Boron problem

The boron problem still exists due to the low rejection of boric acid through the membranes, yet several other solutions exist, as described below. Final mixing of the water is advisable in some cases to increase salt concentration slightly. Small organic compounds dissolved in the feed water may also find their way into the water produced. Salt content depends on feed quality (brackish or seawater) and may vary between 50-600 ppm of TDS. A secondary stage may improve quality with only a... 

Boron, in the form of boric acid, is used in the PWR primary system water to compensate for fuel consumption and to control reactor power (3). The concentration is varied over the fuel cycle. Small amounts of the isotope lithium-7 are added in the form of lithium hydroxide to increase pH and to reduce corrosion rates of primary system materials (4). Primary-side corrosion problems are much less than those encountered on the secondary side of the steam generators. 

The quantity of boric acid maintained in the reactor coolant is usually plant specific. In general, it ranges from ca 2000 ppm boron or less at the start of a fuel cycle to ca 0 ppm boron at the end. Most plants initially used 12-month fuel cycles, but have been extended to 18- and 24-month fuel cycles, exposing the materials of constmction of the fuel elements to longer operating times. Consequendy concern over corrosion problems has increased. 

Sepa.ra.tion of Plutonium. The principal problem in the purification of metallic plutonium is the separation of a small amount of plutonium (ca 200—900 ppm) from large amounts of uranium, which contain intensely radioactive fission products. The plutonium yield or recovery must be high and the plutonium relatively pure with respect to fission products and light elements, such as lithium, beryUium, or boron. The purity required depends on the intended use for the plutonium. The high yield requirement is imposed by the price or value of the metal and by industrial health considerations, which require extremely low effluent concentrations. 

To date, the most extensively studied polyboron hydride compounds in BNCT research have been the icosahedral mercaptoborane derivatives Na2[B22H22SH] and Na [(B22H22S)2], which have been used in human trials with some, albeit limited, success. New generations of tumor-localizing boronated compounds are being developed. The dose-selectivity problem of BNCT has been approached using boron hydride compounds in combination with a variety of deUvery vehicles including boronated polyclonal and monoclonal antibodies, porphyrins, amino acids, nucleotides, carbohydrates, and hposomes. Boron neutron capture therapy has been the subject of recent reviews (254). 

The hydrides of the later main-group elements present few problems of classification and are best discussed during the detailed treatment of the individual elements. Many of these hydrides are covalent, molecular species, though association via H bonding sometimes occurs, as already noted (p. 53). Catenation flourishes in Group 14 and the complexities of the boron hydrides merit special attention (p. 151). The hydrides of aluminium, gallium, zinc (and beryllium) tend to be more extensively associated via M-H-M bonds, but their characterization and detailed structural elucidation has proved extremely difficult. 

The structural complexity of borate minerals (p. 205) is surpassed only by that of silicate minerals (p. 347). Even more complex are the structures of the metal borides and the various allotropic modifications of boron itself. These factors, together with the unique structural and bonding problems of the boron hydrides, dictate that boron should be treated in a separate chapter. 

Boron is unique among the elements in the structural complexity of its allotropic modifications this reflects the variety of ways in which boron seeks to solve the problem of having fewer electrons than atomic orbitals available for bonding. Elements in this situation usually adopt metallic bonding, but the small size and high ionization energies of B (p. 222) result in covalent rather than metallic bonding. The structural unit which dominates the various allotropes of B is the B 2 icosahedron (Fig. 6.1), and this also occurs in several metal boride structures and in certain boron hydride derivatives. Because of the fivefold rotation symmetry at the individual B atoms, the B)2 icosahedra pack rather inefficiently and there... 

Figure 6.4 Crystal structure of ar-tetragonal boron. This was originally thought to be B50 (4Bi2 + 2B) but is now known to be either B50C2 or B50N2 in which the 2C (or 2N) occupy the 2(b) positions the remaining 2B are distributed statistically at other vacant sites in the lattice. Note that this reformulation solves three problems which attended the description of the or-tetragonal phase as a crystalline modification of pure B ...

The only preparative limitation to this method is the occasional coproduction of alkenyl-boronates that presumably arise via a-elimination pathways of the ate complex generated upon addition of the organometallic reagent to the a-haloalkylboronate4,29-30. This problem is illustrated in the synthesis of 5-(rm-butyldimethylsilyloxy)-2-pentenyl-substituted dioxaborolane30. 

Metal-boron compounds — problems and perspectives. G. Schmid, Angew. Chem., Int. Ed. Engl., 1970, 9, 819-830 (89). 

The boron hydrides offer an interesting problem. With boron trivalent, we should expect compounds such as BF3, BH3, etc. 

At a deposition temperature of 1300°C., a low-density material is obtained (1.5 g/cm ). Density increases with increasing temperature and reaches 2.0 g/cm at 1600°C. Vapor phase precipitation can be a problem in the high-temperature range. A more convenient reaction uses boron fluoride ... 

MBE growth of very thin layer of boron and silicon. The problems associated with boron implant and laser anneal can be overcome by growing a very thin (5 nm) layer of silicon with boron atoms on the backside of the thinned CCD (1% boron, 99% silicon). The growth is applied by molecular beam epitaxy (MBE) machines. This process was developed by JPL and MIT/LL. 

The B atoms fill the center points (site 24e) of an antiprism formed by four metal atoms of site 32f and four metal atoms of site 48h. Usually no boron defects occur, but a still unsolved problem is where xs B would be accommodated in the structure... 

A pellet is pressed of an intimate mixture of finely divided reactants and reaction induced either by arc melting and high-T annealing or by solid-state sintering in an electrical or high-frequency furnace. Isolating the borides from reactive container components can be a problem. The use of boron nitride liners has proved effective. In some cases the protective liner is made of sintered boride containing the same elements as the boride in preparation. 

The problems raised by the preparation of some rare-earth borides such as SmB4, YbB4 and TmB2 are comparable to those found for the alkali borides from the point of view of the volatility of the metals. They dissociate through metal evaporation, yielding boron-rich borides as indicated in 6.7.2.4. 

DI water is not equivalent to distilled water in all ways. While the content of most ionic species is very low, it does contain dissolved gases, such as air and carbon dioxide. The latter caused problems in one laboratory when DI water was used for diluting poorly buffered samples for pH measurements. Erratic results were also reported in another case when DI water was used in connection with the determination of trace amounts of boron. The manufacturer explained that when close to exhaustion, the resin used would no longer be effective in holding back traces of this element. 

The metal catalysed hydroboration and diboration of alkenes and alkynes (addition of H-B and B-B bonds, respectively) gives rise to alkyl- or alkenyl-boronate or diboronate esters, which are important intermediates for further catalytic transformations, or can be converted to useful organic compounds by established stoichiometric methodologies. The iyn-diboration of alkynes catalysed by Pt phosphine complexes is well-established [58]. However, in alkene diborations, challenging problems of chemo- and stereo-selectivity control stiU need to be solved, with the most successful current systems being based on Pt, Rh and An complexes [59-61]. There have been some recent advances in the area by using NHC complexes of Ir, Pd, Pt, Cu, Ag and Au as catalysts under mild conditions, which present important advantages in terms of activity and selectivity over the established catalysts. 

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