Accessibility of pores

With respect to porous solids, the surface associated with pores may be called the internal surface. Because the accessibility of pores may depend on the size of the fluid molecules, the extent of the accessible internal surface may depend on the size of the molecules comprising the fluid, and may be different for the various components of a fluid mixture (molecular sieve effect). 

Most solids of high surface area are to some extent porous. The texture of such materials is defined by the detailed geometry of the void and pore space. Porosity, , is a concept related to texture and refers to the pore space in a material. An open pore is a cavity or channel communicating with the surface of a particle, as opposed to a closed pore. Void is the space or interstice between particles. In the context of adsorption and fluid penetration powder porosity is the ratio of the volume of voids plus the volume of open pores to the total volume occupied by the powder. Similarly, particle porosity is the ratio of the volume of open pores to the total volume of the particle. It should be noted that these definitions place the emphasis on the accessibility of pore space to the adsorptive. 

The column packing in SEC comprises porous, spherical gel beads with a defined pore size distribution. Most often, these beads are made from poly(styr-ene-divinylbenzene). (For GFC, cross-linked dextran and agarose gels are often used. ) The sample is dissolved in a suitable solvent that is often used as the mobile phase as well. Separation occurs as a result of differences in accessibility of pore volume. Small molecules can freely access the whole pore volume as a result, the column retards these molecules the greatest. As molecular volume increases, less and less pore volume is accessible for molecules to sample, and elution times decrease. For all molecules with hydrodynamic volumes that are too large to penetrate into the pores of the packing, elution occurs at the (interstitial) void volume of the column. The retention volume for each solute can be described mathematically as ... 

The effect on adsorption of the fixation of oxygen surface complexes is shown in Table 8. In addition to the decrease in V stated before, the adsorption is less energetic after the treatment [28-30] because partial blocking of the pores hinders the access of pores with similar dimension to the molecular size of the adsorbates. Moreover, it is interesting to point out that benzene is adsorbed more strongly on the original than on the oxidized... 

The dimensions and accessibility of pores of zeohtes and microporous solids are confined to the subnanometer scale (<1.5 run), which hmits their applications when processing bulky molecules. Mesoporous materials with pore sizes ranging from 2 to 50 nm overcome these limitations. In contrast with microporous zeolites, these materials lack atomic ordering (crystallinity) in their silica walls as these are usually amorphous. The attractive properties of ordered mesoporous materials include well-defined pore system high surface area and pore sizes narrow pore size distribution tunable up to 100 nm existence of micropores in the amorphous wall (for thicker wall materials) existence of various wall (framework) compositions obtained from direct synthesis, or posttreatment or modification high thermal and hydrothermal stabilities if properly prepared or treated and various controllable regular morphologies on different scales from nanometers to micrometers. 

Electrolytes play an important role in overall ES performance. They exert critical effects on the development of the double-layer and accessibility of pores to electrolyte ions. Normally, electrolyte-electrode interactions and the ionic conductivity of the electrolyte play a significant role in internal resistance. Poor electrolyte stability at different cell operating temperatures and poor chemical stability at high rates can further increase resistances within an ES and reduce cycle life. 

A procedure that is more suitable for obtaining the actual distribution of pore sizes involves the use of a nonwetting liquid such as mercury—the contact angle on glass being about 140° (Table X-2) (but note Ref. 31). If all pores are equally accessible, only those will be filled for which... 

The increase in pore volume brought about by high intrusion pressures may be caused by fracture of the pore walls that gives access to pores... 

It is often important to quantify the contamination of pore fluid in the unsaturated soil 2one, where monitoring wells are ineffective. In this region, suction cup lysimeters are useful (7). These samplers consist of a porous cup, typically ceramic, having two access tubes which are usually Teflon. One access tube provides a pressure-vacuum, the other discharges the sampled fluid to the surface. The porous cup, typically between 2 and 5 cm in diameter, is attached to a PVC sample accumulation chamber. 

The stmcture of activated carbon is best described as a twisted network of defective carbon layer planes, cross-linked by aHphatic bridging groups (6). X-ray diffraction patterns of activated carbon reveal that it is nongraphitic, remaining amorphous because the randomly cross-linked network inhibits reordering of the stmcture even when heated to 3000°C (7). This property of activated carbon contributes to its most unique feature, namely, the highly developed and accessible internal pore stmcture. The surface area, dimensions, and distribution of the pores depend on the precursor and on the conditions of carbonization and activation. Pore sizes are classified (8) by the International Union of Pure and AppHed Chemistry (lUPAC) as micropores (pore width <2 nm), mesopores (pore width 2—50 nm), and macropores (pore width >50 nm) (see Adsorption). 

Scouting and bleaching slightly increase the accessible internal volume, Hquid ammonia treatment of the scoured—bleached cotton decreases it slightly, caustic mercerization substantially enhances accessibiHty, and cross-linking to impart durable press properties reduces this accessible internal pore volume substantially. 

Nickel is the most used catalyst, 20 to 25 percent Ni on a porous siliceous support in the form of flakes that are readily fQterable. The pores allow access of the reacdants to the extended pore surface, which is in the range of 200 to 600 mVg (977 X 10 to 2,931 X 10 ftMbm) of... 

Molecular sieves are available with a variety of pore sizes. A molecular sieve should be selected with a pore size that will admit H2S and water while preventing heavy hydrocarbons and aromatic compound.s from entering the pores. However, carbon dioxide molecules are about the same size as H2S molecules and present problems. Even thougli die COi is non-polar and will not bond to the active sites, the CO2 will entci the pores. Small quantities of CO2 will become trapped in the pores In this way small portions of CO2 are removed. More importantly, CO ih obstruct the access of H2S and water to active sites and decrease the eflectiveness ot the pores. Beds must be sized to remove all water and to pi ovitte for interference from other molecules in order to remove all H i.S. 

With these facts in mind, it seems reasonable to calculate the pore volume from the calibration curve that is accessible for a certain molar mass interval of the calibration polymer. A diagram of these differences in elution volume for constant M or AM intervals looks like a pore size distribution, but it is not [see the excellent review of Hagel et al. (5)]. Absolute measurements of pore volume (e.g., by mercury porosimetry) show that there is a difference on principle. Contrary to the absolute pore size distribution, the distribution calcu-... 

Section 1.9 showed that as long as an oxide layer remains adherent and continuous it can be expected to increase in thickness in conformity with one of a number of possible rate laws. This qualification of continuity is most important the direct access of oxidant to the metal by way of pores and cracks inevitably means an increase in oxidation rate, and often in a manner in which the lower rate is not regained. In common with other phase change reactions the volume of the solid phase alters during the course of oxidation it is the manner in which this change is accommodated which frequently determines whether the oxide will develop discontinuities. It is found, for example, that oxidation behaviour depends not only on time and temperature but also on specimen geometry, oxide strength and plasticity or even on specific environmental interactions such as volatilisation or dissolution. 

Highly active catalysts have been produced by adsorption of lipases onto macroporous acrylate beads, polypropylene particles and phenol-formaldehyde weak anion exchange resins. Protein is bound, presumably essentially as a monolayer, within the pores of the particles. The large surface area of the particles (10m2 g 1) means that substantial amounts of protein can be adsorbed, and the pores are of sufficient size to allow easy access of reactants to this adsorbed protein. 

In view of the accessibility of zeolite A (only linear molecules adsorb) the coupling will take place at the outer surface of the zeolite crystals. Indeed, Ag-Y and especially a Ag-loaded amorphous silica-alumina, containing a spectrum of wider pores, mrned out to be much better promoter-agents (ref. 28). The silica-alumina is etched with aqueous NaOH and subsequently exchanged with Ag(I). 

Figure 4.2. The structure of Faujasite, a more open, larger pore zeolite. Larger molecules can enter this structure, which is more open, and slightly less regular than HZSM5 (Figure 4.1). Nevertheless, there are still many important molecules which cannot enter the pores of this zeolite, one of the most accessible of the class.

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