Volume 46, Issue 1

Understanding the fluctuations by which phenomenological evolution equations with thermodynamic structure can be enhanced is the key to a general framework of nonequilibrium statistical mechanics. These fluctuations provide an idealized representation of microscopic details. We consider fluctuation-enhanced equations associated with Markov processes and elaborate the general recipes for evaluating dynamic material properties, which characterize force-flux constitutive laws, by statistical mechanics. Markov processes with continuous trajectories are conveniently characterized by stochastic differential equations and lead to Green–Kubo-type formulas for dynamic material properties. Markov processes with discontinuous jumps include transitions over energy barriers with the rates calculated by Kramers. We describe a unified approach to Markovian fluctuations and demonstrate how the appropriate type of fluctuations (continuous versus discontinuous) is reflected in the mathematical structure of the phenomenological equations.

For a given thermodynamic system, and a given choice of coarse-grained state variables, the knowledge of a force-flux constitutive law is the basis for any nonequilibrium modeling. In the first paper of this series we established how, by a generalization of the classical fluctuation-dissipation theorem (FDT), the structure of a constitutive law is directly related to the distribution of the fluctuations of the state variables. When these fluctuations can be expressed in terms of diffusion processes, one may use Green–Kubo-type coarse-graining schemes to find the constitutive laws. In this paper we propose a coarse-graining method that is valid when the fluctuations are described by means of general Markov processes, which include diffusions as a special case. We prove the success of the method by numerically computing the constitutive law for a simple chemical reaction A⇄BA\rightleftarrows B. Furthermore, we show that, for such a system, one cannot find a consistent constitutive law by any Green–Kubo-like scheme.

We continue our exploration of thermodynamics at long observational timescales, “slow time,” by including turbulent dynamics leading to a condition of fluctuating local equilibrium. Averaging these fluctuations in wind speed and temperature results in a velocity distribution with heavy tails which, however, are necessarily truncated at some large molecular speed preserving all moments of the velocity distribution including the energy. This leads to an expression for the ideal gas law in slow time which as its core has the superficially familiar term 32Nkθ\frac{3}{2}Nk\theta in addition to a term accounting for the large-scale fluctuations, which is also proportional to the particle number N ; θ is a new temperature including thermalization of wind. The traditional temperature T no longer exists. Likewise, the additional energy term necessitates a new quantity that parallels entropy in the sense that it captures hidden degrees of freedom. Like entropy, it captures physical properties manifesting indirectly, but on scales larger than the familiar laboratory scales. We call this quantity epitropy.

Natural convective flow and heat transfer around a locally heated circular cylinder kept in a rectangular enclosure are investigated. At first, a problem valid for a rectangular domain is formulated and then an analytical coordinate transformation is introduced to map the rectangular domain to the physical domain considered here. Based on the coordinate transformation, a set of governing equations is obtained which is further simulated by imposing appropriate conditions on the walls of the cavity and the inner solid bodies. Numerical solutions are validated through comparison of the present results with the available published data. It is found that streamlines and isotherms are greatly influenced by the width ( w ) and breadth ( b ) of the heat source and the Rayleigh number (Ra\mathit{Ra}). The Nusselt number (Nu\mathit{Nu}) is computed at the surface of the inner and outer cylinders, revealing that it grows considerably when controlling parameters w , b , and Ra\mathit{Ra} are increased. The strength and number of the vortices generated within the velocity field heavily depend on the size and location of the outer cylinder. The span-wise local Nusselt number variation shows some sharp rises compared to the neighboring values in Nui{\mathit{Nu}_{i}} and Nuo{\mathit{Nu}_{o}}, which is due to the large temperature gradient at those points.

Based on an irreversible quantum Carnot heat pump model in which spin-1/2 systems are used as working substance, an exergy-based ecological function and some other important parameters of the model heat pump are derived. Numerical examples are provided to investigate its ecological performance characteristics. The influences of various irreversibility factors on the ecological performance are discussed. Performance comparison and discussion among maximum points of ecological function, heating load, and so on, are conducted. At last, three special cases are discussed.

This study deals with the problem of diffusion for polydisperse colloids. The resolution of this complex problem usually requires computationally expensive numerical models. By considering the number of colloidal particles and their mass as independent variables, the equations of state for a dilute polydisperse colloid are derived on a statistical mechanics basis. Irreversible thermodynamics is then applied to obtain a simple two-moment diffusion model. The validity of the model is illustrated by comparing its results with those obtained by a classical size spectrum approach, in a sedimentation equilibrium problem and in an unsteady one-dimensional diffusion problem in Stokes–Einstein regime, and under the hypothesis that the size spectrum distribution is stochastic. In the first problem, the two-moment diffusion problem allows to represent rigorously the vertical size segregation induced by gravity, while in the second one, it allows a convenient description of the diffusion of polydisperse colloids by using two coupled diffusion equations, with an accuracy comparable with that of the classical size spectrum approach. The contribution of our work lies primarily in the application of a non-equilibrium thermodynamics methodology to a challenging issue of colloid modeling, namely, polydispersity, by going from statistical mechanics to the derivation of phenomenological coefficients, with the two-moment approach as a guideline.

Originally derived by Walther Nernst more than a century ago, the Nernst equation for the open-circuit voltage is a cornerstone in the analysis of electrochemical systems. Unfortunately, the assumptions behind its derivation are often overlooked in the literature, leading to incorrect forms of the equation when applied to complex systems (for example, those with ion-exchange membranes or involving mixed potentials). Such flaws can be avoided by applying a correct thermodynamic derivation independently of the form in which the electrochemical reactions are written. The proper derivation of the Nernst equation becomes important, for instance, in modeling of vanadium redox flow batteries or zinc-air batteries. The rigorous path towards the Nernst equation derivation starts in non-equilibrium thermodynamics.