Mass Transport Selectivity

A membrane is a barrier that allows selective mass transport between two phases. It is selective since various components are able to pass through the membrane more efficiently than others. This makes membranes an appropriate means to separate a mixture of components. That is, a membrane is a permselective barrier between two phases that can be permeated owing to a driving force, such as pressure, concentration, or electric field gradient [18,19], The phases on either side of the membrane can be liquid or gaseous. 

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. 

This section describes selected mass transport correlations for laboratory devices such as the rotating disk and cylinder. These mass transport correlations may be used in order to establish the same mass transport conditions (diffusional boundary layer thicknesses) as those obtained in a pipe or under impinging flow. Essentially, the experimenter may vary the rotation rate and geometry of the cylinder or disk to dial in the same mass transport conditions as obtained in the field for pipes or impinging jets. The user should also verify that the same hydrodynamic conditions also exist through use of Reynolds numbers, as shown above. 

Selective mass transport through permselective hydrogel membranes... 

Biocatalytic membrane reactors combine selective mass transport with chemical reactions and the selective removal of products from the reaction site increases the conversion of product-inhibited or thermodynamically unfavorable reactions. Membrane reactors using biological catalysts can be used in production, processing and treatment operations. Recent advances towards environmentally friendly technologies make these membrane reactors pai ticulaiiy attractive because they do not require additives, are able to function at moderate temperatures and pressrue, and reduce the formation of by-products. The catalytic action of enzymes is extremely efficient and selective compared with chemical catalysts. Uiese enzymes demonstrate higher reaction rates, milder reaction conditions and greater stereospecificity. 

Membrane A thin barrier that permits selective mass transport. 

Faraday s law (p. 496) galvanostat (p. 464) glass electrode (p. 477) hanging mercury drop electrode (p. 509) hydrodynamic voltammetry (p. 513) indicator electrode (p. 462) ionophore (p. 482) ion-selective electrode (p. 475) liquid-based ion-selective electrode (p. 482) liquid junction potential (p. 470) mass transport (p. 511) mediator (p. 500) membrane potential (p. 475) migration (p. 512) nonfaradaic current (p. 512)... 

The flow along the membranes also improves the mass transport there, and the separators between the membranes are constmcted to provide good flow distribution and mixing on the membrane surfaces. Membrane sizes are often about 0.5 x 1 m, spaced about 1 mm apart. Many types of polymers are used to manufacture these ion-exchange-selective membranes, which are often reiaforced by strong fabrics made of other polymers or glass fibers. 

Intraparticle mass transport resistance can lead to disguises in selectivity. If a series reaction A — B — C takes place in a porous catalyst particle with a small effectiveness factor, the observed conversion to the intermediate B is less than what would be observed in the absence of a significant mass transport influence. This happens because as the resistance to transport of B in the pores increases, B is more likely to be converted to C rather than to be transported from the catalyst interior to the external surface. This result has important consequences in processes such as selective oxidations, in which the desired product is an intermediate and not the total oxidation product CO2. 

Rates and selectivities of soHd catalyzed reactions can also be influenced by mass transport resistance in the external fluid phase. Most reactions are not influenced by external-phase transport, but the rates of some very fast reactions, eg, ammonia oxidation, are deterrnined solely by the resistance to this transport. As the resistance to mass transport within the catalyst pores is larger than that in the external fluid phase, the effectiveness factor of a porous catalyst is expected to be less than unity whenever the external-phase mass transport resistance is significant, A practical catalyst that is used under such circumstances is the ammonia oxidation catalyst. It is a nonporous metal and consists of layers of wire woven into a mesh. 

Mass transport selectivity is Ulustrated by a process for disproportionation of toluene catalyzed by HZSM-5 (86). The desired product is -xylene the other isomers are less valuable. The ortho and meta isomers are bulkier than the para isomer and diffuse less readily in the zeoHte pores. This transport restriction favors their conversion to the desired product in the catalyst pores the desired para isomer is formed in excess of the equUibrium concentration. Xylene isomerization is another reaction catalyzed by HZSM-5, and the catalyst is preferred because of restricted transition state selectivity (86). An undesired side reaction, the xylene disproportionation to give toluene and trimethylbenzenes, is suppressed because it is bimolecular and the bulky transition state caimot readily form. 

De Marco R, Mackey DJ, Zirino A (1997) Response of the jalpaite membrane copper(lI) ion-selective electrode in marine waters. Electroanalysis 9 330-334 Kozicki MN, Mitkova M (2006) Mass transport in chalcogenide electrolyte films - materials and applications. J Non-Cryst Solids 352 567-577... 

Worz et al. stress a gain in reaction selectivity as one main chemical benefits of micro-reactor operation [110] (see also [5]). They define criteria that allow one to select particularly suitable reactions for this - fast, exothermic (endothermic), complex and especially multi-phase. They even state that by reaching regimes so far not accessible, maximum selectivity can be obtained [110], Although not explicitly said, maximum refers to the intrinsic possibilities provided by the elemental reactions of a process under conditions defined as ideal this means exhibiting isothermicity and high mass transport. 

Estimation of parameters. Model parameters in the selected model are then estimated. If available, some model parameters (e.g. thermodynamic properties, heat- and mass-transfer coefficient, etc.) are taken from literature. This is usually not possible for kinetic parameters. These should be estimated based on data obtained from laboratory expieriments, if possible carried out isothermal ly and not falsified by heat- and mass-transport phenomena. The methods for parameter estimation, also the kinetic parameters in complex organic systems, and for discrimination between models are discussed in more detail in Section 5.4.4. More information on parameter estimation the reader will find in review papers by Kittrell (1970), or Froment and Hosten (1981) or in the book by Froment and Bischoff (1990). 

The intent of this chapter is to establish a comprehensive framework in which the physicochemical properties of permeant molecules, hydrodynamic factors, and mass transport barrier properties of the transcellular and paracellular routes comprising the cell monolayer and the microporous filter support are quantitatively and mechanistically interrelated. We specifically define and quantify the biophysical properties of the paracellular route with the aid of selective hydrophilic permeants that vary in molecular size and charge (neutral, cationic, anionic, and zwitterionic). Further, the quantitative interrelationships of pH, pKa, partition... 

In Section III, emphasis was placed on flux kinetics across the cultured monolayer-filter support system where the passage of hydrophilic molecular species differing in molecular size and charge by the paracellular route was transmonolayer-controlled. In this situation, the mass transport barriers of the ABLs on the donor and receiver sides of the Transwell inserts were inconsequential, as evidenced by the lack of stirring effects on the flux kinetics. In this present section, the objective is to give quantitative insights into the permeability of the ABL as a function of hydrodynamic conditions imposed by stirring. The objective is accomplished with selected corticosteroid permeants which have been useful in rat intestinal absorption studies to demonstrate the interplay of membrane and ABL diffusional kinetics (Ho et al., 1977 Komiya et al., 1980). 

Therefore, criteria in the selection of an electrode reaction for mass-transfer studies are (1) sufficient difference between the standard electrode potential of the reaction that serves as a source or sink for mass transport and that of the succeeding reaction (e.g., hydrogen evolution following copper deposition in acidified solution), and (2) a sufficiently low surface overpotential and rate of increase of surface overpotential with current density, so that, as the current is increased, the potential will not reach the level required by the succeeding electrode process (e.g., H2 evolution) before the development of the limiting-current plateau is complete. 

In this chapter the theory and practice of limiting-current technique for the measurement of mass-transport coefficients have been described. The selective discussion and tabular compilation of results of investigations that used limiting-current measurements should be indicative of the widespread use of this relatively novel method. 

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