Irreversible processes, equilibrium thermodynamic modeling

In equilibrium thermodynamics model A and in model B not far from equilibrium (and with no memory to temperature) the entropy may be calculated up to a constant. Namely, in both cases S = S(V, T) (2.6)2, (2.25) and we can use the equilibrium processes (2.28) in B or arbitrary processes in A for classical calculation of entropy change by integration of dS/dT or dS/dV expressible by Gibbs equations (2.18), (2.19), (2.38) through measurable heat capacity dU/dT or state Eqs.(2.6>, (2.33) (with equilibrium pressure P° in model B). This seems to accord with such a property as in (1.11), (1.40) in Sects. 1.3, 1.4. As we noted above, here the Gibbs equations used were proved to be valid not only in classical equilibrium thermodynamics (2.18), (2.19) but also in the nonequilibrium model B (2.38) and this expresses the local equilibrium hypothesis in model B (it will be proved also in nonuniform models in Chaps.3 (Sect. 3.6), 4, while in classical theories of irreversible processes [12, 16] it must be taken as a postulate). 

From the point of view of thermodynamics we have now a microscopic model of entropy (see Eq. (52)). Therefore, we can verify that it leads to the basic expressions of thermodynamics of irreversible processes in the neighborhood of equilibrium.29 These expressions were derived until recently in the weakly coupled limit, or for dilute gases. 

The MEIS developers relying on the capabilities of modem computers and computational mathematics started the work whichresulted in an essential expansion of the application area of "good, old" classical thermodynamics and in the possibility to study (using thermodynamics) any states on all possible motion trajectories of a nonequilibrium system. In other words, they put forward the goal to use the models of equilibrium not only to determine the directions of irreversible processes but to estimate the attainability of desired and undesired states on these directions. 

Feasibility of applying the models of equilibrium thermodynamics to the analysis of nonequilibrium irreversible processes were described in Section 2 of this chapter. This section discusses the comparative efficiency of such application to solve diverse theoretical and applied problems. 

Closed equilibrium models are the simplest type they relate to closed uniform objects, which are in equilibrium both dynamically and chemically. In them the flow is absent and velocity of chemical processes provides for instantaneous and total thermodynamic equilibrium in any moment of time. These models disregard irreversible processes. It is assumed that all chemical reactions have values of chemical affinity and saturation index... 

Thus, from the point of view of modem phenomenological thermodynamics, the current outputs of classical equilibrium thermodynamics (e.g. the description of thermochemistry of mixtures) and the tasks of irreversible thermodynamics, like the description of linear transport phenomena and nonlinear chemical kinetics, are valid much more generally, e.g. even when all these processes mn simultaneously. As we noted above, these properties are not expected to be valid in any material models in some models the local equilibrium may not be valid, reaction rates may depend not only on concentrations and temperature, etc. 

The capacitive elements and fields in the model represent equilibrium thermodynamics part of the model. As the simulation proceeds, the matter inside the control volume represented by these elements changes reversibly from one equilibrium state to the next, i.e. the process is assumed to be quasi-static. The R-fields represent the non-equilibrium parts of the model, and they introduce the irreversibilities into the system. The R-field elements represented by MR in Fig. 10.4 introduce the irreversibility due to mass convection into the system (refer to Section 10.2.4). The R-field element represented by RS in Fig. 10.4 introduces the irreversibility due to the over-voltage phenomena (ohmic, concentration and activation losses). The other R-field elements introduce the irreversibilities due to the heat transfer phenomena. 

Relations between the theories of states and trajectories and capabilities of equilibrium thermodynamic analysis to study reversible and irreversible kinetics can be more fully revealed by considering another type of models of extreme intermediate states, namely MEIS of hydraulic circuits (Gorban et al., 2001, 2006 Kaganovich et al., 1997, 2007, 2010). Convenience and clearness of using these models to describe the considered problems are determined by the fact that they are intended to study an essentially irreversible process, i.e. motion of a viscous fluid. Besides, they can be treated as models of the mechanism of fluid transportation from the specified source nodes of a hydraulic system to the specified consumption nodes. The major variable of the hydraulic circuit theory (Khasilev, 1957,1964 Merenkov and Khasilev, 1985), i.e. continuous medium flow, has an obvious kinetic sense. 

As mentioned before, nonequilibrium thermodynamics could be used to study the entropy generated by an irreversible process (Prigogine, 1945, 1947). The concept ofhnear nonequilibrium thermodynamics is that when the system is close to equilibrium, the hnear relationship can be obtained between the flux and the driving force (Demirel and Sandler, 2004 Lu et al, 2011). Based on our previous linear nonequihbrium thermodynamic studies on the dissolution and crystallization kinetics of potassium inorganic compounds (Ji et al, 2010 Liu et al, 2009 Lu et al, 2011), the nonequihbrium thermodynamic model of CO2 absorption and desorption kinetics by ILs could be studied. Figure 17 shows the schematic diagram of CO2 absorption kinetic process by ILs. In our work, the surface reaction mass transport rate and diffusion mass transport rate were described using the Hnear nonequihbrium thermodynamic theory. 

This model, as wets discussed in Chap.6, gives one an opportunity to describe the kinetics of non-ideal gas media in static and fluctuating surface field. Therefore, when approximating the kinetic operators (6.2.4), (6.2.5) one can use the results of quasiparticle method for non-ideal media kinetics (Dubrovskiy and Bogdanov 1979b), theory of liquids (Croxton 1974), theory of Brownian motion (Akhiezer and Peletminskiy 1977), theory of phase transitions, models of equilibrium properties of such systems (Jaycock and Parfitt 1981) with further application of methods of statistical thermodynamics of irreversible processes (Kreuzer and Payne 1988b) and experimental data on pair correlation function (Flood 1967). 

It will apparently be possible to provide coordination between the capabilities of equilibrium models in (1) the analysis of perfection of the energy and substance transformation processes and (2) the analysis of different irreversible phenomena on the basis of dual interpretation of equilibrium processes as being both reversible and irreversible at a time. In the first case they are convenient for interpretation as reversible in terms of the system interaction with the environment and in the second case—as irreversible in terms of their inner content according to Gorban. It is clear that to explain the dual interpretation it is necessary to extend the analysis by Gorban to the nonisolated thermodynamic systems with other characteristic functions to be used along with entropy. 

Development of the "flow" MEIS with the form reminding the models of nonequilibrium thermodynamics seems to be a very promising direction in equilibrium modeling of physical and chemical systems. Application of these models opens prospects for simpler analysis and solution of many complex problems related to the calculations of processes considered to be irreversible in principle. Certainly the flows in MEIS are interpreted statically as the coordinates of states. Thermodynamic interpretations are naturally extended to the kinetic coefficients that relate these flows with forces. Correctness of such interpretations is confirmed by the application of MP, being the theory of equilibrium states, as the terms for MEIS description. 

---