Halide transport

Catalyst-poisoning studies have concentrated on the potential poisons introduced with fuel, particularly on lead, which has been added intentionally to improve the combustion characteristics at the high compression ratios employed in modem internal combustion engines prior to the introduction of exhaust purification catalysts. The lead is usually introduced as motor mix which contains tetraethyllead in a mixture with organic halides, chlorides or bromides. These halides transport the lead in the form of volatile halides out of the engine and into the exhaust, and are hence termed lead scavengers. Thus the potential catalyst-poison elements associated with the additive mixture are Pb, Br, and Cl. 

We shall start with the basic concept that in the oxides formed on metals, (the same also applies to sulfides and halides) transport of material particles occurs only by the motion of inherent defects (Eigen-Storstellen) present in the lattice these defects are assumed to consist essentially of simple particles in interstitial lattice sites or vacancies of the particles constituting the crystal. The free electrons or holes which are present for reasons of electrical neutrality are coupled to the migrating defects and move considerably more rapidly. 

DyAs in a 100 cm quartz ampoule with 6 mg/cm iodine in a gradient 900-> 980°C required three days. Under similar conditions a 10-days run with DyP yielded only octahedra with edge lengths up to 2 mm (Hulliger, 1976). Due to the lower stability of the heavier Ln phosphides (Torbov et al., 1971) halide transport works in fact best for the second half of the Ln elements (we obtained the largest phosphide crystals with Tm (Hulliger, 1976)). 

Meng J, Pandey R, Vail J M and Kunz A B 1989 Impurity potentials derived from embedded quantum olusters Ag" and Cu" transport In alkali halides J. Phys. Condens Matter 1 6049-58... 

The transport of charged ions in alkali halides and, later on, in (insulating) ceramics is a distinct parepisteme, because electric fields play a key role. This large field is discussed in Schmalzried s 1995 book, already mentioned, and also in a review by one of the pioneers (Nowick 1984). This kind of study in turn led on to the developments of superionic conductors, in which ions and not electrons carry substantial currents (touched on again in Chapter 11, Section 11.3.1.1). 

In the absence of die polyether, potassium fluoride is insoluble in benzene and unreactive toward alkyl halides. Similar enhancement of solubility and reactivity of other salts is observed in the presence of crown ethers The solubility and reactivity enhancement result because the ionic compound is dissociated to a tightly complexed cation and a naked anion. Figure 4.13 shows the tight coordination that can be achieved with a typical crown ether. The complexed cation, because it is surrounded by the nonpolar crown ether, has high solubility in the nonpolar media. To maintain electroneutrality, the anion is also transported into the solvent. The cation is shielded from interaction with the anion as a... 

Properties of some halides useful in CVD are listed in Table 3.3. As can be seen, some of these halides are gaseous or liquid at room temperature and, as such, are easily transported in the reaction chamber. The solid halides, however, must be heated to produce sufficient vapor. This sometimes presents a problem which can be bypassed by generating the halide in situ (see Ch. 5). Most halides are available commercially. 

The hydrogen reduction of the metal halides, described in Sec. 1.2, is generally the favored reaction for metal deposition but is not suitable for the platinum-group metals since the volatilization and decomposition temperatures of their halides are too close to provide efficient vapor transport. 1 1 For that reason, the decomposition of the carbonyl halide is preferred. The exception is palladium which is much more readily deposited by hydrogen reduction than by the carbonyl-halide decomposition. 

CVD Reactions. The platinum halides are volatile with a decomposition pointtooclose to thevaporizati on pointtomakethempracticalfor C VD transport. Platinum canbe deposited by the decomposition of the acetylacetonate, although carbonaceous impurities remain in the deposit. The carbonyl halides, specifically dicarbonyl dichloride, are more satisfactory precursors. The decomposition reaction is as follows ... 

CVD Reactions. The rhodium halides, like those of the other platinum group metal s, are volatile with a decomposition pointtoo close to the vaporization point to make them usable for CVD transport. The metal is commonly produced by the decomposition of metallo-organic precur-... 

Growth of single crystals. Crystals of the aluminum selenide halides (needles, maximum length 15 mm) were grown by vapor transport in sealed ampoules between two temperatures (380 and 320°C for Al-SeCl, and 350 and 300°C for AlSeBr and AlSel) over a period of two months. A large excess of the halogenide was used (266). 

If one of the species is anionic and we need to transport it to the organic phase, then a phase-transfer catalyst may be employed. Consider the example of benzyl penicillin where the reaction between phenyl acetic acid and the penicillin carboxylate ion, with penicillin amidase as a catalyst, is relevant, and which at pH 4.5 - 5.0 is shifted in the desired direction. Here a catalyst like tetrabutylammonium halide works, and with chloroform as a solvent 60% yield can be realized in contrast to a yield of only 5 - 10 % in water. 

Polymorphonuclear leucocytes (PMNs) employ a system comprising myeloperoxidase, hydrogen peroxide, and a halide factor to kill microorganisms and tumour cells. This process is sometimes loosely called the respiratory burst , which refers to the sudden rise in oxygen consumption by the phagocytosing neutrophils that is independent of the mitochondrial electron transport chain. 

In some ionic crystals (primarily in halides of the alkali metals), there are vacancies in both the cationic and anionic positions (called Schottky defects—see Fig. 2.16). During transport, the ions (mostly of one sort) are shifted from a stable position to a neighbouring hole. The Schottky mechanism characterizes transport in important solid electrolytes such as Nernst mass (Zr02 doped with Y203 or with CaO). Thus, in the presence of 10 mol.% CaO, 5 per cent of the oxygen atoms in the lattice are replaced by vacancies. The presence of impurities also leads to the formation of Schottky defects. Most substances contain Frenkel and Schottky defects simultaneously, both influencing ion transport. 

As a further approach for novel electrolytes appropriate for selective cation transport, we have prepared poly(organoboron halide)-imidazole complexes.35 Even though boron-amine complexes are widely known materials reported by the early works of H. C. Brown et al.,52-54 they had not been investigated as solvents or electrolytes to the best of our knowledge. 

It is known that organoboron halide-imidazole complexes dissociate diming equilibrium 56 however, charges disappear upon dissociation. In such a matrix, mobile ions should not originate from the matrix. Therefore, the polymer electrolytes composed of boron halide-imidazole complexes were considered to be appropriate for selective ion transport. 

The capacitance determined from the initial slopes of the charging curve is about 10/a F/cm2. Taking the dielectric permittivity as 9.0, one could calculate that initially (at the OCP) an oxide layer of the barrier type existed, which was about 0.6 nm thick. A Tafelian dependence of the extrapolated initial potential on current density, with slopes of the order of 700-1000 mV/decade, indicates transport control in the oxide film. The subsequent rise of potential resembles that of barrier-layer formation. Indeed, the inverse field, calculated as the ratio between the change of oxide film thickness (calculated from Faraday s law) and the change of potential, was found to be about 1.3 nm/V, which is in the usual range. The maximum and the subsequent decay to a steady state resemble the behavior associated with pore nucleation and growth. Hence, one could conclude that the same inhomogeneity which leads to pore formation results in the localized attack in halide solutions. 

The possible mechanisms which one might invoke for the activation of these transition metal slurries include (1) creation of extremely reactive dispersions, (2) improved mass transport between solution and surface, (3) generation of surface hot-spots due to cavitational micro-jets, and (4) direct trapping with CO of reactive metallic species formed during the reduction of the metal halide. The first three mechanisms can be eliminated, since complete reduction of transition metal halides by Na with ultrasonic irradiation under Ar, followed by exposure to CO in the absence or presence of ultrasound, yielded no metal carbonyl. In the case of the reduction of WClfc, sonication under CO showed the initial formation of tungsten carbonyl halides, followed by conversion of W(C0) , and finally its further reduction to W2(CO)io Thus, the reduction process appears to be sequential reactive species formed upon partial reduction are trapped by CO. 

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