Diffusion Basic equations

Basic Equations AU of the processes described in this sec tion depend to some extent on the following background theory. Substances move through membranes by several meoianisms. For porous membranes, such as are used in microfiltration, viscous flow dominates the process. For electrodialytic membranes, the mass transfer is caused by an elec trical potential resulting in ionic conduction. For aU membranes, Ficldan diffusion is of some importance, and it is of dom-... 

The Gaussian diffusion equation is known as the Pasquill and Gifford model, and is used to develop methods for estimating the required diffusion coefficients. The basic equation, already presented in a slightly different form, is restated below ... 

The basic equation and boundary conditions for the symmetrical fluctuations are the same as those for the asymmetrical fluctuations except for the superscript s. The diffusion equation is written in the form... 

There is apparently an inherent anomaly in the heat and mass transfer results in that, at low Reynolds numbers, the Nusselt and Sherwood numbers (Figures. 6.30 and 6.27) are very low, and substantially below the theoretical minimum value of 2 for transfer by thermal conduction or molecular diffusion to a spherical particle when the driving force is spread over an infinite distance (Volume 1, Chapter 9). The most probable explanation is that at low Reynolds numbers there is appreciable back-mixing of gas associated with the circulation of the solids. If this is represented as a diffusional type of process with a longitudinal diffusivity of DL, the basic equation for the heat transfer process is ... 

Whilst there is at present no theoretical basis for the rate of diffusion in liquids comparable with the kinetic theory for gases, the basic equation is taken as similar to that for gases, or for dilute concentrations ... 

As implied in the previous section, the Russian investigators Zeldovich, Frank-Kamenetskii, and Semenov derived an expression for the laminar flame speed by an important extension of the very simplified Mallard-Le Chatelier approach. Their basic equation included diffusion of species as well as heat. Since their initial insight was that flame propagation was fundamentally a thermal mechanism, they were not concerned with the diffusion of radicals and its effect on the reaction rate. They were concerned with the energy transported by the diffusion of species. 

As we saw with the steady-state water-column application of the one-dimensional advection-diffusion-reaction equation (Eq. 4.14), the basic shapes of the vertical concentration profiles can be predicted from the relative rates of the chemical and physical processes. Figure 4.21 provided examples of profiles that exhibit curvatures whose shapes reflected differences in the direction and relative rates of these processes. Some generalized scenarios for sedimentary pore water profiles are presented in Figure 12.7 for the most commonly observed shapes. 

In the model, the internal structure of the root is described as three concentric cylinders corresponding to the central stele, the cortex and the wall layers. Diffu-sivities and respiration rates differ in the different tissues. The model allows for the axial diffusion of O2 through the cortical gas spaces, radial diffusion into the root tissues, and simultaneous consumption in respiration and loss to the soil. A steady state is assumed, in which the flux of O2 across the root base equals the net consumption in root respiration and loss to the soil. This is realistic because root elongation is in general slow compared with gas transport. The basic equation is... 

First a derivative is given of the equations of change for a pure fluid. Then the equations of change for a multicomponent fluid mixture are given (without proof), and a discussion is given of the range of applicability of these equations. Next the basic equations for a multicomponent mixture are specialized for binary mixtures, which are then discussed in considerably more detail. Finally diffusion processes in multicomponent systems, turbulent systems, multiphase systems, and systems with convection are discussed briefly. 

This problem is a good example of the importance of formulating a complex diffusion problem in terms of the equations of change. Hence the simplified treatment given here is discussed in terms of the simplified solutions to the three basic equations. 

This outline, as brief and superficial as it may be (for a more detailed description of basic electrochemical transport objects, the reader is referred to relevant texts, e.g., [1]—[3]) will permit a formulation of basic equations of electro-diffusion. A hierarchy of electro-diffusional phenomena will be sketched next, beginning with the simplest equilibrium ones. Subsequent chapters will be devoted to the study of some particular topics from different levels of this hierarchy. 

This book treats a selection of topics in electro-diffusion—a nonlinear transport process whose essence is diffusion of charged particles, combined with their migration in a self-consistent electric field. Basic equations of electro-diffusion were formulated about 100 years ago by Nernst and Planck in the ionic context [1]—[3]. Sixty years later Van Roosbroeck applied these equations to treat the transport of holes and electrons in semiconductors [4]. Correspondingly, major applications of the theory of electro-diffusion still lie in the realms of chemical and electrical engineering, related to ion separation and semiconductor device technology. Some aspects of electrodiffusion are relevant for electrophysiology. 

Table I presents six basic equations in a general way. Those on the left apply to transfer within a phase A, and those on the right to transfer across a phase boundary AB. The top row expresses the mutual definition of force F, proportionality constant K, and potential . The second row expresses the phenomenological proportionality between flux J and force F. The bottom row states the conservation constraints. The left equation says merely that in a given volume the difference between the accumulation rate and the emanation rate must be attributed to a source S. As stated, these equations apply to any conserved quantity which is diffusing, either within a phase under the influence of a potential gradient or across a phase under the influence of a potential difference.

Let us consider as the basic equations those of the diffusion-controlled stochastic Lotka model which are derived in the superposition approximation, thus neglecting terms having a small parameter 5(t). 

A similar problem exists in determining the diffusivity of a gas in a liquid with which it reacts. Diffusivities are not easy to measure accurately, even under the best experimental circumstances. As in the case of solubility, the diffusivity DAB needed in the basic equations can be estimated from a semi-empirical correlation, and... 

Using these assumptions about the diffusion, we may transform for the gas phase the basic equation of the law of energy conservation written in such a form that it is not violated even when in the presence of the chemical reaction (3.3)... 

Our simulations clearly demonstrate that without thermally driven mass diffusion the spatial variation of the control parameter b(T) due to the local laser heating does not provide the typical pattern evolution observed in the experiments. It is crucial to take the Soret effect in the basic equations into account in order to reproduce the phenomena observed in an experiment with local heating. 

For the solution of a salt composed of two ionizable species (binary electrolyte), the four basic equations can be combined to yield the convective diffusion equation for steady-state systems ... 

Abstract The discussion of relaxation and diffusion of macromolecules in very concentrated solutions and melts of polymers showed that the basic equations of macromolecular dynamics reflect the linear behaviour of a macromolecule among the other macromolecules, so that one can proceed further. Considering the non-linear effects of viscoelasticity, one have to take into account the local anisotropy of mobility of every particle of the chains, introduced in the basic dynamic equations of a macromolecule in Chapter 3, and induced anisotropy of the surrounding, which will be introduced in this chapter. In the spirit of mesoscopic theory we assume that the anisotropy is connected with the averaged orientation of segments of macromolecules, so that the equation of dynamics of the macromolecule retains its form. Eventually, the non-linear relaxation equations for two sets of internal variables are formulated. The first set of variables describes the form of the macromolecular coil - the conformational variables, the second one describes the internal stresses connected mainly with the orientation of segments. 

The basic equation for diffusion through a film of liquid accompanied by a first-order irreversible reaction is ... 

The latter form is the basic equation of diffusion generally identified as Fick s first law, formulated in 1855 [13]. Fick s first law, of course, can be deduced from the postulates of irreversible thermodynamics (Section 3.2), in which fluxes are linearly related to gradients. It is historically an experimental law, justified by countless laboratory measurements. The convergence of all these approaches to the same basic law gives us confidence in the correctness of that law. However, the approach used here gives us something more. 

Most commonly, the basic equation we need to solve is the diffusion equation, relating concentration c to time t and distance x from the electrode surface, given the diffusion coefficient D ... 

The principles and basic equations of continuous models have already been introduced in Section 6.2.2. These are based on the well known conservation laws for mass and energy. The diffusion inside the pores is usually described in these models by the Fickian laws or by the theory of multicomponent diffusion (Stefan-Maxwell). However, these approaches basically apply to the mass transport inside the macropores, where the necessary assumption of a continuous fluid phase essentially holds. In contrast, in the microporous case, where the pore size is close to the range of molecular dimensions, only a few molecules will be present within the cross-section of a pore, a fact which poses some doubt on whether the assumption of a continuous phase will be valid. 

Salame substituted four empirical expressions in this basic equation, which he derived from literature data, viz. for ED, D0, AH and S0. In these expressions he used his parameter re as the characteristic datum of the polymer (instead of Tg used as such in our treatment of Diffusivity given earlier). 

Assuming some simplifications, analytical solutions for the transport equation may be inferred from arguments by analogy with the basic equations of heat conduction and diffusion (e.g. Lau et al. (1959), Sauty (1980), Kinzelbach (1983), and Kinzelbach (1987)). 

---