Free path length

At the present time there exist no flux relations wich a completely sound cheoretical basis, capable of describing transport in porous media over the whole range of pressures or pore sizes. All involve empiricism to a greater or less degree, or are based on a physically unrealistic representation of the structure of the porous medium. Existing models fall into two main classes in the first the medium is modeled as a network of interconnected capillaries, while in the second it is represented by an assembly of stationary obstacles dispersed in the gas on a molecular scale. The first type of model is closely related to the physical structure of the medium, but its development is hampered by the lack of a solution to the problem of transport in a capillary whose diameter is comparable to mean free path lengths in the gas mixture. The second type of model is more tenuously related to the real medium but more tractable theoretically. 

When Che diameter of the Cube is small compared with molecular mean free path lengths in che gas mixture at Che pressure and temperature of interest, molecule-wall collisions are much more frequent Chan molecule-molecule collisions, and the partial pressure gradient of each species is entirely determined by momentum transfer to Che wall by mechanism (i). As shown by Knudsen [3] it is not difficult to estimate the rate of momentum transfer in this case, and hence deduce the flux relations. 

The Stefan-Maxwell equations have been presented for the case of a gas in the absence of a porous medium. However, in a porous medium whose pores are all wide compared with mean free path lengths it is reasonable to guess that the fluxes will still satisfy relations of the Stefan-Maxwell form since intermolecular collisions still dominate molecule-wall collisions. 

Finally we require a case in which mechanism (lii) above dominates momentum transfer. In flow along a cylindrical tube, mechanism (i) is certainly insignificant compared with mechanism (iii) when the tube diameter is large compared with mean free path lengths, and mechanism (ii) can be eliminated completely by limiting attention to the flow of a pure substance. We then have the classical Poiseuille [13] problem, and for a tube of circular cross-section solution of the viscous flow equations gives 2... 

The limiting cases of greatest interest correspond to conditions in which the mean free path lengths are large and small, respectively, compared with the pore diameters. Recall from the discussion in Chapter 3 that the effective Knudsen diffusion coefficients are proportional to pore diameter and independent of pressure, while the effective bulk diffusion coefficients are independent of pore diameter and inversely proportional to pressure. 

It ls not surprising chat such a relation should hold at the Limit of Knudsen diffusion, since Che Knudsen diffusion coefficients are themselves inversely proportional to the square roots of molecular weights, but the pore diameters in Graham s stucco plugs were certainly many times larger chan the gaseous mean free path lengths at the experimental conditions. 

Knudseci s very careful experiments on a long uniform capillary show that N L/ Pj -p ) passes through a marked minimum when plotted as a function of (P +P2)/2, at a value of the mean pressure such that the capillary diameter and the mean free path length are comparable. At higher values of the mean pressure, N L/(pj " 2 rises linearly, as in the case of a porous medium. 

Figure 6 Mean free path lengths as a function of KE, determined for (a) metals and (b) inorganic compounds. ...

M. P. Seah and W. A Dench. Surf. Interface Anal. 1,1, 1979. Of the many compilations of measured mean free path length versus KE, this is the most thorough, readable, and useful. 

This discussion of geometric effects ignored the attenuation of radiation by material through which the radiation must travel to reach the receptor. The number of particles, dN, penetrating material, equals the number of particles incident N times a small penetration distance, dx, divided by the mean free path length of the type of particle in the type of material (equation 8.3-8). Integrating gives the transmission coefficient for the radiation (equation 8.3-9). 

Assuming that A << /o and that /o varies appreciably only over distances x L, it is easy to show that A//o —XjL, where A is the mean free path length i.e. /o is a good approximation if the characteristic wavelengths of p, T and u are all much greater than the mean free path. The exact solution / can then be expanded in powers of the factor X/L. This systematic expansion is called the CAia.pma.n-Enskog expansion, and is the subject of the next section. 

This is an indication of the collective nature of the effect. Although collisions between hard spheres are instantaneous the model itself is not binary. Very careful analysis of the free-path distribution has been undertaken in an excellent old work [74], It showed quite definite although small deviations from Poissonian statistics not only in solids, but also in a liquid hard-sphere system. The mean free-path X is used as a scaling length to make a dimensionless free-path distribution, Xp, as a function of a free-path length r/X. In the zero-density limit this is an ideal exponential function (Ap)o- In a one-dimensional system this is an exact result, i.e., Xp/(Xp)0 = 1 at any density. In two dimensions the dense-fluid scaled free-path distributions agree quite well with each other, but not so well with the zero-density scaled distribution, which is represented by a horizontal line (Fig. 1.21(a)). The maximum deviation is about... 

Fig. 1.21. Ratio of free-path distribution Xp to the scaled zero-density free-path distribution plotted as a function of reduced free-path length r/X for two-dimensional (a) and three-dimensional (b) liquids. Circles, inverted triangles and upright triangles refer to reduced volumes V/V0 of 1.6, 2, and 3, respectively (V0 is the volume of the system at close packing) [74].

In case of the doped semiconductor of -type under consideration the situation gets simple due to large thickness of SCR if compared to the free path length of the carriers. Therefore, substituting expression (1.42) into (1.41) under condition of applicability of the Boltzmann statistics for the free electrons and holes leads to expression... 

When considering boundary conditions, a useful dimensionless hydrodynamic number is the Knudsen number, Kn = X/L, the ratio of the mean free path length to the characteristic dimension of the flow. In the case of a small Knudsen number, continuum mechanics will apply, and the no-slip boundary condition assumption is valid. In this formulation of classical fluid dynamics, the fluid velocity vanishes at the wall, so fluid particles directly adjacent to the wall are stationary, with respect to the wall. This also ensures that there is a continuity of stress across the boundary (i.e., the stress at the lower surface—the wall—is equal to the stress in the surface-adjacent liquid). Although this is an approximation, it is valid in many cases, and greatly simplifies the solution of the equations of motion. Additionally, it eliminates the need to include an extra parameter, which must be determined on a theoretical or experimental basis. 

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