Statistics of distinguishable particles and resolution of the Gibbs paradox of the first kind (Q616225)

The author studies the analysis of Gibbs paradox I. (GB1), that is that two particles are taken distinguishable if they are either non-identical (they have different properties, or they are identical but there are in microstates which change under transposition of the particles). Here one is concerned with the false increase in entropy (calculated from the process of combining two gases of the same kind of distinguishable particles). The procedure is the following. For an ensemble of particles compositions the quantum-mechanical state is defined, the union of multiple phase space is introduced as a set of representatives for classical microstates. Then the conventional definition for particle transposition is extended. The statistical treatment is outlined for systems of distinguishable (non-identical) and identical classical particles and the uncertainty about the particle composition in the entropy is studied. The motion of a harmonic distinguishable system is introduced and it is shown that this is not a necessary property for systems of nonidentical particles; but this property has an important feature: the probabilites of possible compositions of a closed system cannot change in time, so for closed systems of non-identical particles the composition probabilities are part of the complete characterization of an equilibrium state. For harmonic systems the entropy is not additive and therefore loses its thermodynamic meaning. For such systems the reduced entropy is a good thermodynamic potential, and can take over its thermodynamic role. The situation produced by this consequence is discussed.