Transport mechanisms Knudsen diffusion

Gas separation is possible even with the two extreme types of membrane considered, i.e. porous and non-porous. The transport mechanisms through these two types of membrane, however, are completely different. Gas separation is performed using membranes based on three general transport mechanisms Knudsen diffusion, solution-diffusion, molecular sieving. Industrially relevant are solution-diffusion based membranes. 

Inspection of Fig. 15.3 reveals that while for jo 0.1 nAcm , the effectiveness factor is expected to be close to 1, for a faster reaction with Jo 1 p,A cm , it will drop to about 0.2. This is the case of internal diffusion limitation, well known in heterogeneous catalysis, when the reagent concentration at the outer surface of the catalyst grains is equal to its volume concentration, but drops sharply inside the pores of the catalyst. In this context, it should be pointed out that when the pore size is decreased below about 50 nm, the predominant mechanism of mass transport is Knudsen diffusion [Malek and Coppens, 2003], with the diffusion coefficient being less than the Pick diffusion coefficient and dependent on the porosity and pore stmcture. Moreover, the discrete distribution of the catalytic particles in the CL may also affect the measured current owing to overlap of diffusion zones around closely positioned particles [Antoine et ah, 1998]. 

The catalyst structure is assumed to be macro-porous, so that transport mechanisms like viscous transport or Knudsen diffusion can be neglected. It is assumed that the component mass transport inside the particle is described by Pick s law of diffusion (due to the relatively low concentrations of the relevant components). 

The viscous flow mechanism is important when the pressure of the system is reasonably high. When this is the case, the constitutive flux equation describes a combined transport of Knudsen diffusion and viscous flow as ... 

The model accounts for three different transport mechanisms, molecular diffusion, Knudsen diffusion, and viscous transport. The total diffusive flux in DGM results from molecular diffusion acting in series with Knudsen diffusion. The viscous porous media flow (Darcy flow) acts in parallel with diffusive flux. The DGM can be written as an implicit relationship among molar concentrations, fluxes, concentration gradients and pressure gradient as... 

The reactant gas species transport to reaction sites through the porous electrodes based on the concept of gas diffusion in porous media. In porous media, the diffusion mechanism can be of three different types ordinary diffusion, Knudsen diffusion, and surface diffusion. If the pores are much larger than the mean free path length, then the molecules collide with each other more frequently than with the pore walls, and ordinary diffusion is assumed to be the dominant diffusion mechanism. Knudsen diffusion is encoimtered in smaller pores or at lower pressure or density. In this case, molecules collide more frequently with the walls than with other gas molecules. The Knudsen diffusion coefficient given is based on kinetic theory as... 

Gas transport can occur in porous membranes by four different idealized mechanisms Knudsen diffusion, partial condensation/diffiision, selective adsorption/diffusion, and molecular sieving (Rao and Sirkar, 1993a,b). Knudsen diffusion occurs when the mean free path of the molecule is greater than the size of the pore therefore, the di sing gas molecule collides more often with the pore wall than with other molecules. Knudsen diffusion can be described using Eq. (23.1) (Hines and Maddox, 1985) ... 

A quantitative answer to above questions may be given through the theoretical modeling of non-isobaric, non-isothermal single component gas phase adsorption. External heat and mass transfer, intrapai ticle mass transport through Knudsen diffusion, Fickian diffusion, sorbed phase diffusion and viscous flow as well as intraparticle heat conduction are accounted for. Fig. 1 presents the underlying assumption on the combination of the different mass transport mechanisms in the pore system. It is shown elsewhere that the assumption of instantaneous... 

FIGt 22-48 Transport mechanisms for separation membranes a) Viscous flow, used in UF and MF. No separation achieved in RO, NF, ED, GAS, or PY (h) Knudsen flow used in some gas membranes. Pore diameter < mean free path, (c) Ultramicroporoiis membrane—precise pore diameter used in gas separation, (d) Solution-diffusion used in gas, RO, PY Molecule dissolves in the membrane and diffuses through. Not shown Electro-dialysis membranes and metallic membranes for hydrogen. 

In Figure 2 we presented the permeability coefficient K of oxygen as a function of the mean gas pressure experimentally obtained for a sample of porous material from acetylene black modified with 35% PTFE. The experimental linear dependence is obtained. The intercept with the abscissa corresponds to the Knudsen term DiK. The value obtained is 2,89.1 O 2 cm2/s. The slope of the straight line is small, so that the ratio K,/ Dik at mean gas pressure 1 atm. is small ( 0.1) which means that the gas flow is predominantly achieved by Knudsen diffusion and the viscous flow is quite negligible. At normal conditions (1 atm, 25°C) the mean free path of the air molecules (X a 100 nm) is greater than the mean pore radii in the hydrophobic material (r 20 nm), so that the condition (X r) for the Knudsen-diffusion mechanism of gas transport is fulfilled. 

It can be concluded that the predominating mode of gas transport in the investigated nano-porous hydrophobic material is Knudsen diffusion, so that the diffusion is the main mechanism of gas transport in electrochemical systems based on such material and operating with gaseous reactants. 

The main emphasis in this chapter is on the use of membranes for separations in liquid systems. As discussed by Koros and Chern(30) and Kesting and Fritzsche(31), gas mixtures may also be separated by membranes and both porous and non-porous membranes may be used. In the former case, Knudsen flow can result in separation, though the effect is relatively small. Much better separation is achieved with non-porous polymer membranes where the transport mechanism is based on sorption and diffusion. As for reverse osmosis and pervaporation, the transport equations for gas permeation through dense polymer membranes are based on Fick s Law, material transport being a function of the partial pressure difference across the membrane. 

Mitrovic and Knezic (1979) also prepared ultrafiltration and reverse osmosis membranes by this technique. Their membranes were etched in 5% oxalic acid. The membranes had pores of the order of 100 nm, but only about 1.5 nm in the residual barrier layer (layer AB in Figure 2.15). The pores in the barrier layer were unstable in water and the permeability decreased during the experiments. Complete dehydration of alumina or phase transformation to a-alumina was necessary to stabilize the pore structure. The resulting membranes were found unsuitable for reverse osmosis but suitable for ultrafiltration after removing the barrier layer. Beside reverse osmosis and ultrafiltration measurements, some gas permeability data have also been reported on this type of membranes (Itaya et al. 1984). The water flux through a 50/im thick membrane is about 0.2mL/cm -h with a N2 flow about 6cmVcm -min-bar. The gas transport through the membrane was due to Knudsen diffusion mechanism, which is inversely proportional to the square root of molecular mass. 

Summarizing it can be stated that the separation by gas phase transport (Knudsen diffusion) has a limited selectivity, depending on the molecular masses of the gases. The theoretical separation factor is decreased by effects like concentration-polarization and backdiffusion. However, fluxes through the membrane are high and this separation mechanism can be applied in harsh chemical and thermal environments with currently available membranes (Uhlhorn 1990, Bhave, Gillot and Liu 1989). 

The species diffusivity, varies in different subregions of a PEFC depending on the specific physical phase of component k. In flow channels and porous electrodes, species k exists in the gaseous phase and thus the diffusion coefficient corresponds with that in gas, whereas species k is dissolved in the membrane phase within the catalyst layers and the membrane and thus assumes the value corresponding to dissolved species, usually a few orders of magnitude lower than that in gas. The diffusive transport in gas can be described by molecular diffusion and Knudsen diffusion. The latter mechanism occurs when the pore size becomes comparable to the mean free path of gas, so that molecule-to-wall collision takes place instead of molecule-to-molecule collision in ordinary diffusion. The Knudsen diffusion coefficient can be computed according to the kinetic theory of gases as follows... 

Besides Knudsen diffusion, permselective transport of gases can occur by various mechanisms involving molecular scale interactions of the sorption-diffusion type. These can be broadly classified into three groups as described below and pictured in Fig. 7. 

There are four well-known types of diffusion in solids [10] gaseous or molecular diffusion [75], Knudsen diffusion [76-80], liquid diffusion [10], and atomic diffusion. In Figure 5.27, the possible transport mechanisms in porous media are schematically shown [77], Gaseous flow (Figure 5.27a)... 

FIGURE 5.27 Transport mechanisms in porous media molecular or gaseous flow, (a) Knudsen flow, (b) surface diffusion, (c) multilayer diffusion, (d) capillary condensation, and (e) configurational diffusion. 

Studies with many types of porous media have shown that for the transport of a pure gas the Knudsen diffusion and viscous flow are additive (Present and DeBethune [52] and references therein). When more than one type of molecules is present at intermediate pressures there will also be momentum transfer from the light (fast) molecules to the heavy (slow) ones, which gives rise to non-selective mass transport. For the description of these combined mechanisms, sophisticated models have to be used for a proper description of mass transport, such as the model presented by Present and DeBethune or the Dusty Gas Model (DGM) [53], In the DGM the membrane is visualised as a collection of huge dust particles, held motionless in space. 

In this treatment only the ordinary and Knudsen diffusion mechanisms will be considered. Then, mass transport in isothermal, multicomponent gas phase systems is described by the following constitutive equation ... 

Hindered diffusion, the primary transport mechanism in porous solids, can be qualitatively described as a series of hops by the analyte, via gas-phase diffusion, from one surface site to the next. Thus, hindered diffusion is composed of two main components a pure diffusion-related term, often Fickian in nature, associated with movement of the analyte in the gas phase and a term describing the noninstantaneous equilibration between gas-phase analyte and the solid surface at each point where the analyte touches down (adsorbs). In extended porous solids (e.g., a chromatographic column tightly packed with porous beads), transport is often more complex, requiring the consideration of such factors as eddy diffusion and Knudsen effusion. This is important if there is a significant pressure drop along the path of the analyte [109]. Finally, the presence of any external fields (thermal, electric, etc.) must be considered as well. 

All these different mechanisms of mass transport through a porous medium can be studied experimentally and theoretically through classical models (Darcy s law, Knudsen diffusion, molecular dynamics, Stefan-Maxwell equations, dusty-gas model etc.) which can be coupled or not with the interactions or even reactions between the solid structure and the fluid elements. Another method for the analysis of the species motion inside a porous structure can be based on the observation that the motion occurs as a result of two or more elementary evolutions that are randomly connected. This is the stochastic way for the analysis of species motion inside a porous body. Some examples that will be analysed here by the stochastic method are the result of the particularisations of the cases presented with the development of stochastic models in Sections 4.4 and 4.5. 

The preceding section assumed that the mass-transport mechanism in a fluid medium is dominated by molecule-molecule collisions. However, the mean free path of gases often exceeds the dimensions of small pores typical of solid catalysts. In this situation, called Knudsen diffusion, molecules collide more often with the pore walls than with other molecules. According to Equation (6.3.1), the Knudsen diffu-sivity of component A, D a, is proportional to r / , but is independent of both pressure and the presence of other species ... 

The transport of a sub-critical Lennard-Jones fluid in a cylindrical mesopore is investigated here, using a combination of equilibrium and non-equilibrium as well as dual control volume grand canonical molecular dynamics methods. It is shown that all three techniques yield the same value of the transport coefficient for diffusely reflecting pore walls, even in the presence of viscous transport. It is also demonstrated that the classical Knudsen mechanism is not manifested, and that a combination of viscous flow and momentum exchange at the pore wall governs the transport over a wide range of densities. 

Capillary condensation provides the possibility of blocking pores of a certain size with the liquid condensate simply by adjusting the vapor pressure. A permporometry lest usually begins at a relative pressure of 1, thus all pores filled and no unhindered gas transport. As the pressure is reduced, pores with a size corresponding to the vapor pressure applied become emptied and available for gas transport. The gas flow through the open mesopores is dominated by Knudsen diffusion as will be discussed in Section 4.3.2 under Transport Mechanisms of Porous Membranes. The flow rate of the noncondensable gas is measured as a function of the relative pressure of the vapor. Thus it is possible to express the membrane permeability as a function of the pore radius and construct the size distribution of the active pores. Although the adsorption procedure can be used instead of the above desorption procedure, the equilibrium of the adsorption process is not as easy to attain and therefore is not preferred. 

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