Mean 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. 

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. 

Thus the mean free path length X for the particle number density n is, in accordance with equation (1.1), inversely proportional to pressure p. Thus the following relationship holds, at constant temperature T, for every gas... 

Used to calculate the mean free path length X for any arbitrary pressures and various gases are Table III and Fig. 9.1 in Chapter 9. The equations in gas kinetics which are most important for vacuum technology are also summarized (Table IV) in chapter 9. 

The gas molecules fly about and among each other, at every possible velocity, and bombard both the vessel walls and collide (elastically) with each other. This motion of the gas molecules is described numerically with the assistance of the kinetic theory of gases. A molecule s average number of collisions over a given period of time, the so-called collision index z, and the mean path distance which each gas molecuie covers between two collisions with other molecules, the so-called mean free path length X, are described as shown below as a function of the mean molecule velocity c the molecule diameter 2r and the particle number density molecules n - as a very good approximation ... 

With the acceptance of the atomic view of the world - accompanied by the necessity to explain reactions in extremely dilute gases (where the continuum theory fails) - the kinetic gas theory was developed. Using this it is possible not only to derive the ideal gas law in another manner but also to calculate many other quantities involved with the kinetics of gases - such as collision rates, mean free path lengths, monolayer formation time. 

Molecular flow prevails In the high and ultrahigh vacuum ranges. In these regimes the molecules can move freely, without any mutual Interference. Molecular flow Is present where the mean free path length for a particle Is very much larger than the diameter of the pipe X d. 

Fig. 2.1 Processes like chemical vapor deposition must sometimes consider the effects of submicron features at the deposition surfaces. When the features sizes are on the order of the mean-free-path length, then continuum assumptions can be questionable.

Consider a molecular-level view of a portion of the fluid shown schematically in Fig. 12.9. A test plane is placed at height z, where the temperature is T (z). Molecules in the upper plane at z + L (L is the mean-free-path length) have temperature T + L(dT/dz) molecules in the lower plane at z — L have temperature T — L(dT/dz). Because of the temperature gradient, the average energy per molecule e will vary with height ... 

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