Volume 43, Issue 2 - Special Issue: The 14th Joint European Thermodynamics Conference (JETC 2017)

Thermodynamically admissible evolution equations for non-equilibrium systems are known to possess a distinct mathematical structure. Within the GENERIC ( g eneral e quation for the n on- e quilibrium r eversible– i rreversible c oupling) framework of non-equilibrium thermodynamics, which is based on continuous time evolution, we investigate the possibility of preserving all the structural elements in time-discretized equations. Our approach, which follows Moser’s [1] construction of symplectic integrators for Hamiltonian systems, is illustrated for the damped harmonic oscillator. Alternative approaches are sketched.

We show that to prove the Onsager relations using the microscopic time reversibility one necessarily has to make an ergodic hypothesis, or a hypothesis closely linked to that. This is true in all the proofs of the Onsager relations in the literature: from the original proof by Onsager, to more advanced proofs in the context of linear response theory and the theory of Markov processes, to the proof in the context of the kinetic theory of gases. The only three proofs that do not require any kind of ergodic hypothesis are based on additional hypotheses on the macroscopic evolution: Ziegler’s maximum entropy production principle (MEPP), the principle of time reversal invariance of the entropy production, or the steepest entropy ascent principle (SEAP).

Entropy generation minimization is a method that helps improve the efficiency of real processes and devices. In this article, we study the entropy production (due to chemical reactions, heat exchange and friction) in a conventional reactor that synthesizes dimethyl ether and minimize it by modifying different operating variables of the reactor, such as composition, temperature and pressure, while aiming at a fixed production of dimethyl ether. Our results indicate that it is possible to reduce the entropy production rate by nearly 70 % and that, by changing only the inlet composition, it is possible to cut it by nearly 40 %, though this comes at the expense of greater dissipation due to heat transfer. We also study the alternative of coupling the reactor with another, where dehydrogenation of methylcyclohexane takes place. In that case, entropy generation can be reduced by 54 %, when pressure, temperature and inlet molar flows are varied. These examples show that entropy generation analysis can be a valuable tool in engineering design and applications aiming at process intensification and efficient operation of plant equipment.

Rate-Controlled Constrained-Equilibrium (RCCE) modeling of complex chemical kinetics provides acceptable accuracies with much fewer differential equations than for the fully Detailed Kinetic Model (DKM). Since its introduction by James C. Keck, a drawback of the RCCE scheme has been the absence of an automatable, systematic procedure to identify the constraints that most effectively warrant a desired level of approximation for a given range of initial, boundary, and thermodynamic conditions. An optimal constraint identification has been recently proposed. Given a DKM with S species, E elements, and R reactions, the procedure starts by running a probe DKM simulation to compute an S-vector that we call overall degree of disequilibrium (ODoD) because its scalar product with the S-vector formed by the stoichiometric coefficients of any reaction yields its degree of disequilibrium (DoD). The ODoD vector evolves in the same (S-E)-dimensional stoichiometric subspace spanned by the R stoichiometric S-vectors. Next we construct the rank-(S-E) matrix of ODoD traces obtained from the probe DKM numerical simulation and compute its singular value decomposition (SVD). By retaining only the first C largest singular values of the SVD and setting to zero all the others we obtain the best rank-C approximation of the matrix of ODoD traces whereby its columns span a C-dimensional subspace of the stoichiometric subspace. This in turn yields the best approximation of the evolution of the ODoD vector in terms of only C parameters that we call the constraint potentials. The resulting order-C RCCE approximate model reduces the number of independent differential equations related to species, mass, and energy balances from S+2 to C+E+2, with substantial computational savings when C ≪ S-E.

This paper presents a general property of endoreversible thermal engines known as the Semisum property previously studied in a finite-time thermodynamics context for a Curzon–Ahlborn (CA) engine but now extended to a simplified version of the CA engine studied by Agrawal in 2009 (A simplified version of the Curzon–Ahlborn engine, European Journal of Physics 30 (2009), 1173). By building the Ecological function, proposed by Angulo-Brown (An ecological optimization criterion for finite-time heat engines, Journal of Applied Physics 69 (1991), 7465–7469) in 1991, and considering two heat transfer laws an analytical expression is obtained for efficiency and power output which depends only on the heat reservoirs’ temperature. When comparing the existing efficiency values of real power plants and the theoretical efficiencies obtained in this work, it is observed that the Semisum property is satisfied. Moreover, for the Newton and the Dulong–Petit heat transfer laws the existence of the g function is demonstrated and we confirm that in a Carnot-type thermal engine there is a general property independent of the heat transfer law used between the thermal reservoirs and the working substance.

The Novikov engine is a model for heat engines that takes the irreversible character of heat fluxes into account. Using this model, the maximum power output as well as the corresponding efficiency of the heat engine can be deduced, leading to the well-known Curzon–Ahlborn efficiency. The classical model assumes constant heat bath temperatures, which is not a reasonable assumption in the case of fluctuating heat sources. Therefore, in this article the influence of stochastic fluctuations of the hot heat bath’s temperature on the optimal performance measures is investigated. For this purpose, a Novikov engine with fluctuating heat bath temperature is considered. Doing so, a generalization of the Curzon–Ahlborn efficiency is found. The results can help to quantify how the distribution of fluctuating quantities affects the performance measures of power plants.

Many works have been devoted to finite time thermodynamics since the Curzon and Ahlborn [1] contribution, which is generally considered as its origin. Nevertheless, previous works in this domain have been revealed [2], [3], and recently, results of the attempt to correlate Finite Time Thermodynamics with Linear Irreversible Thermodynamics according to Onsager’s theory were reported [4]. The aim of the present paper is to extend and improve the approach relative to thermodynamic optimization of generic objective functions of a Carnot engine with linear response regime presented in [4]. The case study of the Carnot engine is revisited within the steady state hypothesis, when non-adiabaticity of the system is considered, and heat loss is accounted for by an overall heat leak between the engine heat reservoirs. The optimization is focused on the main objective functions connected to engineering conditions, namely maximum efficiency or power output, except the one relative to entropy that is more fundamental. Results given in reference [4] relative to the maximum power output and minimum entropy production as objective function are reconsidered and clarified, and the change from finite time to finite physical dimension was shown to be done by the heat flow rate at the source. Our modeling has led to new results of the Carnot engine optimization and proved that the primary interest for an engineer is mainly connected to what we called Finite Physical Dimensions Optimal Thermodynamics.

A model for semiconductor crystals and superlattices with dislocations proposed in a previous paper is used here to study the thermal, electrical and mechanical properties of these defective materials. The standard procedures of non-equilibrium thermodynamics with internal variables are applied to derive in the linear approximation constitutive equations as well as rate equations for the dislocation, charges and heat flux fields, containing coupled effects among the different fields. A new dislocation tensor is used to describe the geometry of the dislocation lines, because their relative orientation with respect to the superlattice interfaces is very relevant.

In this paper the heat conduction in viscous fluids is described by using the theory of classical irreversible thermodynamics with internal variables. In this theory, the deviation from the local equilibrium is characterized by vectorial internal variables and a generalized entropy current density expressed in terms of so-called current multipliers. Cross effects between heat conduction and viscosity are also considered and some phenomenological generalizations of Fourier’s and Newton’s laws are obtained.

The de-mixing properties of heterogeneous viscous fluids are determined by an interplay of diffusion, surface tension and a superposed velocity field. In this contribution a variational model of the decomposition, based on the Navier–Stokes equations for incompressible laminar flow and the extended Korteweg–Cahn–Hilliard equations, is formulated. An exemplary numerical simulation using C1{C}^{1}-continuous finite elements demonstrates the capability of this model to compute phase decomposition and coarsening of the moving fluid.