Nernst film

These two thin liquid films, which are also called diffusion films, diffusion layers, or Nernst films, have thicknesses that range between 10 and 10 cm (in this chapter centimeter-gram-second (CGS) units are used, since most published data on diffusion and extraction kinetics are reported in these units comparison with literature values is, therefore, straightforward). 

Even where ion exchange is not affected by the above factors, the Nernst-Planck equations are not very useful for diffusion phenomena in the film. After all, the Nernst film is somewhat enigmatic and there is a combination of diffusive and convective mass transfer that changes from the bulk solution to the particle surface. Nernst (1904) originally defined the outer limit of film only as the point where the concentration profile, if linearly extrapolated from the particle surface, reaches the concentration level of the bulk solution. 

The concentration polarization occurring in electrodialysis, that is, the concentration profiles at the membrane surface can be calculated by a mass balance taking into account all fluxes in the boundary layer and the hydrodynamic conditions in the flow channel between the membranes. To a first approximation the salt concentration at the membrane surface can be calculated and related to the current density by applying the so-called Nernst film model, which assumes that the bulk solution between the laminar boundary layers has a uniform concentration, whereas the concentration in the boundary layers changes over the thickness of the boundary layer. However, the concentration at the membrane surface and the boundary layer thickness are constant along the flow channel from the cell entrance to the exit. In a practical electrodialysis stack there will be entrance and exit effects and concentration... 

Commonly, mass transfer in the liquid is modeled as diffusion in a fic-litious liquid film adhering to the particle Nernst film (Nernst, 1889 Planck, 1890). Intraparticle diffusion and film diffusion are the two possible rate-controlling steps (Helfferich, 1962a). 

A brief comment should be made concerning the use of the Nernst-Planck equations for ion transport across the liquid film (e.g., Copeland and Marchello [1969], Kataoka et al. [1987]). This is a nonlinear, three-ion problem because of the presence of at least one coion at comparable concentration. The Nernst film model relies on the assumption of a linear concentration gradient in the liquid film. The film has no physical reality, and the calculation of nonlinear concentration profiles in it overburdens the model and offers little improvement over the much simpler linear driving force approximation. For higher accuracy, more refined and complex hydrodynamic models would have to be used (Van Brocklin and David, 1975). 

The Nernst film model is used to quantify diffusional transport through the static boundary layer. This model approximates the low velocity boundary layer as a thin, static film between the surface and the free fiowing solution. Pick s first law gives the diffusional flux (/, mol/m sec) through this film (Figure 7.6). 

At high velocities where turbulence dominates, the main body of flowing fluid is well mixed in the direction normal to the flow, minor differences in temperature and concentration can be neglected, and the film concept can be applied. This describes the flow as if all gradients for temperature and concentration are in a narrow film along the interface with the solid (Nernst 1904), and inside the film conduction and diffusion are the transfer mechanisms. This film concept greatly simplifies the engineering calculation of heat and mass transfer. 

When paint films are immersed in water or solutions of electrolytes they acquire a charge. The existence of this charge is based on the following evidence. In a junction between two solutions of potassium chloride, 0 -1 N and 0 01 N, there will be no diffusion potential, because the transport numbers of both the and the Cl" ions are almost 0-5. If the solutions are separated by a membrane equally permeable to both ions, there will still be no diffusion potential, but if the membrane is more permeable to one ion than to the other a diffusion potential will arise it can be calculated from the Nernst equation that when the membrane is permeable to only one ion, the potential will have the value of 56 mV. 

Steady diffusion across a thin film is mathematically straightforward but physically subtle. Dissolution film theory, suggested initially by Nernst and Brunner, is essentially based on steady diffusion across a thin film. 

Early investigators assumed that this so-called diffusion layer was stagnant (Nernst-Whitman model), and that the concentration profile of the reacting ion was linear, with the film thickness <5N chosen to give the actual concentration gradient at the electrode. In reality, however, the thin diffusion layer is not stagnant, and the fictitious t5N is always smaller than the real mass-transfer boundary-layer thickness (Fig. 2). However, since the actual concentration profile tapers off gradually to the bulk value of the concentration, the well-defined Nernst diffusion layer thickness has retained a certain convenience in practical calculations. 

The stagnant film theory was developed by Nernst (1904). In this theory, a stagnant film exists on both sides of the interface, as illustrated in Figure 8.8. The thickness of the film is controlled by turbulence and is constant. 

The film model referred to in Chapters 2 and 5 provides, in fact, an oversimplified picture of what happens in the vicinity of interface. On the basis of the film model proposed by Nernst in 1904, Whitman [2] proposed in 1923 the two-film theory of gas absorption. Although this is a very useful concept, it is impossible to predict the individual (film) coefficient of mass transfer, unless the thickness of the laminar sublayer is known. According to this theory, the mass transfer rate should be proportional to the diffusivity, and inversely proportional to the thickness of the laminar film. However, as we usually do not know the thickness of the laminar film, a convenient concept of the effective film thickness has been assumed (as... 

The theories vary in the assumptions and boundary conditions used to integrate Fick s law, but all predict the film mass transfer coefficient is proportional to some power of the molecular diffusion coefficient D", with n varying from 0.5 to 1. In the film theory, the concentration gradient is assumed to be at steady state and linear, (Figure 3-2) (Nernst, 1904 Lewis and Whitman, 1924). However, the time of exposure of a fluid to mass transfer may be so short that the steady state gradient of the film theory does not have time to develop. The penetration theory was proposed to account for a limited, but constant time that fluid elements are exposed to mass transfer at the surface (Higbie, 1935). The surface renewal theory brings in a modification to allow the time of exposure to vary (Danckwerts, 1951). 

For reversible stripping reactions, the applied potential controls the concentration at the mercury-solution interface (according to the Nernst equation). Because of the rapid depletion of all the metal from thin mercury films, the stripping behavior at these electrodes follows a thin-layer behavior. The peak current for the linear scan operation at thin mercury film electrodes is thus given by... 

A more general theoretical approach for dissolution modeling called the Film-Model Theory was postulated by Nernst (1904) and expanded upon by Brunner (1904) in an effort to deconvo-lute the components of the dissolution constinIBoth Nernst and Brunner made the following assumptions ... 

Fig. 6-11. Scheme of the modified electrode (polymer film thickness 0) in contact with a solution containing a redox substrate. <5 is the Nernst layer thickness defined for a rotating disc electrode. From [85]. 

Also, in the late 1950s and 1960s some particularly seminal papers on ion exchange kinetics appeared by Helfferich (1962b, 1963, 1965) that are classics in the field. In this research it was definitively shown that the rate-limiting steps in ion exchange phenomena were film diffusion (FD) and/ or particle diffusion (PD). Additionally, the Nernst-Planck theories were explored and applied to an array of adsorbents (Chapter 5). 

In most common separation processes, the main mass transfer is across an interface between a gas and a liquid or between two liquid phases. At fluid-fluid interfaces, turbulence may persist to the interface. A simple theoretical model for turbulent mass transfer to or from a fluid-phase boundary was suggested in 1904 by Nernst, who postulated that the entire resistance to mass transfer in a given turbulent phase lies in a thin, stagnant region of that phase at the interface, called a him, hence the name film theory.2 4,5 Other, more detailed, theories for describing the mass transfer through a fluid-fluid interface exist, such as the penetration theory.1,4... 

The final part of the transmission line circuit is the charge transfer elements at the electrode/film interface and at the film/solution interface. In the former case, at low AC frequency electrons are transferred from the electrode to the trimer centres. We have shown [5] that this process is controlled by the Nernst driving potential, and that the interfacial resistance is given by... 

An important example of the system with an ideally permeable external interface is the diffusion of an electroactive species across the boundary layer in solution near the solid electrode surface, described within the framework of the Nernst diffusion layer model. Mathematically, an equivalent problem appears for the diffusion of a solute electroactive species to the electrode surface across a passive membrane layer. The non-stationary distribution of this species inside the layer corresponds to a finite - diffusion problem. Its solution for the film with an ideally permeable external boundary and with the concentration modulation at the electrode film contact in the course of the passage of an alternating current results in one of two expressions for finite-Warburg impedance for the contribution of the layer Ziayer = H(0) tanh(icard)1/2/(iwrd)1/2 containing the characteristic - diffusion time, Td = L2/D (L, layer thickness, D, - diffusion coefficient), and the low-frequency resistance of the layer, R(0) = dE/dl, this derivative corresponding to -> direct current conditions. 

Additional deviations from the Nernst law [Eq. (4)] can come from kinetic effects in other words, if the potential scan is too fast to allow the system to reach thermal equilibrium. Two cases should be mentioned (1) ion transport limitation, and (2) electron transfer limitation. In case 1 the redox reaction is limited because the ions do not diffuse across the film fast enough to compensate for the charge at the rate of the electron transfers. This case is characterized by a square-root dependence of the current peak intensity versus scan rate Ik um instead of lk u. Since the time needed to cross the film, tCT, decreases as the square of the film thickness tCT d2, the transport limitation is avoided in thin films (typically, d < 1 xm for u < 100 mV/s). The limitation by the electron transfer kinetics (case 2) is more intrinsic to the polymer properties. It originates from the fact that the redox reaction is not instantaneous in particular, due to the fact that the electron transfer implies a jump over a potential barrier. If the scan... 

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