Thermodynamics is the science that deals with all the phenomena that involve the transfer of energy, i.e. heat and work. Its development started in 1824 with the efforts of Sadi Carnot to improve the closed-cycle steam engine discovered by James Watt in 1764. In 1850, R. Clausius laid the foundations of the laws of thermodynamics. Soon thereafter a conflict between the second law of Thermodynamics and the laws of mechanics was pointed out by Maxwell in 1871 and was illustrated clearly by what has come to be known as Maxwell’s demon. This conflict was addressed by Brillouin (1949) based on the work of Szilard (1929) and of many others. They all claimed that although the objective state of a system is fully describable by mechanics, classical or quantum, and evolves according to the laws of mechanics, some states of the system as perceived by an observer are subjective and reflect the lack of information the observer has about the actual mechanical state of the system. This point of view is, in effect, the information-theory interpretation of thermodynamics which, currently, is widely accepted. The central point of this paper is to describe the reasons why the information-theory interpretation of thermodynamics is contrary to physical reality. It shows that a logically viable hypothesis which reconciles mechanics with thermodynamics is the existence in nature of physical states that have objective uncertainties broader than those implied in quantum theory as it is traditionally formulated. The consequences of this hypothesis are presented in the Unified Quantum Theory of Mechanics and Thermodynamics, by Hatsopoulos and Gyftopoulos.An initial version of this paper was published inJuly of 2006 in the proceedings of ECOS’06, AghiaPelagia, Crete, Greece.
Thermodynamics is the science that deals with all the phenomena that involve the transfer of energy, i.e. heat and work. Its development started in 1824 with the efforts of Sadi Carnot to improve the closed-cycle steam engine discovered by James Watt in 1764. In 1850, R. Clausius laid the foundations of the laws of thermodynamics. Soon thereafter a conflict between the second law of Thermodynamics and the laws of mechanics was pointed out by Maxwell in 1871 and was illustrated clearly by what has come to be known as Maxwell’s demon. This conflict was addressed by Brillouin (1949) based on the work of Szilard (1929) and of many others. They all claimed that although the objective state of a system is fully describable by mechanics, classical or quantum, and evolves according to the laws of mechanics, some states of the system as perceived by an observer are subjective and reflect the lack of information the observer has about the actual mechanical state of the system. This point of view is, in effect, the information-theory interpretation of thermodynamics which, currently, is widely accepted. The central point of this paper is to describe the reasons why the information-theory interpretation of thermodynamics is contrary to physical reality. It shows that a logically viable hypothesis which reconciles mechanics with thermodynamics is the existence in nature of physical states that have objective uncertainties broader than those implied in quantum theory as it is traditionally formulated. The consequences of this hypothesis are presented in the Unified Quantum Theory of Mechanics and Thermodynamics, by Hatsopoulos and Gyftopoulos.An initial version of this paper was published inJuly of 2006 in the proceedings of ECOS’06, AghiaPelagia, Crete, Greece.
In 1824, the French physicist Nicolas Léonard Sadi Carnot, better known as Sadi Carnot, in Refl ections on the Motive Power of Fire settled the principles of the modern theory of thermodynamics by pointing out that motive power (concept later identi- ed as work) is due to the fall of caloric (concept later identi ed as heat) from a hot to cold body (working substance). ese ideas that provided the scienti c support for the technological jump based on the steam engine were not well understood at that time. ey were actually discovered and further elaborated 30 years later by the German Rudolf Clausius and the British William omson (Lord Kelvin). e fundamental principles ruling the operation of the thermal engines were then summarized in the two basic laws of thermodynamics. While the rst law simply stresses the conservation of the energy, the second one deals with the subtle distinction between a kind of energy that can be used and another one that is dissipated in a physical process, as well as on the balance between both of them.
The purpose of this paper is to discuss the hypothesis that the second law of thermodynamics and its corollaries are manifestations of microscopic quantum effects of the same nature but more general than those described by the Heisenberg uncertainty principle. This hypothesis is new to physics. Energy is a property of matter that has unified our understanding of physical phenomena. It appears prominently in both mechanical and thermodynamic theories. It is defined by the first law of thermodynamics, and its conservation is one of the keystones of analyses of both microscopic and macroscopic phenomena. Adiabatic availability--the amount of work that can be extracted from a system adiabatically--is also a property of matter but has not been accepted with the same unanimity as energy. Experience, especially with large bodies, indicates that not all the energy of a system is available in the form of work. For a given system, say atoms
The author presents his experience in teaching at a graduate level the quantal exposition of a new non-statistically based paradigm of physics and thermodynamics. This paradigm, called the Unified Quantum Theory of Mechanics and Thermodynamics, applies to all systems large or small (including one particle systems) either in a state of thermodynamic (i.e. stable) equilibrium or not in a state of thermodynamic equilibrium. It uses as its primitives inertial mass, force, and time and introduces the laws of thermodynamics in the most unambiguous and general formulations found in the literature. Starting with a precise definition of system and of state followed by statements and corollaries of the laws of thermodynamics, the thermodynamic formalism is developed without circularity and ambiguity. In this quantal exposition of the new paradigm, a brief review of the formalism of thermodynamics as a general science not limited to stable equilibrium and large (macroscopic) systems as well as a very brief summary of the three prevalent formalisms in classical physics are presented followed by a presentation and development of solutions for a number of elementary problems in quantum physics (e.g., a particle in a box, a harmonic oscillator, a rigid rotor, etc.). These solutions and the maximum entropy principle are then used in a constrained optimization to develop the canonical and grand canonical distributions for Fermi-Dirac and Bose-Einstein types of particles, i.e. for fermions and bosons. This is done without the use of analogies between statistical and thermodynamic results and without additional hypotheses such as the ergodic hypothesis of statistical mechanics. These distributions are then employed under various assumptions (i.e. the Boltzmann, constant-potential, point-particle, and continuous eigenvalue-spectrum approximations) to derive the corresponding thermodynamic property expressions for perfect, semi-perfect (ideal), and Sommerfeld gases as well as for mixtures of ionized and dissociated gases. In a similar fashion but with a change from a single- to a multi-particle partition function and with the addition of various inter-particle potentials for two-particle interactions (e.g., the Lennard-Jones potential, the square-well potential, etc.), expressions for the thermodynamic properties of dense gases are developed and presented.An initial version of this paper was published inJuly of 2006 in the proceedings of ECOS’06, AghiaPelagia, Crete, Greece.
In Chapter 3 the introduction of entropy as a state function was facilitated by the realization that there exist possible and impossible processes, and by an examination of the heat and work effects occurring during these processes. From the formal statement of the Second Law of Thermodynamics, as developed from Classical Thermodynamics arguments, it is difficult to assign a physical significance or a physical quality to entropy. In this respect entropy differs from internal energy in spite of the fact that, within the scope of Classical Thermodynamics, both properties are simply mathematical functions of the state of a system. The ready acceptance of the First Law of Thermodynamics, after its enunciation, was due to the easily understood physical significance of internal energy, whereas the lack of corresponding understanding of entropy caused the acceptance of the Second Law of Thermodynamics to be slow. From the classical viewpoint the Second Law is only valid as a direct result of the fact that, to date, human ingenuity has failed to invent a perpetual motion machine. Thus, within the scope of Classical Thermodynamics, the Second Law is a “law” only because it has not yet been disproved. The physical interpretation of entropy had to await the development of quantum theory and statistical mechanics.
With a class of quantum heat engines which consists of two-energy-eigenstate systems undergoing, respectively, quantum adiabatic processes and energy exchanges with heat baths at different stages of a cycle, we are able to clarify some important aspects of the second law of thermodynamics. The quantum heat engines also offer a practical way, as an alternative to Szilard's engine, to physically realize Maxwell's demon. While respecting the second law on the average, they are also capable of extracting more work from the heat baths than is otherwise possible in thermal equilibrium.
Thermodynamics is one of the main pillars of theoretical physics, and it has a special appeal of having wide applicability to a large variety of different physical systems. However, many assumptions in thermodynamics apply only to systems which are bulk material, i.e. consisting a large number of microscopic classical particles. Due to the advancement of designing nanoscale engines, especially in the light of devices that are used today in the processing of quantum information, is thermodynamics still applicable? Can we refine the core principles of thermodynamics to suit such nanoscale quantum systems as well? The central aim of this thesis is to construct a theory of thermodynamics that holds for nanoscale quantum systems, even those as small and simple as a single qubit. We do this by starting out from the core basics of quantum theory: unitary dynamics on closed quantum systems. We adapt a resource theoretic approach inspired by quantum information theory, which defines the quantum states and operations allowed to be used in a thermodynamic evolution. With this framework that naturally adopts the first law as an energy preserving condition, we show the refinement of both the zeroeth and second law of thermodynamics. The zeroeth law explains the physical significance of the Gibbs thermal state. On the other hand, we show that the second law sees refinement in the quantum nanoregime: instead of having the free energy as the sole quantity dictating the possibility of a thermodynamic state transition, we derive a family of generalized free energies that also constitute necessary conditions for a transition to occur. Moreover, these conditions become sufficient for states which are block-diagonal in the energy eigenbasis. In this thesis, we also brought our approach of thermodynamics to the next step: we apply our findings on the second laws, in order to analyze the maximum achievable efficiency for quantum heat engines. In classical thermodynamics, the Carnot efficiency has been long known as the theoretical maximum which does not depend on the specific structure of the thermal baths used, but only on its temperature. With the additional free energies we discover, we show that although quantum heat engines may achieve the Carnot efficiency, such an achievability is no longer independent of the Hamiltonians of the thermal baths. In other words, we find additional restrictions that surface in the study of quantum nanoscale heat engines, which are a direct consequence of the generalized second laws. This has provided us with a deeper understanding into the fundamental limitations of how efficient devices can be made in the realm of microscopic quantum systems.