A generalized treatment of gas transport in porous media is presented as developed on the basis of the ``dusty-gas'' model, a model in which a porous medium is described as consisting of uniformly distributed, giant molecules (dust) held stationary in space. The problem is broken down into a series of special cases which involve the various combinations of gradients in composition, pressure, and temperature. Equations are given for the description of several well-known phenomena. These include isobaric, isothermal diffusion; diffusion under the influence of a pressure gradient; Poiseuille's flow equation, including the Knudsen minimum; the Kramers—Kistemaker effect; thermal transpiration; and the effect of pressure on the thermal-diffusion factor. The results are likewise applicable to capillaries by a suitable substitution for geometric parameters.
A model is presented for the diffusion of gases in porous media in the absence of pressure gradients, in which the porous medium is visualized as a collection of uniformly distributed ``dust'' particles which are constrained to be stationary. By formally considering the dust particles as giant molecules, it is possible to derive all the desired results very simply from rigorous kinetic theory as special cases of multicomponent mixtures. By formally varying the mole fractions of the real gas molecules, the entire pressure range from the Knudsen region to the normal diffusion region can be covered. This model permits the first satisfactory theoretical derivation of the experimentally discovered fact that the flux ratio for binary mixtures is equal to (m2/m1)½ at all pressures (not just in the Knudsen region). It also permits a rigorous theoretical treatment of the entire transition region for the first time, from which is obtained the usual Bosanquet interpolation formula and a differential equation for diffusion which covers the entire range (and appears to be new). The model gives no quantitative a priori characterization of the porous medium itself, but if one gas mixture is measured in a given medium, then the behavior of other gas mixtures in the same medium can be predicted.
A previously proposed model for the diffusion of gases in porous media at uniform pressure is extended to allow for pressure gradients. The porous medium is visualized as a collection of ``dust'' particles constrained to remain stationary in space. As before, the entire range of intermediate mechanisms from the Knudsen to the normal diffusion region can be covered by varying the mole fraction of real gases. The effect of pressure gradients is to introduce into the fundamental kinetic theory equations both a pressure diffusion term and an external force term, which is needed to keep the porous medium from being pushed along by the pressure gradient. Somewhat surprisingly, there is a considerable cancellation of terms, and the final diffusion equation has the same form as in the uniform pressure case. No additional parameters beyond those necessary to define a diffusing system at uniform pressure are thus required to compute the diffusion rates when pressure gradients are present. The coefficients of the diffusion equation, however, now depend on position through their dependence on pressure, and the net flux J of all molecules is an undetermined quantity. A complete solution requires also a forced flow equation giving J as a function of the pressure gradient. A forced flow equation is derived on the basis of the dusty gas model, but one parameter must be made disposable in order to compensate for the fact that the model permits only a diffusive mechanism for flow, never a viscous mechanism. Another forced flow equation is derived by analogy with Poiseuille flow, in which the porous medium is visualized as a group of capillaries. The two models are shown to be not inconsistent in viscous flow regimes, and complement rather than contradict each other. The Poiseuille model is mathematically very cumbersome, however, and has been used only at one especially simple point (at which J=0) to give an independent evaluation of the disposable parameter occurring in the dusty gas model. Agreement of the calculations with available experimental data is good. As in the uniform pressure case, the model does not give an a priori characterization of any porous medium, but rather permits prediction of the behavior of different gas mixtures under a variety of conditions on the basis of three parameters which can be obtained from only a few experimental measurements.
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