics forbids negative absolute temperatures," Nature Physics, {\bf 10}, 67 (2014), and Hilbert, Hänggi, and Dunkel, "Thermodynamic laws in isolated systems," Phys. Rev. E {\bf 90}, 062116 (2014) have presented an unusual view of thermodynamics that sets aside several properties that have traditionally have been assumed to be true. Among other features, their results do not satisfy the postulates of thermodynamics originally proposed by Tisza and Callen. In their theory, differences in the temperatures of two objects cannot determine the direction of …
The issue of the thermodynamics of a system of distinguishable particles is discussed in this paper. In constructing the statistical mechanics of distinguishable particles from the definition of Boltzmann entropy, it is found that the entropy is not extensive. The inextensivity leads to the so-called Gibbs paradox in which the mixing entropy of two identical classical gases increases. Lots of literature from different points of view were created to resolve the paradox. In this paper, starting from the Boltzmann entropy, we present the thermodynamics of the system of distinguishable particles. …
Recently, Ozawa and Berthier [J. Chem. Phys., 2017, 146, 014502] studied the configurational and vibrational entropies $S_c$ and $S_v$ from the relation $S_{tot}=S_c+S_v$ for polydisperse mixtures of spheres. They noticed that because $S_{tot}/N$ shall contain the mixing entropy per particle $k_B s_m$ and $S_v/N$ shall not, the configurational entropy per particle $S_c/N$ shall diverge in the thermodynamic limit for continuous polydispersity due to the diverging $s_m$. They also provided a resolution for this paradox and related problems-it relies on a careful redefining of $S_c$ and $S_v$. He…
Consistent statistical physical description is given for systems where the elementary excitations are composite objects. Explicit calculational scheme is constructed for the energy density and the total number of thermodynamical degrees of freedom, based on the spectral function of the system. One demonstrates through characteristic examples that single quasiparticle contributions combine non-linearly in these quantities. Relation to the Gibbs paradox is also discussed.
Recently, a non-trivial relation between the quasi-particle spectrum and entanglement entropy production was discovered in non-integrable quenches in the paramagnetic Ising quantum spin chain. Here we study the dynamics of analogous quenches in the quantum Potts spin chain. Tuning the parameters of the system, we observe a sudden increase in the entanglement production rate, which is shown to be related to the appearance of new quasiparticle excitations in the post-quench spectrum. Our results demonstrate the generality of the effect and support its interpretation as the non-equilibrium versio…
Based on the property of extensivity (mathematically, homogeneity of first degree), we derive in a mathematically consistent manner the explicit expressions of the chemical potential $μ$ and the Clausius entropy $S$ for the case of monoatomic ideal gases in open systems within phenomenological thermodynamics. Neither information theoretic nor quantum mechanical statistical concepts are invoked in this derivation. Considering a specific expression of the constant term of $S$, the derived entropy coincides with the Sackur-Tetrode entropy in the thermodynamic limit. We demonstrate however, that t…
