Migration, ion

Nevertheless, the technique suffers from a severe time scale problem -the trajectories are computed for (at most) a few nanoseconds. This is far too short compared to times required for many processes in biophysics. For example, the ii to T conformational transition in hemoglobin lasts tens of microseconds [1], and the typical time for ion migration through the gramicidin channel is hundreds of nanoseconds. This limits (of course) our ability to make a meaningful comparison to experiments, using MD. 

The benzyltnmethylammonium ion migrates to the butyl bromide phase carrying a cyanide ion along with it... 

Several aqueous systems should be considered in a similar manner. For example, in the selective removal of divalent cations from a saturated salt solution, the hydrated resin gives up a portion of its normal water content as it contacts the salt stream. In so doing, the particles shrink, and the inner pathways for ion migration become smaller. 

The 2eohte sodium X (type 13X) has a crystallographic aperture of 0.74 nm. This compares well with the adsorbate value of 0.81 nm. ZeoHte calcium X exhibits a smaller apparent pore si2e of 0.78 nm (lOX). This difference is probably due to some distortion of the aluminosihcate framework upon dehydration and calcium ion migration. 

Oxygen concentration is held almost constant by water flow outside the crevice. Thus, a differential oxygen concentration cell is created. The oxygenated water allows Reaction 2.2 to continue outside the crevice. Regions outside the crevice become cathodic, and metal dissolution ceases there. Within the crevice. Reaction 2.1 continues (Fig. 2.3). Metal ions migrating out of the crevice react with the dissolved oxygen and water to form metal hydroxides (in the case of steel, rust is formed) as in Reactions 2.3 and 2.4 ... 

Corrosion products are almost always absent in stainless steel crevices. Areas just outside stainless crevices are stained brown and orange with oxides (Figs. 2.20 and 2.21). Metal ions migrate out of the crevice. Precipitation occurs by reactions similar to Reactions 2.3 and 2.4. Crevice interiors remain relatively free of rust (Figs. 2.16 and 2.17). 

The hydroxyl ions migrate inward, attracted by the positive charge that is produced by the ferrous ion generated near the corroding surface (Fig. 3.4). Other anions such as carbonate, chloride, and sulfate also concentrate beneath the shell. Carbonate may react with ferrous ions to form siderite (FeCOa) as in Reaction 3.4 (Fig. 3.7) ... 

Bu4N F , THF. When Bu4N F is used to remove the TIPDS group, ester groups can migrate because of the basic nature of fluoride ion. Migration can be prevented by the addition of Pyr - HCl. ... 

Similarly if tlris electrolyte is made into a composite with SrS, SrC2 or SrH2, the system may be used to measure sulphur, carbon and hydrogen potentials respectively, tire latter two over a resuicted temperamre range where the carbide or hydride are stable. The advantage of tlrese systems over the oxide electrolytes is that the conductivity of the fluoride, which conducts by F ion migration, is considerably higher. 

Both reactions indicate that the pH at the cathode is high and at the anode low as a result of the ion migration. In principle, the aeration cell is a concentration cell of H ions, so that the anode remains free of surface films and the cathode is covered with oxide. The J U curves in Fig. 2-6 for anode and cathode are kept apart. Further oxidation of the corrosion product formed according to Eq. (4-4) occurs at a distance from the metal surface and results in a rust pustule that covers the anodic area. Figure 4-2 shows the steps in the aeration cell. The current circuit is completed on the metal side by the electron current, and on the medium side by ion migration. 

Ion migration can be explained by Eq. (2-23). The electrical voltages involved range from a few tenths to several volts and arise from the following causes [8-10] ... 

A consequence of ion migration is electrolytic blister formation. In the case of anodic blisters the coated surface shows pitting, whereas in the case of cathodic blisters there is no change in the metal surface or there is merely the formation of thin oxide layers with annealing color. 

An important consequence of ion migration is the formation of cells where the coated surface acts as a cathode and the exposed metal at the damage acts as an anode (see Section 4.3). The reason for this is that at the metal/coating interface, the cathodic partial reaction of oxygen reduction according to Eq. (2-17) is much less restricted than the anodic partial reaction according to Eq. (2-21). The activity of such cells can be stimulated by cathodic protection. 

Organic acids yield lemon-yellow zones on a blue background [1]. Halide ions migrate as ammonium salts in ammoniacal mobile phases and are also colored yellow. The colors fade rapidly in the air. This can be delayed for some days by covering the chromatogram with a glass plate. 

Film rearrangement resulting in the formation of oxide subgrain and grain boundaries these paths of easy ion migration promote the formation of oxide islands and result in an increase in the growth rate of the oxide. 

The development of acidity within an occluded cell is by no means a new concept, and it was used by Hoar s as early as 1947 in his Acid Theory of Pitting to explain the pitting of passive metals in solutions containing Cl ions. According to Hoar the Cl ions migrate to the anodic sites and the metal ions at these sites hydrolyse with the formation of HCl, a strong acid that inhibits the formation of a protective film of oxide or hydroxide. Edeleanu and Evans followed the pH changes when aluminium was made anodic in Cl solutions and found that the pH decreased from 8-8 to 5-3. 

The explicit mathematical treatment for such stationary-state situations at certain ion-selective membranes was performed by Iljuschenko and Mirkin 106). As the publication is in Russian and in a not widely distributed journal, their work will be cited in the appendix. The authors obtain an equation (s. (34) on page 28) similar to the one developed by Eisenman et al. 6) for glass membranes using the three-segment potential approach. However, the mobilities used in the stationary-state treatment are those which describe the ion migration in an electric field through a diffusion layer at the phase boundary. A diffusion process through the entire membrane with constant ion mobilities does not have to be assumed. The non-Nernstian behavior of extremely thin layers (i.e., ISFET) can therefore also be described, as well as the role of an electron transfer at solid-state membranes. 

The conductivity of liquid and glass membranes is determined by ion-migration (absence of an excess of supporting electrolyte is assumed) in the diffusion layer. Equation (25) should then be written as ... 

Sodium ions migrate out of the cavities Ca2+ ions from die hard water move in to replace them. 

Two product barrier layers are formed and the continuation of reaction requires that A is transported across CB and C across AD, assuming that the (usually smaller) cations are the mobile species. The interface reactions involved and the mechanisms of ion migration are similar to those already described for other systems. (It is also possible that solid solutions will be formed.) As Welch [111] has pointed out, reaction between solids, however complex they may be, can (usually) be resolved into a series of interactions between two phases. In complicated processes an increased number of phases, interfaces, and migrant entities must be characterized and this requires an appropriate increase in the number of variables measured, with all the attendant difficulties and limitations. However, the careful selection of components of the reactant mixture (e.g. the use of a common ion) or the imaginative design of reactant disposition can sometimes result in a significant simplification of the problems of interpretation, as is seen in some of the examples cited below. 

Figure 1.5. Schematic representation of a metal electrode deposited on a 02 -conducting (left) and on a Na -conducting (right) solid electrolyte, showing the location of the metal-electrolyte double layer and of the effective double layer created at the metal/gas interface due to potential-controlled ion migration (backspillover).

This perturbation is then propagated via the spatial constancy of the Fermi level Ef throughout the metal film to the metal-gas interface G, altering its electronic properties thus causing ion migration and thus influencing catalysis, i.e. catalytic reactions taking place on the metal-gas interface G. 

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