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arXiv:1109.6204

Canonical formulation of Thermodynamics, and corresponding wave equation for far from equilibrium case

Adrian Faigon

Published Sep 28, 2011• 0 citations
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Abstract

Lagrange and Hamilton equations for thermodynamic evolution near equilibrium as well as Schrodinger-like equation for the non-equilibrium case are obtained extending the CPDQ Principle (Constancy of the product momentum-oordinate uncertainty) to a new conjugate pair where the momentum f is the extension of the mechanical f=p.δq product for the case the coordinate q is not directly observable. Applied to the case of a particle in a one dimension box, the results are in agreement with reported calculated and measured thermal conductance.

DOI
10.48550/arxiv.1109.6204

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Lagrange and Hamilton equations for thermodynamic evolution near equilibrium as well as Schrodinger-like equation for the non-equilibrium case are obtained extending the CPDQ Principle (Constancy of the product momentum-oordinate uncertainty) to a new conjugate pair where the momentum f is the extension of the mechanical f=p.δq product for the case the coordinate q is not directly observable. Applied to the case of a particle in a one dimension box, the results are in agreement with reported calculated and measured thermal conductance.
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Abstract Quantum thermodynamics describes dynamic processes by means of the operators of entropy production P and time t . P and t do not commute. It exists the non-vanishing t–P commutator [ t , P ]=ik. Here the Boltzmann constant k has the physical meaning of a quantum of entropy. The t–P commutator immediately leads us to the t–P uncertainty relation ΔtΔP≥k/2. Hence the observables t and P are not sharply defined simultaneously. Similar uncertainty relations can also be expected for other pairs of conjugate variables with products of the physical meaning of an entropy. The free energy F and the reciprocal temperature (1/T) are the respective conjugate variables of an isolated system of many particles, which leads us to the F–(1/T) uncertainty relation ǀΔFǁΔ(1/T)ǀ≥k/2. It can be traced back to the t–P uncertainty relation mentioned above. In this way the Helmholtz free energy F and the temperatur T are introduced into quantum thermodynamics. The uncertainties ǀΔFǀ→0 and ǀΔTǀ→0 are negligible at low temperatures T→0, and quantum thermodynamics turns into the time-independent classical thermodynamics. Against this the uncertainties ǀΔFǀ→∞ and ǀΔTǀ→∞ grow unlimited at high temperatures T→∞, and classical thermodynamics loses its sense. In the limit of one particle the uncertainties cannot be neglected even at low temperatures. However a detailed discussion shows that the free energy f of a single particle vanishes within the whole range of temperatures T. This defines the particle entropy σ=ε/T=ak. The dimensionless entropy number a connects the particle energy ε=akT with the temperature T. The entropy number a of a single (s) independent particle can be calculated with the extended, temperature-dependent Schrödinger equation A s φ=aφ. Here A s=−(Λ 2/4π)∇2 means the dimensionless entropy operator describing the entropy number a and thus the particle entropy σ=ak. Λ is the thermal de Broglie wave length. Finally we calculate by means of quantized particle entropies σ the internal energy E, the Helmholtz free energy F, the entropy S, the chemical potential μ, and the equation of state of an ideal gas of N monatomic free particles in full agreement with classical thermodynamics. We also calculate the partition function q=V/Λ 3 of a single free particle within the volume V. Here Λ 3 is a small volume element taking into account the wave–particle dualism of a single free particle of mass m at temperature T. Extension to a system of N free particles leads us to a simple geometrical model and to the conclusion that an ideal gas of independent particles becomes instable below a critical temperature T C. T C corresponds to the critical temperature T BE of Bose–Einstein condensation.
The usual Heisenberg uncertainty relation, ΔX ΔP ≥ ℏ/2, may be replaced by an exact equality for suitably chosen measures of position and momentum uncertainty, which is valid for all wavefunctions. This exactuncertainty relation, δX ΔPnc ≡ ℏ/2, can be generalised to other pairs of conjugate observables such as photon number and phase, and is sufficiently strong to provide the basis for moving from classical mechanics to quantum mechanics. In particular, the assumption of a nonclassical momentum fluctuation, having a strength which scales inversely with uncertainty in position, leads from the classical equations of motion to the Schrödinger equation.
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Mechanics can be founded on a principle relating the uncertainty delta-q in the trajectory of an observable particle to its motion relative to the observer. From this principle, p.delta-q=const., p being the q-conjugated momentum, mechanical laws are derived and the meaning of the Lagrangian and Hamiltonian functions are discussed. The connection between the presented principle and Hamilton's Least Action Principle is examined. Wave mechanics and Schrodinger equation appear without additional assumptions by choosing the representation for delta-q in the case the motion is not trajectory describable. The Cramer-Rao inequality serves that purpose. For a particle hidden from direct observation, the position uncertainty determined by the enclosing boundaries leads to thermodynamics in a straightforward extension of the presented formalism. The introduction of uncertainty in classical mechanics formulation enables the translation of mechanical laws into the wide ranging conceptual framework of information theory. The boundaries between classical mechanics, thermodynamics and quantum mechanics are defined in terms of informational changes associated with the system evolution. As a direct application of the proposed formulation upper bounds for the rate of information transfer are derived.