The entropy flux and the evolution equations for the fluxes including nonlocal terms from the point of view of extended irreversible thermodynamics

The expression for the entropy flux is analysed from the point of view of irreversible thermodynamics. In connection with this problem the evolution equations for the heat flux and for the electric current density including nonlocal terms are derived and discussed. The relation for the entropy flux is compared with that obtained by the statistical nonequilibrium thermodynamics on the basis founded on a generalized Gibbs' ensemble method for nonequilibrium systems.     

Relationship between the thermodynamics of nonequilibrium state and the thermodynamics of nonequilibrium processes

The concept and equations of the thermodynamics of nonequilibrium state are compared with the postulates of linear thermodynamics of nonequilibrium processes. It is shown that all the four basic postulates can be obtained as consequences of the equations of the thermodynamics of nonequilibrium state. In the limiting case of small deviations from equilibrium, the thermodynamics of nonequilibrium state are reduced to linear thermodynamics of nonequilibrium processes.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 10–14, December, 1990.     

Generalization of the second law for a transition between nonequilibrium states

The maximum work formulation of the second law of thermodynamics is generalized for a transition between nonequilibrium states. The relative entropy, the Kullback-Leibler divergence between the nonequilibrium states and the canonical distribution, determines the maximum ability to work. The difference between the final and the initial relative entropies with an effective temperature gives the maximum dissipative work for both adiabatic and isothermal processes. Our formulation reduces to both the Vaikuntanathan-Jarzynski relation and the nonequilibrium Clausius relation in certain situations. By applying our formulation to a heat engine the Carnot cycle is generalized to a circulation among nonequilibrium states.     

Molecular derivation of the hydrodynamic equations for a binary fluid

In this paper, the hydrodynamic equations and the associated transport coefficients are derived for a simple binary fluid from molecular considerations. This is a generalization of the methods of Felderhof and Oppenheim and of Selwyn to multicomponent systems. A linear response formalism is used to describe the relaxation of the binary system from an initial nonequilibrium state. Explicit molecular expressions are given for the transport coefficients in terms of time correlation functions of generalized current densities. These densities have the useful property of not containing a conserved part. The correlation functions are then related to a set of phenomenological coefficients in the theory of nonequilibrium thermodynamics. This explicit identification enables one to relate the correlation functions to experimentally measured transport coefficients.Supported by the National Science Foundation.     

Escort entropies and divergences and related canonical distribution

We discuss two families of two-parameter entropies and divergences, derived from the standard Rényi and Tsallis entropies and divergences. These divergences and entropies are found as divergences or entropies of escort distributions. Exploiting the nonnegativity of the divergences, we derive the expression of the canonical distribution associated to the new entropies and a observable given as an escort-mean value. We show that this canonical distribution extends, and smoothly connects, the results obtained in nonextensive thermodynamics for the standard and generalized mean value constraints.     

On a kinetic justification of the generalized nonequilibrium thermodynamics of multicomponent systems

The problem of the kinetic justification of the generalized thermodynamics of nonequilibrium processes using the method of moments for solving the kinetic equation for a multicomponent gas mixture is examined. Generalized expressions are obtained for the entropy density, entropy flux density, and entropy production as functions of an arbitrary number of state variables (moments of the distribution function). Different variants of writing the relations between fluxes and thermodynamic forces are considered, which correspond to the Onsager version for spatially homogeneous systems and, in a more general case, lead to the generalized thermodynamic forces of a complicated form, including derivatives of the fluxes with respect to time and spatial coordinates. Some consequences and new physical effects, following from the obtained equations, are analyzed. It is shown that a transition from results of the method of moments to expressions for the entropy production and the corresponding phenomenological relations of the generalized nonequilibrium thermodynamics is possible on the level of a linearized Barnett approximation of the Chapman–Enskog method.     

Phenomenological equations for multicomponent fluids

Ahydrodynamic equation of motion for each component of a multicomponent fluid is derived on the basis of nonequilibrium thermodynamics. Special care has been directed to the choice of state variables. In some limiting cases, this equation leads to customary phenomenological equations, such as the equation for diffusion and the Navier-Stokes equation. The viscosity is a consequence of nonlocal coupling of forces and fluxes. The reciprocity between the linear coefficients is examined closely.     

Locally Anisotropic Kinetic Processes and Thermodynamics in Curved Spaces

The kinetic theory is formulated with respect to anholonomic frames of reference on curved spacetimes. By using the concept of nonlinear connection we develop an approach to modelling locally anisotropic kinetic processes and, in corresponding limits, the relativistic nonequilibrium thermodynamics with local anisotropy. This leads to a unified formulation of the kinetic equations on (pseudo) Riemannian spaces and in various higher dimensional models of Kaluza–Klein type and/or generalized Lagrange and Finsler spaces. The transition rate considered for the locally anisotropic transport equations is related to the differential cross section and spacetime parameters of anisotropy. The equations of states for pressure and energy in locally anisotropic thermodynamics are derived. The obtained general expressions for heat conductivity, shear, and volume viscosity coefficients are applied to determine the transport coefficients of cosmic fluids in spacetimes with generic local anisotropy. We emphasize that such local anisotropic structures are induced also in general relativity if we are modelling physical processes with respect to frames with mixed sets of holonomic and anholonomic basis vectors which naturally admits an associated nonlinear connection structure.     

Nonlinear fluctuation-dissipation relations and stochastic models in nonequilibrium thermodynamics: I. Generalized fluctuation-dissipation theorem

The paper is devoted to the theory of thermal fluctuations in nonlinear macroscopic systems and to the derivation of variational principles of nonlinear nonequilibrium thermodynamics. In the first part of the paper rigorous universal fluctuation-dissipation relations for nonlinear classical and quantum systems, subjected to dynamic as well as thermodynamic perturbations, are derived and analyzed. General expressions for dissipative fluxes and nonlinear transfer coefficients with the help of fluctuation cumulants are found. The canonical structure of nonlinear evolution equations of macrovariables is derived and the rule of introducing langevinian random forces into these equations, in accordance with fluctuation-dissipation relations. A Markovian theory of fluctuations in a stationary nonequilibrium state is constructed.     

Effective first law of thermodynamics of black holes with two horizons

For a black hole with two horizons, the effective entropy is assumed to be a linear combination of the two entropies of the outer and inner horizons. In terms of the effective thermodynamic quantities the effective Bekenstein-Smarr formula and the effective first law of thermodynamics are derived.     

On thermoluminescence build-up in ionic crystals

Thermoluminescence build-up in ionic crystals is studied with a kinetic model utilizing subsidiary conditions from linear nonequilibrium thermodynamics. The equations obtained are successfully applied to CaF₂ and KCl excited by soft X-rays at room temperature. The experimental results show the effect of X-ray absorption in the samples.     

Hierarchy of equations for the surface tension of solids

Of the four main equations in thermodynamics for the surface tension of condensed matter, i.e. the generalized and classical Lippmann equations and the Shuttleworth and Gokhshtein equations, only the classical Lippmann and Gokhshtein equations have been confirmed experimentally. The generalized Lippmann (Couchman–Davidson) equation is considered to be more universal, since three other equations could be derived from it. Although this fact has been widely accepted, it was recently reevaluated in two opposite ways. In the first approach, the experimental verification of the Gokhshtein equation should support the correctness of the generalized Lippmann and Shuttleworth equations. In the second approach, the incompatibility of the Shuttleworth equation with Hermann's mathematical structure of thermodynamics throws doubts upon all its corollaries, including the generalized Lippmann and Gokhshtein equations. However, both of these approaches are here shown to be erroneous, since the Gokhshtein equation cannot be correctly derived from any of the above-mentioned equations, and the opposite is also true: neither the generalized Lippmann nor Shuttleworth equations could be derived from the Gokhshtein equation.     

Nonequilibrium Thermodynamics of the First and Second Kind: Averages and Fluctuations

We elaborate and compare two approaches to nonequilibrium thermodynamics, the two-generator bracket formulation of time-evolution equations for averages and the macroscopic fluctuation theory, for a purely dissipative isothermal driven diffusive system under steady state conditions. The fluctuation dissipation relations of both approaches play an important role for a detailed comparison. The nonequilibrium Helmholtz free energies introduced in these two approaches differ as a result of boundary conditions. A Fokker-Planck equation derived by projection operator techniques properly reproduces long range fluctuations in nonequilibrium steady states and offers the most promising possibility to describe the physically relevant fluctuations around macroscopic averages for time-dependent nonequilibrium systems.     

The time derivative of information gain as excess entropy production

An information gain depending on two nonequilibrium coarse-grained statistical operators is discussed. The relation between the time derivative of information gain and excess entropy production is derived. Prigogine's stability criterion is expressed by means of the information gain. It is shown in the domain of linear nonequilibrium thermodynamics that zero time derivative of information gain corresponds to a minimum of entropy production and K theorem can be formulated.     

Nonlinear mean field Fokker-Planck equations. Application to the chemotaxis of biological populations

We study a general class of nonlinear mean field Fokker-Planck equations in relation with an effective generalized thermodynamical (E.G.T.) formalism. We show that these equations describe several physical systems such as: chemotaxis of bacterial populations, Bose-Einstein condensation in the canonical ensemble, porous media, generalized Cahn-Hilliard equations, Kuramoto model, BMF model, Burgers equation, Smoluchowski-Poisson system for self-gravitating Brownian particles, Debye-Hückel theory of electrolytes, two-dimensional turbulence... In particular, we show that nonlinear mean field Fokker-Planck equations can provide generalized Keller-Segel models for the chemotaxis of biological populations. As an example, we introduce a new model of chemotaxis incorporating both effects of anomalous diffusion and exclusion principle (volume filling). Therefore, the notion of generalized thermodynamics can have applications for concrete physical systems. We also consider nonlinear mean field Fokker-Planck equations in phase space and show the passage from the generalized Kramers equation to the generalized Smoluchowski equation in a strong friction limit. Our formalism is simple and illustrated by several explicit examples corresponding to Boltzmann, Tsallis, Fermi-Dirac and Bose-Einstein entropies among others.     

Nonequilibrium evolution thermodynamics of vacancies

An alternative approach, nonequilibrium evolution thermodynamics, is compared with the classical Landau approach. A statistical justification of the approach is done with the help of a probability distribution function on an example of a solid with vacancies. Two kinds of kinetic equations are derived in terms of the internal energy and the modified free energy.     

Generalization of the Gibbsian relation for dilute systems

The Gibbsian relation is of fundamental importance to the thermodynamics of nonequilibrium systems. In this paper, we shall present an analytical derivation and several generalizations of this relation for dilute, nonequilibrium and certain highly nonequilibrium, systems. Our analysis will beindependent of the collision dynamics, because it will be based on the general kinetic equation witharbitrary collision integrals. Consequently, our analysis can provide athermodynamic derivation and several generalizations of the Gibbsian relation. Our distribution functions can also admit some arbitrary, nonequilibrium and highly nonequilibrium, forms. With the help of the generalized Gibbsian relation and a fundamental axiom to be postulated, the entropy production rates and the generalized forces and fluxes will be studied for our highly nonequilibrium systems. The second law of thermodynamics will be postulated and verified in specific cases. Onsager's reciprocity relations will be discussed.     

Time-dependent statistics of binary linear lattices

The time-dependent statistics of binary linear lattices is investigated on the basis of a master equation at the microscopic level. It is assumed that the kinetics may be formulated as transformations of specified sequences of clusters ofA units andB units into other specified sequences. On the basis of aStosszahlansatz, a master equation at the macroscopic level is derived. In the limit of a large system, the densities of clusters of all types satisfy rate equations similar to the equations of chemical kinetics. AnH-theorem is proven and the nonequilibrium thermodynamics of the system is studied. The theory has application to the kinetics of the helix-coil phase transition in biopolymers.