Adsorbed impurities

Actual crystal planes tend to be incomplete and imperfect in many ways. Nonequilibrium surface stresses may be relieved by surface imperfections such as overgrowths, incomplete planes, steps, and dislocations (see below) as illustrated in Fig. VII-5 [98, 99]. The distribution of such features depends on the past history of the material, including the presence of adsorbing impurities [100]. Finally, for sufficiently small crystals (1-10 nm in dimension), quantum-mechanical effects may alter various physical (e.g., optical) properties [101]. 

Pharmaceutical. Ion-exchange resins are useful in both the production of pharmaceuticals (qv) and the oral adrninistration of medicine (32). Antibiotics (qv), such as streptomycin [57-92-17, neomycin [1404-04-2] (33), and cephalosporin C [61-24-5] (34), which are produced by fermentation, are recovered, concentrated, and purified by adsorption on ion-exchange resins, or polymeric adsorbents. Impurities are removed from other types of pharmaceutical products in a similar manner. Resins serve as catalysts in the manufacture of intermediate chemicals. 

Ideally, straight-line isotherm plots are obtained. However there may occasionally be departures from linearity. A curve as shown in Figure 30 (A) may be obtained if a non-adsorbable impurity is present in the liquid being treated. For such simations subtracting Cj from Q and re-plotting the isotherm will usually yield a straight line. 

In this situation computer simulation is useful, since the conditions of the simulation can be chosen such that full equihbrium is established, and one can test the theoretical concepts more stringently than by experiment. Also, it is possible to deal with ideal and perfectly flat surfaces, very suitable for testing the general mechanisms alluded to above, and to disregard in a first step all the complications that real substrate surfaces have (corrugation on the atomistic scale, roughness on the mesoscopic scale, surface steps, adsorbed impurities, etc.). Of course, it may be desirable to add such complications at a later stage, but this will not be considered here. In fact, computer simulations, i.e., molecular dynamics (MD) and Monte Carlo (MC) calculations, have been extensively used to study both static and dynamic properties [11] in particular, structural properties at interfaces have been considered in detail [12]. 

The platinum electrode is also very convenient for investigating various adsorption phenomena in electrochemical systems. The surface of platinum is very stable and reproducible. As will be shown in what follows, the true working area can be determined with high accuracy for platinum surfaces with appreciable roughness and even for electrodes with highly dispersed platinum deposits. It is comparatively easy to clean the surface of adsorbed impurities and to control the state of the surface. 

Platinum surfaces Mith (111) and (100) orientations treated in this May have been checked by using LEED characterization on as received" samples, both shoued the characteristic LEED pattern Hith their respective (lxl) surface symmetry. The non observation of the (5x20) symmetry for the (100) orientation Mas due to the presence of residual adsorbed impurities at the surface of as received samples. Simply this confirms the crystalline surface quality of the platinum samples prepared according to this technique (10). 

Pretreatment of carbon. In all experiments it has to be ascertained that no adsorbed impurities are present on the carbon surface. 

In the majority of impurity removal processes, the adsorbent functions both as a catalyst and as an adsorbent (catalyst/adsorbent). The impurity removal process often involves two steps. First, the impurities react with the catalyst/adsorbent under specified conditions. After the reaction, the reaction products are adsorbed by the catalyst/adsorbent. Because this is a chemical adsorption process, a severe regeneration condition, or desorption, of the adsorbed impurities from the catalyst/adsorbent is required. This can be done either by burning off the impurities at an elevated temperature or by using a very polar desorbent such as water to desorb the impurities from the catalyst/adsorbent. Applications to specific impurities are covered in the followings section. The majority of industrial applications involve the removal of species containing hetero atoms from bulk chemical products as purification steps. 

Occlusion. Adsorbed impurities on the surface of the crystal are trapped by subsequent strata during crystal accretion. 

Rinse the SPE cartridge with a strong solvent to remove adsorbed impurities. 

A second mechanism by which impurities present in the solution interfere with measurements in electrode kinetics is associated less with their providing alternative paths to reactions and more with their adsorption on the electrode surface. The presence of adsorbed impurity material on the electrode surface may affect the rate of an intended reaction, particularly where there is an intermediate in the mechanism of the intended reaction.25 Thus, the adsorbed impurity may block reactive sites on the electrode. Since the intended reaction (say, the reduction of oxygen) cannot now use the blocked active sites on the electrode surface, its kinetics are slowed down, particularly when the impurity adsorbs on the most active catalytic sites on the electrode. Again,... 

Scavenging of residual impurities in the solution may be necessary ifth e rate-potential relation betrays the effects of impurities in the solution by some kind of aberrant behavior. One introduces a large auxiliary electrode of high area platinum black and changes the potential on it slowly and cyclically over the range of potentials of the intended experiment (Bockris and Conway, 1949). A day or so of this cycling may be necessary and the platinum black sheet (which now contains deposited or adsorbed impurities) must be removed carefully with the potential still on (so that the impurities do not desorb back into the solution). 

Figure 25-4 HPLC column with replaceable guard column to collect irreversibly adsorbed impurities. Titanium frits distribute the liquid evenly over the diameter of the column. [Courtesy Upchurch Scientific, Oak Harbor. WAJ...

Adsorbed impurities are bound to the surface of a crystal. Absorbed impurities (within the crystal) are classified as inclusions or occlusions. Inclusions are impurity ions that randomly occupy sites in the crystal lattice normally occupied by ions that belong in the crystal. Inclusions are more likely when the impurity ion has a size and chaige similar to those of one of the ions that belongs to the product. Occlusions are pockets of impurity that are literally trapped inside the growing crystal. 

In each step in the process there is a change in the adsorbate (impurity) loading on the adsorbent bed and a change in the total gas storage within the adsorber vessel. These changes are caused by ... 

The laser is used in two ways. In the first strike, it is defocused and its beam is used simply to clear adsorbed impurities, films, etc., from the area, a small portion of which (say, a micron in dimension) is to be the object of a pothole excavation. In the second strike, the laser is intensely focused after passing through a lens system, and the intensity of its strike vaporizes metal to form a hole. The size of the potholes is as little as 0.1 pm in diameter and about 1 pm in depth. A hard vacuum (10 10 to 10 y mm Hg) is necessary to give the quadrupole mass spectrometer the required sensitivity. A diagram of the technique is shown in Fig. 12.95. 

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