Iodide transport process

The method of choice for the preparation of Pa metal is a somewhat modified van Arkel-De Boer process, which uses protactinium carbide (Section II,C) as the starting material. The carbide and iodine are heated to form protactinium iodide, which is thermally dissociated on a hot filament 12-15). An elegant variation is to replace the filament with an inductively heated W or Pa sphere 109). A photograph of a 1.4-g sample of Pa metal deposited on a radiofrequency-heated W sphere is shown in Fig. 6. From the analytical data presented in Table V, the impurities present before and after application of this modified iodide transport process (Sections II,D and III,C) can be compared. 

Iodide refining, while belonging to the group of processes known as chemical transport processes, is also a good example of the class of processes known as chemical vapor deposition (CVD). 

Protactinium metal was first prepared in 1934 by thermal decomposition of a pentahalide on a hot filament 50). It has since been prepared from PaF4 by metallothermic reduction (Section II,A) with barium 26, 27, 34,102), lithium 40), and calcium 73, 74). However, the highest purity metal is achieved using the iodide transport (van Arkel-De Boer) process (Section II,D). 

Disease can be defined according to the sites and types of specific biochemical processes. The disease originally called Graves Disease and now called hyperthyroidism is manifest by increased expression of the sodium/iodide transporter, which results in increased accumulation of iodide, increased synthesis of thyroxin and other thyroid hormones, and increased cellular metabolism. Detection of one or more of these abnormal processes can be holons in the diagnosis of a patient s disease. 

Compounds (107 R, R = Me) and (108) transport chloride and bromide ions from one aqueous solution to another. The cyclotrisilane (109), prepared from commercially available 3-chloro-propyltrimethoxysilane in nine steps <88TL297>, was structurally assigned by mass spectrometry and H and C NMR spectroscopy. A solution of (109) in dichloromethane transported chloride or bromide ions from one aqueous solution to another, but not fluoride or iodide ions host-guest complexes of type (110) (Equation (10)) were postulated as intermediates in the transport processes. 

Mukherjee studied the gas phase equilibria and the kinetics of the possible chemical reactions in the pack-chromising of iron by the iodide process. One conclusion was that iodine-etching of the iron preceded chromis-ing also, not unexpectedly, the initial rate of chromising was controlled by transport of chromium iodide. Neiri and Vandenbulcke calculated, for the Al-Ni-Cr-Fe system, the partial pressures of chlorides and mixed chlorides in equilibrium with various alloys and phases, and so developed for pack aluminising a model of gaseous transport, solid-state transport, and equilibria at interfaces. 

Figure 42-11. Model of iodide metabolism in the thyroid follicle. A follicular cell is shown facing the follicular lumen (top) and the extracellular space (at bottom). Iodide enters the thyroid primarily through a transporter (bottom left). Thyroid hormone synthesis occurs in the follicular space through a series of reactions, many of which are peroxidase-mediated. Thyroid hormones, stored in the colloid in the follicular space, are released from thyroglobulin by hydrolysis inside the thyroid cell. (Tgb, thyroglobulin MIT, monoiodotyrosine DIT, diiodotyro-sine Tj, triiodothyronine T4, tetraiodothyronine.) Asterisks indicate steps or processes that are inherited enzyme deficiencies which cause congenital goiter and often result in hypothyroidism.

The thyroid is able to concentrate T against a strong electrochemical gradient. This is an energy-dependent process and is linked to the Na -K ATPase-dependent thyroidal T transporter. The ratio of iodide in thyroid to iodide in serum (T S ratio) is a reflection of the activity of this transporter. This activity is primarily controlled by TSH and ranges from 500 1 in animals chronically stimulated with TSH to 5 1 or less in hy-pophysectomized animals (no TSH). The T S ratio in humans on a normal iodine diet is about 25 1. 

The Van Arkel process can also be used to prepare actinide metals if the starting compound reacts easily with the transporting agent (I2). The thorium and protactinium carbides react with I2 to give volatile iodides above 350°C these are unstable above 1200°C and decompose into the actinide metals and iodine. Attempts to prepare other actinides, such as U and Pu, through the process were not successful, because from Th to Pu along the actinide series, the vapour pressure of the iodide decreases and the thermal stability increases. 

Thyroxine synthesis begins when iodide (I-) is transferred from the blood stream to the thyroid follicle cell by an active ATP-driven membrane pump mechanism this process is stimulated by cAMP following TSH stimulation of the gland. Iodide is transported through the follicular cell and secreted into the lumen of the follicle where it is oxidized to iodine and incorporated in to tyrosine residues by the enzyme thyroid peroxidase (TPO). 

Fig. 17.6 (a) Overview of processes and typical time constants under working conditions (1 sun) in a Ru-dye-sensitized solar cell with iodide/triiodide electrolyte. Recombination processes are indicated by red arrows. Reprinted with permission from [30]. Copyright 2010, American Chemical Society. Electron transport across nanostructured semiconductor films (b) in the absence and (c) in the presence of a nanotube support architecture. Reprinted with permission from [38]. Copyright 2007, American Chemical Society. 

The van Arkel-De Boer process is widely used to refine metals. A transporting agent such as Ij reacts with the metal (M) to be refined to form a volatile iodide. This iodide is then decomposed at a higher temperature into the refined metal and I2, which becomes available again to react with the impure metal, thus sustaining the process ... 

This reaction occurs in about 10 ns when R is an iodide ion in the 0.5 M concentration range [5]. Diffusion of 2 through the nanocrystalline Ti02 film to the substrate Sn02 electrode and diffusion of the oxidized redox species, R +, through the solution to the counterelectrode allow both charge carriers to be transferred to the external circuit where useful work is performed. The transport of electrons [7,24-29] and redox species [30] will not be considered further except insofar as they relate to the interfacial processes that are the focus of this chapter. 

Inspection of Table 11 shows that p for the reaction of aryl halides with tri-u-butyltin hydride was not solvent-dependent, whereas p for the reaction with magnesium was. The small values of p for the reaction of aryl bromide with magnesium in a polar solvent were again interpreted [81c] in terms of a mass transport-limited process. Thus reactions of aryl bromides would be transport-limited in THF and more polar solvents, but not in diethyl ether and less polar solvent. On the other hand, the rate of reaction of aryl iodides with magnesium seemed to be transport-limited, even in diethyl ether, whereas the rate of reaction of chlorobenzene with magnesium, which was lO slower than that of bromobenzene, was not. 

Thorium and Pa are most conveniently prepared from carbides, but at low temperatures made possible by an iodide intermediate in the iodine vapor process, based on the reaction of carbide with iodine vapor at 300 C. The actinoid iodide is transported to a hot surface (such as a W wire or sphere at 1200°C), where it decomposes and deposits the actinoid metaF". The overall reaction sequence is... 

The perchlorate anion is a tetrahedron with four oxygen molecules at the comers and a chlorine molecule at the center. Perchlorate, with a partial molal ionic volume of 44.5, has a similar ionic size as iodide with a partial molal ionic volume of 36.7 at 25°C. Because of its chemical properties, perchlorate is a competitive inhibitor of the process by which iodide circulating in the blood is actively transported into thyroid follicular cells. The site of this inhibition is... 

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