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Helmuth W. Zimmermann
Particle Entropies and Entropy Quanta: IV. The Ideal Gas, the Second Law of Thermodynamics, and the P–t Uncertainty Relation
The quantum thermodynamics of the ideal gas is treated by means of the particle entropies σ=ka. The non-dimensional entropy numbers a are calculated by the extended, temperature-dependent Schrödinger equation applying periodic boundary conditions. The Boltzmann constant k represents the atomic entropy unit. The quantized particle entropies a are used to calculate the Boltzmann distribution f=exp(α−a), the density of entropy levels D(a), the dimensionless chemical potential α=μ/kT, etc. – The thermodynamics of the ideal gas is treated on the basis of entropy quanta by means of the density matrix formalism. In this way we obtain the total particle entropy A, the thermodynamic entropy S (equation of Sackur-Tetrode), the internal and the Helmholtz free energy E and F, respectively, etc. Moreover, it can also be shown on the basis of entropy quanta that the entropy of a closed system in thermal equilibrium has a maximum value, S=Smax. Against this, the entropy S′ of an arbitrary non-equilibrium state is always smaller, S′ < Smax (second law of thermodynamics). – Application of ordinary density matrix theory to a closed system of N particles leads to the result that the entropy S does not change in time, dS/dt=0, regardless whether we consider an equilibrium state, S=Smax, or a non-equilibrium state, S=S′. Consequently, S cannot irreversibly change from S′ to Smax. However, any irreversible process is accompanied by a positive entropy production P=dS/dt>0. In order to overcome this obvious contradiction, we discuss the entropy evolution in time by means of the commutator equation G=i[P,t], which is deduced from very general assumptions. Here P and t are the operators of the entropy production P and the time t. Accordingly, P and t do not commute in general, and hence P and t are not sharply defined simultaneously. Instead we have uncertainties ΔP and Δt, which are expressed by the uncertainty relation of the N-particle system, ΔPΔt≥(1/2)
Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag
Print ISSN: 0942-9352
Volume: 217, 01/2003
Pages: 055