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AIP conference proceedings

Gibbs Paradox as Property of Observation, Proof of II. Principle of Thermodynamics

Bohdan Hejna, Daniel M. Dubois

Published Jan 1, 2010• 5 citations
Publisher

Abstract

Our way to deal with the given topic is a connection of both the mathematical definitions of information entropies and their mutual relations within a system of stochastic quantities especially with thermodynamic entropies defined on an isolated system in which a realization of our (repeatable) observation is performed [it is a (cyclic) transformation of heat energy of an observed, measured system].We use the information description to analyze Gibbs paradox reasoning it as a property of such observation, measuring of an (equilibrium) thermodynamic system.We state a logical proof of the II. P.T. as a derivation of relations among the entropies of a system of stochastic variables, realized physically, and, the Equivalence Principle of the I., II. and III. Principle of Thermodynamics is formulated.

DOI
10.1063/1.3527148

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Our way to deal with the given topic is a connection of both the mathematical definitions of information entropies and their mutual relations within a system of stochastic quantities especially with thermodynamic entropies defined on an isolated system in which a realization of our (repeatable) observation is performed [it is a (cyclic) transformation of heat energy of an observed, measured system].We use the information description to analyze Gibbs paradox reasoning it as a property of such observation, measuring of an (equilibrium) thermodynamic system.We state a logical proof of the II. P.T. as a derivation of relations among the entropies of a system of stochastic variables, realized physically, and, the Equivalence Principle of the I., II. and III. Principle of Thermodynamics is formulated.
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 note is essentially pedagogical; we add to their analysis by examining the paradox from the point of view of information theory. Our argument is based on that ‘grouping’ property of entropy that Shannon recognized, by including it among his axioms, as an essential requirement on any measure of information. Not only does it provide the right connection between different entropies but, in addition, it draws our attention to the obvious fact that addressing issues of distinguishability and of counting states requires a clear idea about what precisely do we mean by a state.
The physical meaning of the entropy defect and information in quantum systems is analyzed in connection with Gibbs paradox and the M(uimLun work obtainable by use of a non-equilibrium system. The question is studied of the maximum amount of heat that can be converted into mechanical work in the process of isothermic mixing of two gases, whose molecules differ only in their quantum states, having non-commuting density matrices. It is shown that schemes for producing work that involve direct discrimination of nonorthogonal states (such as the method of semipermeable partitions) yield an amount of work that is determined not by the entropy ddect. but by the information in the system about its state, which reflects the fundamental irreversibility of the measurement process. An equivalence relation is suggested between quantum information and work.
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 between the gases. The proper approach employs quantum thermodynamics, which deals with finite quantum systems coupled to a large bath and a macroscopic work source. Within quantum thermodynamics, entropy generally loses its dominant place and the target of the paradox is naturally shifted to a decrease of the maximally available work before and after mixing (mixing ergotropy). In contrast to entropy this is an unambiguous quantity. For almost identical gases the mixing ergotropy continuously goes to zero, thus resolving the paradox. In this approach the concept of "difference between the gases" gets a clear operational meaning related to the possibilities of controlling the involved quantum states. Difficulties which prevent resolutions of the paradox in its entropic formulation do not arise here. The mixing ergotropy has several counterintuitive features. It can increase when less precise operations are allowed. In the quantum situation (in contrast to the classical one) the mixing ergotropy can also increase when decreasing the degree of mixing between the gases or when decreasing their distinguishability. These points go against a direct association of physical irreversibility with lack of information.
The Gibbs paradox in statistical mechanics is often taken to indicate that already in the classical domain particles should be treated as fundamentally indistinguishable. This paper shows, on the contrary, how one can recover the thermodynamical account of the entropy of mixing, while treating states that only differ by permutations of similar particles as distinct. By reference to the orthodox theory of thermodynamics, it is argued that entropy differences are only meaningful if they are related to reversible processes connecting the initial and final state. For mixing processes, this means that processes should be considered in which particle number is allowed to vary. Within the context of statistical mechanics, the Gibbsian grandcanonical ensemble is a suitable device for describing such processes. It is shown how the grandcanonical entropy relates in the appropriate way to changes of other thermodynamical quantities in reversible processes, and how the thermodynamical account of the entropy of mixing is recovered even when treating the particles as distinguishable.
The Gibbs Paradox is an important question in thermodynamics. In this thesis I search for a solution for the paradox from a classical, philosophical and quantum mechanical point of view. A common way to solve the Gibbs Paradox is by using the reduced entropy. However, this definition of entropy should not be interpreted as an argument for the indistinguishability of identical particles, because all other particles which have unique trajectories through space-time are distinguishable in principle. The Gibbs paradox could be solved in a few ways, but each solution has certain constrains.
Thermodynamics and information have intricate interrelations. Often thermodynamics is considered to be the logical premise to justify that information is physical - through Landauer's principle -, thereby also linking information and thermodynamics. This approach towards information has been instrumental to understand thermodynamics of logical and physical processes, both in the classical and quantum domain. In the present work, we formulate thermodynamics as an exclusive consequence of information conservation. The framework can be applied to the most general situations, beyond the traditional assumptions in thermodynamics: we allow systems and thermal baths to be quantum, of arbitrary sizes and even possessing inter-system correlations.Here, systems and baths are not treated differently, rather both are considered on an equal footing. This leads us to introduce a ''temperature''-independent formulation of thermodynamics. We rely on the fact that, for a fixed amount of information, measured by the von Neumann entropy, any system can be transformed to a state with the same entropy that possesses minimal energy. This state, known as a completely passive state, acquires Boltzmann-Gibbs canonical form with an intrinsic temperature. We introduce the notions of bound and free energy and use them to quantify heat and work, respectively. Guided by the principle of information conservation, we develop universal notions of equilibrium, heat and work, Landauer's principle and universal fundamental laws of thermodynamics. We demonstrate that the maximum efficiency of a quantum engine with a finite bath is in general lower than that of an ideal Carnot engine. We introduce a resource theoretic framework for our intrinsic temperature based thermodynamics, within which we address the problem of work extraction and state transformations. Finally, the framework is extended to multiple conserved quantities.