Information-theoretic stability and evolution criteria in irreversible thermodynamics

Generalized information gains are used to derive stability conditions, for steady states, periodic orbits and invariant sets, and general evolution criteria, both global and local with respect to the time variable, in irreversible thermodynamics. Meixner's passivity condition and the Glansdorff-Prigogine stability and evolution criteria are found to be special cases thereof. The information gain quantities include Kullback's three kinds of divergences, the first two of which are dual to each other and yield criteria which are symmetric in the average densities of the system's extensive variables and the conjugate parameters, but which are nonsymmetric in the irreversible fluxes and forces, while the third one does not involve the entropy function of the system. Furthermore, Renyi's information gain of order and Csiszar'sf-divergence are treated. The latter is used to construct a most general information gain quantity as a Liapunov function and evolution criterion, which, however, for local stability and evolution conditions is still equivalent to the use of the second-order variation of the entropy.Supported by the Deutsche Forschungsgemeinschaft.     

The kinetic foundation of extended irreversible thermodynamics revisited

Extended irreversible thermodynamics (EIT) has been used mainly to study the short-time behavior of fluids and some other systems. It has also been shown how the structure of the equations of motion constructed for the so-called relaxation variables coincides with those obtained by means of Grad's method in kinetic theory. In this work we calculate the generalized entropy from the one-particle distribution function up to 26 moments. We find that the characteristics of such entropy and the equations of motion for the relaxing variables are supported by the kinetic theory. This is not the case for the hierarchical relaxation hypothesis which is used in the applications of EIT to the generalized hydrodynamic regime.On temporary leave at the Universidad Iberoamericana, Mexico.     

非平衡热力学中传热过程熵产表达式的修正

熵产是非平衡热力学中的核心物理量,传统上表示为广义力(驱动力)与广义流的乘积.这种表达存在两方面缺陷:一是广义力与广义流的拆分具有任意性;更重要的是,以其计算热波传递时熵产可以为负值,从而违反热力学第二定律.本文基于热质理论分析表明,传热过程的熵产实质上是由热质流体的热质能耗散引起的,所以熵产中的力不是驱动力而是阻力,并且具有力的量纲.由此提出的熵产修正表达式,不仅在计算热波传递过程中熵产恒为正值,与扩展不可逆热力学中的熵产表达式一致,而且不存在力和流拆分的任意性.     

A kinetic derivation of extended irreversible thermodynamics

The basic postulates of the extended irreversible thermodynamics are derived from the kinetic model for a dilute monoatomic gas. Using the Grad 13-moment method to solve the full nonlinear Boltzmann equation for molecules conceived as soft spheres we obtain the microscopic expressions for the entropy flux, the entropy production, and the generalized Pfaffian for the extended definition of entropy as required by such a theory. Some of the physical implications of these results are discussed.Member, Colegio Nacional.     

Non-equilibrium thermodynamic potential and flux fluctuation theorem

A flux fluctuation theorem proposed recently [Seitaridou, et al., J. Phys. Chem. B 111 (2007) 2288] on the relative probability of direct and reverse diffusion fluxes in a non-equilibrium steady state is related here to a non-equilibrium thermodynamic potential used in extended irreversible thermodynamics. This connection allows one to provide a new derivation of the theorem, which complements the previous one, to generalize it to other fluxes, and illustrates the thermodynamic relevance of this theorem.     

Anomalous light scattering at the surface of growing ice crystals and thermodynamics of irreversible processes

The framework of nonequilibrium thermodynamics is used to study the phenomenon of enhanced Rayleigh scattering from the liquid-solid interface of a growing crystal. The scattering is treated as resulting from small objects of finite lifetime produced at the interface by the growth process and confined thereafter to one phase or the other. The thermodyanmic analysis leads to the formation, adjacent to the interface, of a boundary layer, various properties of which are studied. The analysis is then used to discuss the data obtained in two different experiments on the anomalous light scattering from the ice-water interface. It is found that the various data presented in these two experiments cannot be reconciled with each other in all respects.     

Mesoscopic transport equations and contemporary thermodynamics: an introduction

The local equilibrium hypothesis is a very successful basis for non-equilibrium thermodynamics over a wide range of phenomena and physical situations. However, the increasing interest in small systems in nanotechnology, in rarefied gases in high-altitude aeronautics, in high-frequency behaviour in information processing, or the search for new materials with sophisticated internal microstructures and tailored thermal properties have led one to ask about the limits of validity of this hypothesis, and to go beyond it. Here we do so in a constructive way, i.e. not only pointing out at these limits, but also embedding the local-equilibrium theory in a more general framework which explicitly exhibits these limits and suggests how to go beyond them, in search for a wider range of applications and a deeper understanding of the foundations.     

热力学第二定律理论体系的讨论

热力学第二定律原有的两个理论体系都有明显的不足之处,为此,综全各种方法的优点,利用我们提出的简单物质可逆补热循环以及微分方程基本理论,简单明确地直接由热力学第二定律的开尔文表述推导克劳修斯等式、不等式,在推导过程中自然地引出绝对温度,得到热力学熵和增加原理,从而建立起热力学第二定律的新理论体系。     

LocalH-theorem for a kinetic variational theory

A localH-theorem is derived for a recently proposed extension of Enskog kinetic theory to a dense model fluid composed of particles with interactions extending beyond a hard core.On leave from: Katedra Fizyki, Uniwersytetu Szczecinskiego, 70-451 Szczecin, Poland.     

Nonequilibrium thermodynamics and the transport phenomena in magnetically confined plasmas

The neoclassical theory of transport in magnetically confined plasmas is reviewed. The emphasis is laid on a set of relationships existing among the banana transport coefficients. The surface-averaged entropy production in such plasmas is evaluated. It is shown that neoclassical effects emerge from the entropy production due to parallel transport processes. The Pfirsch-Schlüter effect can be clearly interpreted as due to spatial fluctuations of parallel fluxes on a magnetic surface: the corresponding entropy production is the measure of these fluctuations. The banana fluxes can be formulated in a quasithermodynamic form in which the average entropy production is a bilinear form in the parallel fluxes and the conjugate generalized stresses. A formulation as a quadratic form in the thermodynamic forces is also possible, but leads to anomalies, which are discussed in some detail.     

On the Enskog-Thorne theory for a binary mixture of dissimilar rigid spheres

Thorne's method for obtaining transport coefficients in a binary rigid-sphere mixture is reexamined. First, a close look is taken at the way in which the point where the Enskog functionsx _ij are evaluated is introduced. Second, the calculation of the fluxes in the system and the transport coefficients is given. Thorne's results are found to be correct and independent of the choice of the point where the transfer plane is located. This does not hold true for the diffusion flux. It is shown that a different diffusion force is obtained for each selection and that only those diffusional effects which are of first order in the density are consistent with irreversible thermodynamics.     

On applicability of Gibbs thermodynamics to nanoparticles

The problem of applicability of thermodynamics to small objects has been investigated. It is shown that the Gibbs surface phase method may be extended to nanoparticles if the effective surface tension (the specific excess free energy) is interpreted as a function of the particle radius. Dedicated to the Centennial of J.W. Gibb's Death     

Fluctuation Theorem for Currents and Schnakenberg Network Theory

A fluctuation theorem is proved for the macroscopic currents of a system in a nonequilibrium steady state, by using Schnakenberg network theory. The theorem can be applied, in particular, in reaction systems where the affinities or thermodynamic forces are defined globally in terms of the cycles of the graph associated with the stochastic process describing the time evolution.     

Core potential of intermolecular forces applied to third virial coefficients and transport coefficients of polyatomic gases

The three-molecular cluster integrals for oxygen, nitrogen, and carbon tetrafluoride and the coefficients of viscosity and self-diffusion for nitrogen and carbon dioxide are discussed on the basis of the Kihara convex-core potential of intermolecular forces. For the equilibrium property, the relative size of the core is essential; for the transport properties, the nonspherical character of the molecule plays an important role.     

H-theorem for the (modified) nonlinear Enskog equation

We construct anH-function suitable for a system of dense hard spheres satisfying the (modified) nonlinear Enskog equation and we show that _t H 0. The equality sign holds only when the system has reached absolute equilibrium, in which caseS=– k_B H becomes the exact equilibrium entropy of the hard-sphere fluid.     

Markovian description of irreversible processes and the time randomization

A certain class of kinetic equations, which describe the Markov-type irreversible evolution of the system, consistent with the second law of thermodynamics and with the relaxation postulate, has been distinguished. The physical meaning of these kinetic equations is that they describe thermally activated processes. The time asymmetry, observed on the macrolevel as the thermodynamical irreversibility of the process, is represented on the microlevel by the Markov-type randomization of the moments of the jump-like change of the microstates of the system. As an example, the thermodynamical interpretation of the one-particle stochastic model of the many-body system is discussed. The authors of this paper have agreed to not receive the proofs for correction