Entropy is the distinguishing and most important concept of our efforts to understand and regularize our observations of a very large class of natural phenomena, and yet, it is one of the most contentious concepts of physics. In this article, we review two expositions of thermodynamics, one without reference to quantum theory, and the other quantum mechanical without probabilities of statistical mechanics. In the first, we show that entropy is an inherent property of any system in any state, and that its analytical expression must conform to eight criteria. In the second, we recognize that quantum thermodynamics: (i) admits quantum probabilities described either by wave functions or by nonstatistical density operators; and (ii) requires a nonlinear equation of motion that is delimited by but more general than the Schroedinger equation, and that accounts for both reversible and irreversible evolutions of the state of the system in time. Both the more general quantum probabilities, and the equation of motion have been defined, and the three laws of thermodynamics are shown to be theorems of this equation.
Entropy is the distinguishing and most important concept of our efforts to understand and regularize our observations of a very large class of natural phenomena, and yet, it is one of the most contentious concepts of physics. In this article, we review two expositions of thermodynamics, one without reference to quantum theory, and the other quantum mechanical without probabilities of statistical mechanics. In the first, we show that entropy is an inherent property of any system in any state, and that its analytical expression must conform to eight criteria. In the second, we recognize that quantum thermodynamics: (i) admits quantum probabilities described either by wave functions or by nonstatistical density operators; and (ii) requires a nonlinear equation of motion that is delimited by but more general than the Schroedinger equation, and that accounts for both reversible and irreversible evolutions of the state of the system in time. Both the more general quantum probabilities, and the equation of motion have been defined, and the three laws of thermodynamics are shown to be theorems of this equation.
In the scientific and engineering literature, entropy—the distinguishing feature of thermodynamics from other branches of physics—is viewed with skepticism, and thought to be not a physical property of matter—like mass or energy—but a measure either of disorder in a system, or of lack of information about the physics of a system in a thermodynamic equilibrium state, and a plethora of expressions are proposed for its analytical representation. In this article, I present briefly two revolutionary nonstatistical expositions of thermodynamics (revolutionary in the sense of Thomas Kuhn, The Structure of Scientific Revolutions, U. Chicago Press, 1970) that apply to all systems (both macroscopic and microscopic, including one spin or a single particle), to all states (thermodynamic equilibrium, and not thermodynamic equilibrium), and that disclose entropy as an intrinsic property of matter.The first theory is presented without reference to quantum mechanics even though quantum theoretic ideas are lurking behind the exposition. The second theory is a unified quantum theory of mechanics and thermodynamics without statistical probabilities, that is, I am not presenting another version of statistical quantum mechanics.
Numerous expressions exist in the scientific literature purporting to represent entropy. Are they all acceptable? To answer this question, we review the thermodynamic definition of entropy, and establish eight criteria that must be satisfied by it. The definition and criteria are obtained by using solely the general, nonstatistical statements of the first and second laws presented in Thermodynamics: Foundations and Applications [Elias P. Gyftopoulos and Gian Paolo Beretta (Macmillan, New York, 1991)]. We apply the eight criteria to each of the entropy expressions proposed in the literature and find that only the relation S=-kTr\ensuremath{\rho}ln \ensuremath{\rho} satisfies all the criteria, provided that the density operator \ensuremath{\rho} corresponds to a homogeneous ensemble of identical systems, identically prepared. Homogeneous ensemble means that every member of the ensemble is described by the same density operator \ensuremath{\rho} as any other member, that is, the ensemble is not a statistical mixture of projectors (wave functions).
Abstract Numerous expressions exist in the scientific literature purporting to represent entropy. Are they all acceptable? To answer this question, we review the thermodynamic definition of entropy, and establish eight criteria that must be satisfied by it. The definition and criteria are obtained by using solely the general, nonstatistical statements of the first and second laws presented in Thermodynamics: Foundations and Applications by Gyftopoulos and Beretta (1991). We apply the eight criteria to each of the expressions proposed in the literature and, for the first time, find that only the relation S = −kTrρlnρ satisfies all the criteria, provided that the density operator ρ corresponds to a homogeneous ensemble of identical systems, identically prepared. Homogeneous ensemble means that every member of the ensemble is described by the same density operator ρ as any other member, that is, the ensemble is not a statistical mixture of projectors (wave functions).
A general quantum theory encompassing Mechanics, Thermodynamics and irreversible dynamics is presented in two parts. The first part is concerned exclusively with the description of the states of any individual physical system. It is based on a new nonlinear quantum equation of motion, which reduces to the Schroedinger equation of motion of motion of conventional quantum dynamics only under special conditions. It accounts for the implications of the laws of Thermodynamics as well as for irreversible phenomena, such as the natural tendency of an isolated system to transit from any non-equilibrium state to an equilibrium state of higher entropy. Conversely, the laws of Thermodynamics and irreversibility emerge as manifestations of the fundamental quantum dynamical behaviour of the elementary constituents of any material system. We call this part Quantum Thermodynamics. The second part of the theory, which contains the first as a special case, is concerned with the description of stochastic distributions of states in an ensemble of identical physical systems each of which individually obeys the laws of Quantum Thermodynamics. It is based on a new measure-theoretic description of ensembles. It accounts unambiguously for the essential distinction between two types of uncertainties that are generally present in an ensemble, namely, quantal uncertainties due to the inherent quantal nature of the states of each individual member system and nonquantal uncertainties due to the stochastic distribution of states. We call this part Quantum Statistical Thermodynamics.
What is the physical significance of entropy? What is the physical origin of irreversibility? Do entropy and irreversibility exist only for complex and macroscopic systems? The bulk of the physics community accepts and teaches that all these fundamental questions are rationalized within statistical mechanics. Indeed, for everyday laboratory physics, the mathematical formalism of statistical mechanics (canonical and grandcanonica1, Boltzmann, Bose-Einstein and Fermi-Dirac distributions) allows a successful description of the thermodynamic equilibrium properties of matter, including entropy values. But an ever growing handful of physicists (Schrodinger among the first) have realized that, even in its explanation of the meaning of entropy, statistical mechanics is impaired by ambiguities and logical inconsistencies. They have started to search for a better theory to eliminate these stumbling blocks while maintaining the mathematical formalism that has been so successful in so many applications. This handful of upstreamers must not be confused with the many schools of physicists that have thrived on the more renowned incompleteness of statistical mechanics, namely, the lack of a quantitative (and the weakness of the qualitative) explanation of the origin of irreversibility. In these studies the thrust is provided by the discovery that the macroscopic dynamics of certain complex systems may be modeled using a few-degrees-of-freedom nonlinear Hamiltonian with singularities that give rise to bifurcations and chaotic behavior. These results have generated successful ways to describe irreversible behavior, but their link to the origin of irreversibility is still only heuristic (what is the connection between the nonlinear model Hamiltonian and the true full Hamiitonian?) and does not provide yet a rigorous resolution of the century-old paradox of the conflict between the irreversibiiity of macroscopic behavior, and the reversibility of the laws of mechanics. To resolve both the problem of the meaning of entropy and that of the origin of irreversibility we have built entropy and irreversibility into the laws of mechanics. The result is a theory that we call quantum thermodynamics that has all the necessary properties to combine mechanics and thermodynamics uniting all the successful results of both theories, eliminating the logical inconsistencies of statistical mechanics and the paradox on irreversibiiity, and providing an entirely new perspective on the microscopic origin of irreversibility, nonlinearity and therefore chaotic behavior. The mathematical formalism of quantum thermodynamics differs from that of statistical mechanics mainly in the equation of motion which is nonlinear but has solutions identical to those of the Schrodinger equation for all the states for which statistical mechanics reduces to quantum mechanics. The physical meaning of the formalism of quantum thermodynamics differs more drastically from that of statistical mechanics. The significance of the state operator of quantum thermodynamics is entirely different from that of the density operator of statistical mechanics, even though the two are mathematically equivalent. Indeed they obey different equations of motion. In particular, quantum thermodynamics is concerned only with those systems for which quantum mechanics would describe the states with vectors in Hilbert space or, equivalently, projection operators. Using a well known jargon, we can say that quantum thermodynamics like quantum mechanics is concerned only with pure quantum states. However, it postulates that the set of pure quantum states of a system is much broader than contemplated by quantum mechanics. Pure quantum states must be described by operators defined by all the features of projection operators except the condition of idempotence. As a result, an operator that within statistical mechanics would describe a mixed quantum state (that is, the average state of a statistical mixture of identical systems in different pure quantum states) in quantum thermodynamics describes a pure quantum state, a state that neither quantum mechanics non statistical mechanics would contemplate. Conceptually, the increased richness of pure quantum states is a new revolutionary postulate of quantum physics. But from the point of view of the statistical mechanics practitioners the new theory is not as traumatic as it seems. Whenever one uses a nonidempotent density operator to describe a thermodynamic equilibrium state one simply has to reinterpret it as one of the new pure quantum states. One even saves the usual ad hoc arguments on thermal baths and reservoirs that are usually required in statistical mechanics to justify the use of a nonidempotent density operator to describe the state of a system. In this paper we discuss the background and formalism of quantum thermodynamics including its nonlinear equation of motion and the main general results. Our objective is to show in a not-too-technical manner that this theory provides indeed a complete and coherent resolution of the century-old dilemma on the meaning of entropy and the origin of irreversibility. As a byproduct, we discuss a long set of criteria that a theory should meet in order to afford the same claim.
The prevailing beliefs in the scientific and engineering literature are that: (i) thermodynamics is explained and justified by statistical mechanics; (ii) entropy is a statistical measure of disorder; and (iii) for given values of energy, volume, and amounts of constituents, the largest value of entropy corresponds to both a thermodynamic equilibrium state and the ultimate disorder. In this paper, we provide: (i) a summary of the beliefs as stated by some eminent scientists; (ii) experimental evidence that casts serious doubt about the validity of the beliefs; (iii) an outline of a nonstatistical unified quantum theory of mechanics and thermodynamics; (iv) an outline of a nonquantal, nonstatistical exposition of thermodynamics, valid for all systems (both macroscopic and microscopic), and for all states (both thermodynamic equilibrium and not thermodynamic equilibrium); (v) the definition and analytical expression of the entropy of thermodynamics; (vi) the interpretation of entropy as both a measure of the quantum-theoretic spatial shape of a molecule, and an indicator of order; and (vii) nonstatistical answers to the questions that motivated the introduction of statistical mechanics.