Nonuniform distribution

Some studies of potential commercial significance have been made. For instance, deposition of catalyst some distance away from the pore mouth extends the catalyst s hfe when pore mouth deactivation occui s. Oxidation of CO in automobile exhausts is sensitive to the catalyst profile. For oxidation of propane the activity is eggshell > uniform > egg white. Nonuniform distributions have been found superior for hydrodemetaUation of petroleum and hydrodesulfuriza-tion with molybdenum and cobalt sulfides. Whether any commercial processes with programmed pore distribution of catalysts are actually in use is not mentioned in the recent extensive review of GavriUidis et al. (in Becker and Pereira, eds., Computer-Aided Design of Catalysts, Dekker, 1993, pp. 137-198), with the exception of monohthic automobile exhaust cleanup where the catalyst may be deposited some distance from the mouth of the pore and where perhaps a 25-percent longer life thereby may be attained. 

However, in most cases the AW(D) dependencies are distinctly nonlinear (Fig. 9), which gives impulse to further speculations. Clearly, dependencies of this type can result only from mutual suppression of the hydrogel particles because of their nonuniform distribution over the pores as well as from the presence of a distribution with respect to pore size which does not coincide with the size distribution of the SAH swollen particles. A considerable loss in swelling followed from the W(D) dependencies, as shown in Fig. 9, need a serious analysis which most probably would lead to the necessity of correlating the hydrogel particle sizes with those of the soil pores as well as choice of the technique of the SAH mixing with the soil. Attempts to create the appropriate mathematical model have failed, for they do not give adequate results. 

The work [40] deals with the redistribution of filler particles in the process of injection molding. In this case nonuniform distribution may occur both in the cross-section of a sample and along its length. Both kinds of nonuniformity are linked together if particle moves away from the mold walls it enters the zone of high velocity flow, therefore, a deficit of particles near the walls should be accompanied with a surplus of them far from the inlet. It should be noted that all the works mentioned consider spherical particles there are no theoretical or experimental studies of the redistribution of particles of other shapes, say, fibers or bars. 

The question arises whether an internal standard can be relied upon to eliminate physical differences among samples, the Class II deviations of Section 7.8. No clear answer is possible. Variations in intensity ratios with particle size and with length of grinding time have been observed, especially in the analysis of minerals, but these effects seem due primarily to a nonuniform distribution of the internal standard, and not to particle size as such. These two possible causes of nonuniformity are difficult to separate. 

Lowering the temperature has a similar effect on the deuterium spectra as does increased loadings. In Figure 3, spectra for benzene-d6/(Na)X at 0.7 molecules/supercage over the temperature range 298 to 133 K are shown. It is observed that both benzene species are detected simultaneously between 228 and 188 K. Below this temperature the oriented benzene species becomes the predominant form. A similar situation occurs for polycrystalline benzene-dg in which two quadrupole patterns, one static and the other motionally narrowed due to C rotation, are observed to coexist at temperatures between 110 and 130 K (7). This behavior has been attributed to sample imperfections (8) which give rise to a narrow distribution in correlation times for reorientation about the hexad axis. For benzene in (Na)X and (Cs,Na)X such imperfections may result from the ion/benzene interaction, and a nonuniform distribution of benzene molecules and ions within the zeolite. These factors may also be responsible for producing the individual species. However, from the NMR spectra it is not possible to... 

In multicomponent systems such as solutions, diffusion will arise when at least one of the components is nonuniformly distributed, and its direction will be such as to level the concentration gradients. The diffusion flux (in the direction of decreasing concentrations) is proportional to the concentration gradient of the diffusing substance ... 

When an electrode is in contact with an electrolyte, the interphase as a whole is electroneutral. However, electric double layers (EDLs) with a characteristic potential distribution are formed in the interphase because of a nonuniform distribution of the charged particles. 

Two types of EDL are distinguished superficial and interfacial. Superficial EDLs are located wholly within the surface layer of a single phase (e.g., an EDL caused by a nonuniform distribution of electrons in the metal, an EDL caused by orientation of the bipolar solvent molecules in the electrolyte solution, an EDL caused by specific adsorption of ions). Tfie potential drops developing in tfiese cases (the potential inside the phase relative to a point just outside) is called the surface potential of the given phase k. Interfacial EDLs have their two parts in dilferent phases the inner layer with the charge density in the metal (because of an excess or deficit of electrons in the surface layer), and the outer layer of counterions with the charge density = -Qs m in the solution (an excess of cations or anions) the potential drop caused by this double layer is called the interfacial potential... 

A nonuniform distribution of the reactions may arise when the metal s surface is inhomogeneous, particularly when it contains inclusions of other metals. In many cases (e.g., zinc with iron inclusions), the polarization of hydrogen evolution is much lower at the inclusions than at the base metal hence, hydrogen evolution at the inclusions will be faster (Fig. 22.3). Accordingly, the rate of the coupled anodic reaction (dissolution of the base metal) will also be faster. The electrode s OCP will become more positive under these conditions. At such surfaces, the cathodic reaction is concentrated at the inclusions, while the anodic reaction occurs at the base metal. This mechanism is reminiscent of the operation of shorted galvanic couples with spatially separated reactions Metal dissolves from one electrode hydrogen evolves at the other. Hence, such inclusions have been named local cells or microcells. 

Bartle et al. [286] described a simple model for diffusion-limited extractions from spherical particles (the so-called hot-ball model). The model was extended to cover polymer films and a nonuniform distribution of the extractant [287]. Also the effect of solubility on extraction was incorporated [288] and the effects of pressure and flow-rate on extraction have been rationalised [289]. In this idealised scheme the matrix is supposed to contain small quantities of extractable materials, such that the extraction is not solubility limited. The model is that of diffusion out of a homogeneous spherical particle into a medium in which the extracted species is infinitely dilute. The ratio of mass remaining (m ) in the particle of radius r at time t to the initial amount (mo) is given by ... 

With nickel/alumina catalysts (cf. 4 ) preparation by coprecipitation or by the decomposition of a high dispersion of nickel hydroxide on fresh alumina hydrogel, yields nickel aluminate exclusively. On the other hand, when, as in impregnation, larger particles of nickel compound are deposited, the calcination product is a mixture of nickel oxide and nickel aluminate. The proportion of nickel oxide increases when occlusion of the impregnation solution leads to a very nonuniform distribution (49). 

Figure 2.8 Temporary dipoles and induced dipoles in nonpolar molecules resulting from a nonuniform distribution of electrons at a given instant.

Stolzberg [143] has reviewed the potential inaccuracies of anodic stripping voltammetry and differential pulse polarography in determining trace metal speciation, and thereby bio-availability and transport properties of trace metals in natural waters. In particular it is stressed that nonuniform distribution of metal-ligand species within the polarographic cell represents another limitation inherent in electrochemical measurement of speciation. Examples relate to the differential pulse polarographic behaviour of cadmium complexes of NTA and EDTA in seawater. 

The electrodeposited precursor films prepared in our laboratory that produced high-efficiency devices were Cu-rich films. These precursor films required additional In, Ga, and Se, deposited by PVD, to adjust their final composition to Culni xGaxSe2. During this second step, the substrate temperature was maintained at 560 °C 10 °C. Figure 7.7 presents the Auger analysis of the final absorber and shows nonuniform distribution of Ga in the absorber and more Ga near the surface. This result is primarily from the second-stage PVD addition. The Ga hump is not helpful for hole collection. The device efficiencies are expected to increase by optimizing the Ga distribution in the absorber layers. The optimized layers should have less Ga in the front and more Ga on the back, which facilitates hole collection. 

Despite extensive efforts toward covalent immobilization on the solid phase, surface adsorption is still the most widely used method for immobilization. Most adsorptions are carried out by empirically adjusting conditions to avoid or minimize immunoreactivity loses. Other factors that may affect the success of immobilization include (1) limited surface area availability, (2) nonuniform distributions of the immune complexes on the solid phase (3) the nature of random absorption of the immunoreactive species on the solid surface. 

Active centers, nature of, 10 96 Active site, 27 210-221 in catalysts, 17 103-104, 34 1 for olefin chemisorption, 17 108-113 dual-site concept, 27 210 electrical conductivity, 27 216, 217 ESCA, 27 218, 219 ESR, 27 214-216 infrared spectroscopy, 27 213, 214 model, 27 219-221 molybdena catalyst, 27 304-306 Mdssbauer spectroscopy, 27 217, 218 nonuniform distribution, transport-limited pellets, 39 288-291... 

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