Phenomenological Transport Relationship Irreversible thermodynamics

Phenomenological transport relationships can be developed even in the absence of any knowledge of the mechanisms of transport through the membrane or any information about the membrane structure. The basis of irreversible thermodynamics assumes that if the system is divided into small enough subsystems in which local equilibrium exists, thermodynamic equations can be written for the subsystems. 

As with the finely-porous model, (Chapter 4.1.3), the mathematical representation of solvent and solute fluxes for the irreversible thermodynamic model is quite complex and beyond the scope of this work. However, it is recommended that readers consider references and for details on this transport model. 

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Dialysis transport relations need not start with Eickian diffusion they may also be derived by integration of the basic transport equation (7) or from the phenomenological relationships of irreversible thermodynamics (8,9). 

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 theory treating near-equilibrium phenomena is called the linear nonequilibrium thermodynamics. It is based on the local equilibrium assumption in the system and phenomenological equations that linearly relate forces and flows of the processes of interest. Application of classical thermodynamics to nonequilibrium systems is valid for systems not too far from equilibrium. This condition does not prove excessively restrictive as many systems and phenomena can be found within the vicinity of equilibrium. Therefore equations for property changes between equilibrium states, such as the Gibbs relationship, can be utilized to express the entropy generation in nonequilibrium systems in terms of variables that are used in the transport and rate processes. The second law analysis determines the thermodynamic optimality of a physical process by determining the rate of entropy generation due to the irreversible process in the system for a required task. 

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