We show that the second law of thermodynamics is rooted in quantum mechanics, inasmuch as allowing the substitution of the Boltzmann constant k and temperature with respectively the Planck constant and quantum numbers. In particular, we will see that the entropy S becomes proportional to the natural logarithm of the average of the squared quantum numbers n2‾, where each quantum number is associated with a quantum state of the constituents of the thermodynamical system under consideration. It is important to stress that the present approach furnishes the corrected Boltzmann entropy expression. Thus, instead of S=klnΩ, with Ω in the former signifying the number of Boltzmann microstates, we land at S=klnn2‾ The results obtained are discussed.
We show that the second law of thermodynamics is rooted in quantum mechanics, inasmuch as allowing the substitution of the Boltzmann constant k and temperature with respectively the Planck constant and quantum numbers. In particular, we will see that the entropy S becomes proportional to the natural logarithm of the average of the squared quantum numbers n2‾, where each quantum number is associated with a quantum state of the constituents of the thermodynamical system under consideration. It is important to stress that the present approach furnishes the corrected Boltzmann entropy expression. Thus, instead of S=klnΩ, with Ω in the former signifying the number of Boltzmann microstates, we land at S=klnn2‾ The results obtained are discussed.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
Abstract The 2nd law of thermodynamics is derived from the principle of least action, positing that the quantum of action is the indivisible and indestructible basic building block of everything. On their least-time paths to balance, the quanta move from the system to its surroundings, or vice versa, so that the kinetic, potential, and dissipated energy tally. When re-expressed in logarithmic terms, this current toward more probable states with decreasing free energy equates to the principle of increasing entropy, the 2nd law of thermodynamics, including path-independent dynamic and path dependent geometric phase shifts. Despite being exact, the equation of evolution to entropy maximum, equivalent to free energy minimum, cannot be solved because evolution, consuming its own driving forces, becomes path dependent. Thus, the future remains open within free energy bounds. As discussed, the entropy derived from the statistical physics of open quantum systems sums states distinguishable in energy; whereas, Boltzmann’s entropy enumerates microstates indistinguishable in energy. Consequently, the statistical physics of open systems differs from that of closed systems: The irreversible evolution in the state space toward thermodynamic balance contrasts with the steady-state revolution in phase space between conceivable configurations. This concrete comprehension explains, among other things, that increasing disorder is not a law of nature itself but a consequence of the law to attain balance with incoherent surroundings in the least time.
Abstract 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=S max. Against this, the entropy S ′ of an arbitrary non-equilibrium state is always smaller, S′ < S max (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=S max, or a non-equilibrium state, S=S′. Consequently, S cannot irreversibly change from S′ to S max. 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)|〈 G 〉|=(γ/2)k. This P − t uncertainty relation easily allows a discussion of the evolution of the entropy S in time t from S′ to S max. Now the irreversible steps are correctly described by the entropy production P=dS/dt > 0, and the thermal equilibrium by P=0, ∆P=0, and thus the lifetime ∆t=∞.
Abstract Part II of this two-part paper refutes the beliefs about the statistical interpretation of thermodynamics, and the association of entropy with disorder that are summarized in Part I. The refutation of the statistical approach is based on either a nonstatistical unified quantum theory of mechanics and thermodynamics, or an almost equivalent, novel, nonquantal exposition of thermodynamics. Entropy is shown to be: (i) valid for any system (both macroscopic and microscopic, including one-particle systems), and any state (both thermodynamic or stable equilibrium, and not stable equilibrium); (ii) a measure of the quantum-theoretic pliable shape of the molecules of a system; and (iii) a monotonic indicator of order. In contrast to statistics which associates a thermodynamic equilibrium macrostate with the largest number of compatible microstates, the second law avers that, for each set of values of energy, volume, and amounts of constituents of either a macroscopic or a microscopic system, there exists one and only one thermodynamic or stable equilibrium state. So, even if Boltzmann’s definition were used, a thermodynamic equilibrium state is one of perfect order.