Force-flux relationship irreversible

Table 3-2. Number of coefficients needed to describe relationships between forces (represented by differences in chemical potential) and fluxes in irreversible thermodynamics for systems with one, two, or three components.

Irreversible thermodynamics has also been used sometimes to explain reverse osmosis [14,15]. If it can be assumed that the thermodynamic forces responsible for reverse osmosis are sufficiently small, then a linear relationship will exist between the forces and the fluxes in the system, with the coefficients of proportionality then referred to as the phenomenological coefficients. These coefficients are generally notoriously difficult to obtain, although some progress has been made recently using approaches such as cell models [15]. 

Some of the elements of thermodynamics of irreversible processes were described in Sections 2.1 and 2.3. Consider the system represented by n fluxes of thermodynamic quantities and n driving forces it follows from Eqs (2.1.3) and (2.1.4) that n(n +1) independent experiments are needed for determination of all phenomenological coefficients (e.g. by gradual elimination of all the driving forces except one, by gradual elimination of all the fluxes except one, etc.). Suitable selection of the driving forces restricted by relationship (2.3.4) leads to considerable simplification in the determination of the phenomenological coefficients and thus to a complete description of the transport process. 

The power (work by the system per unit time) is thus W = —Fx = —JiXiT. The work is performed under the influence of a heat flux Q leaving the hot reservoir at temperature Ti. The cold reservoir is at temperature T2 (where T > T2). The corresponding thermodynamic force is X2 = I/T2 — 1/Ti, and the flux is J2 = Q. The temperature difference Ti —T2 = AT is assumed to be small compared to T2 T kT, so one can also write X2 = AT/T. Linear irreversible thermodynamics is based on the assumption of local equilibrium with the following linear relationship between the fluxes and forces ... 

This relationship shows that if the flux of an irreversible process i is affected by thermodynamic force Xj of another irreversible process j through the mediation of coefficient Ly, then the flux of process j is also influenced by thermodynamic force Xj through the mediation of the same coefficient Lj = Ly In the case of interacting chemical processes, this statement reflects the principles of detailed (intimate) equihbrium and mass balance of the reactants that underlie the concepts of chemical kinetics. 

Electrokinetic phenomena are irreversible processes, in which an electric force induces a coupled mechanical flux or a mechanical force induces a coupled electric flux, in the direction tangential to a charged surface. The potential is calculated from the phenomenological coefficients in the relationships between the force and the coupled flux in these phenomena. 

The relationship between ionic conductivity and Onsager s theory can now be presented in terms of the electrochemical potential. By expressing the force leading to the transport of ions in terms of the gradient of jr,-, one finds important relationships between the diffusion coefficients of the ions, and the molar conductivity and mobility. Furthermore, when the force has the correct Newtonian units, one is also in a position to calculate the rate of entropy production. On the basis of the thermodynamics of irreversible processes, the relationship between the flux of ion i and the force Vp,- is... 

When there are several different fluxes and forces brought into play in a system, then the thermodynamics of linear irreversible processes postulates that there is a matrix relationship between the different fluxes and forces (with a symmetrical matrix ONSAGER relations). The non-zero non-diagonal terms in the matrix signify that a coupling of the phenomena is taking place. 

Using linear relationships between the fluxes and forces in accordance with the concept of irreversible thermodynamics and assuming isothermal conditions the forces can be described as the gradient of the chemical potential, i.e. 

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. 

If the steady state concentrations of the components are shifted, but not too far from their equilibrium values, the interconnection between the fluxes and chemical forces (chemical affinities, in our case) should satisfy the well-known linear relationships that are usually postulated in the linear thermodynamics of irreversible processes [15-18]. We do not consider here the phenomenological equations of nonequilibrium thermodynamics. For details the reader can refer to numerous excellent monographs and review articles devoted to the applications of nonequilibrium thermodynamics in the description of chemical reactions and biological processes (see, for instance, [22-30]). In many cases, the conventional phenomenological approaches of linear and nonlinear nonequilibrium thermodynamics appear to be useful tools for the... 

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