System arsenic

In addition to sulphate, selenate (J. M. Bigham, unpubl.) and chromate (S. Regen-spurg unpubl.) can also be incorporated in the tunnels of synthetic schwertmannite. Whether or not two different Se-O distances (based on EXAFS) attributable to surface and tunnel selenate, respectively, exist in the Se-form is still under discussion (Waychunas et al., 1995, 1995 a). The Cr form has the bulk composition Fei6Oi6(OH)i0.23(CrO4)2.gg. In fact, synthetic schwertmannite formed in the sul-phate/arsenate system tolerates arsenate only up to a As/(As-rS) mole ratio of ca. 0.5, and it is likely that most of this arsenate is surface-bound. Above this ratio, a new, very poorly ordered Fe-hydroxy arsenate with two broad XRD peaks at ca. 0.31 and 0.16 nm and BhfS at 4.2K and ca. 1.5 K of 41.6 and 47.3T, respectively, forms (Carlson et al. 2002). From this one may conclude that, whereas the tetrahedral oxyanions with hexavalent central cations (S Se Cr) can be accomodated in the tunnel positions, the pentavalent cations can not, or not as easily. Schwertmannite from acid mine water contained between 6 and 70 g kg As (Carlson et al. 2002). 

The methyl arsenic system compromises two well-defined species, the pentamer (MeAs)5, a yellow pyrophoric oil (m.p. 12°C) and the purple black double-chain polymer, [(MeAs)2] (m.p. 204 °C). A red solid that is possibly the linear chain compound (MeAs) has also been described. The polymers are formed when samples of the pentamer are exposed to impurities like arsenic halides that are able to react with the arsenic-arsenic bond and may act as end groups. The most widely used method for the preparation of larger amounts of (MeAs)j is the reduction of methylarsonic acid, MeAsO(OH)2, or its sodium salt with hypophosphoric acid " °. Samples prepared by this method, however, may contain between 5 and 15% of impurities. A method that minimizes impurities is the reaction of MeAsHj with dibenzylmercury (equation 3) °. 

The preparative chemistry of the t-butylantimony rings is related to the arsenic systems. Dehalogenation of t-BuSbCl2 with Mg in THF gives the tetramer (t-BuSb)4 as the main product along with small amounts of (f-BuSb)5 as side product A t-butylantimony... 

In addition, two morphotrophic phase boundaries may intersect within the solid solution system so as to produce a maximum critical temperature (Type II MPD in Fig. 6c) or a minimum critical temperature (Type III MPD in Fig. 6d). The Type II MPD is similar to that of the diopside-jadeite (CaMgSi206-NaAlSi206) solid solution (Carpenter 1980, Holland 1990, Holland and Powell 1996). Each endmember has a monoclinic structure with space group C2/c, but the midpoint of the solid solution, omphacite, has a reduced symmetry (S.G. P2 n) due to an ordering transition. Salje et al. (1991) argue that this midpoint composition actually represents the pure component of the omphacite join. A Type III MPD is observed in the lead phosphate-arsenate system (Bismayer et al. 1986). 

Phosphides.—An arc melting technique, which offers advantages in purity of product and higher attainable temperatures over the conventional approach to phosphide preparation, has been used to re-examine the V-P system (the V-As and Cr-As systems were also investigated). The phases in the V-P system were confirmed, but in the corresponding arsenic system two new orthorhombic phases have been identified. 

For several reasons the development of the chemistry of 6n heteroaromatic arsenic systems, for example arsinine (3), was much less vigorous than that of the phosphinines. While t-butylphos-phaethyne (4) and several other phosphaethynes are important building blocks for the synthesis of six-membered aromatic phosphorus heterocycles with more than one heteroatom, only one compound with a C=As triple bond, the 2,4,6-tri- -butylphenyl derivative (5), has been described <86AG(E)264>, and this has not been thoroughly studied. The only six-membered As-heteroaromatic system with more than one heteroatom is the l,3A -azarsinine (6) <88TL535>. Since pentavalent... 

The influence of the heteroatom on the structure of a series of dinaphtho-fused five membered potentially aromatic ring systems (317), including the phosphorus and arsenic systems, has been studied by crystallographic techniques. A theoretical study has shown that the incorporation of two o, X -phosphorus atoms into the phosphole ring system decreases the ring strain and significantly lowers the inversion barrier about the phosphole pyramidal phosphorus. Pyramidalisation at phosphorus in phospholes has been shown to increase on... 

Table II List of Model Parameters for Arsenic System ...

A phase with this type of structure also crystallizes in the tin-arsenic system, but from phase analytical data the composition is near to Sn3As2. The substitutional solution of tin is believed to account for the deviation from the stoichiometric composition Sn4As347. 

CHjSH CHSH-CHjOH. Usually obtained as an oil, m.p. 77 C. Developed as an antidote to poisoning by organic arsenicals by external application, it is of use in poisoning by Hg, Cu, Zn, Cd but not Pb. It acts by forming a chelate with the metal and so removing it from the system. 

In addition to flame fronts, which have been extensively studied experimentally, front instabilities have been investigated for the isothennal cubic autocatalytic iodate arsenous acid system [70] as well as for polymerization... 

The arsenate(lll) ion can be reduced by systems which generate hydrogen (for example metal/acid) to give arsine, for example... 

The preferable theoretical tools for the description of dynamical processes in systems of a few atoms are certainly quantum mechanical calculations. There is a large arsenal of powerful, well established methods for quantum mechanical computations of processes such as photoexcitation, photodissociation, inelastic scattering and reactive collisions for systems having, in the present state-of-the-art, up to three or four atoms, typically. " Both time-dependent and time-independent numerically exact algorithms are available for many of the processes, so in cases where potential surfaces of good accuracy are available, excellent quantitative agreement with experiment is generally obtained. In addition to the full quantum-mechanical methods, sophisticated semiclassical approximations have been developed that for many cases are essentially of near-quantitative accuracy and certainly at a level sufficient for the interpretation of most experiments.These methods also are com-... 

In a generalized sense, acids are electron pair acceptors. They include both protic (Bronsted) acids and Lewis acids such as AlCb and BF3 that have an electron-deficient central metal atom. Consequently, there is a priori no difference between Bronsted (protic) and Lewis acids. In extending the concept of superacidity to Lewis acid halides, those stronger than anhydrous aluminum chloride (the most commonly used Friedel-Crafts acid) are considered super Lewis acids. These superacidic Lewis acids include such higher-valence fluorides as antimony, arsenic, tantalum, niobium, and bismuth pentafluorides. Superacidity encompasses both very strong Bronsted and Lewis acids and their conjugate acid systems. 

A major advantage of this hydride approach lies in the separation of the remaining elements of the analyte solution from the element to be determined. Because the volatile hydrides are swept out of the analyte solution, the latter can be simply diverted to waste and not sent through the plasma flame Itself. Consequently potential interference from. sample-preparation constituents and by-products is reduced to very low levels. For example, a major interference for arsenic analysis arises from ions ArCE having m/z 75,77, which have the same integral m/z value as that of As+ ions themselves. Thus, any chlorides in the analyte solution (for example, from sea water) could produce serious interference in the accurate analysis of arsenic. The option of diverting the used analyte solution away from the plasma flame facilitates accurate, sensitive analysis of isotope concentrations. Inlet systems for generation of volatile hydrides can operate continuously or batchwise. 

Arsenic Peroxides. Arsenic peroxides have not been isolated however, elemental arsenic, and a great variety of arsenic compounds, have been found to be effective catalysts ia the epoxidation of olefins by aqueous hydrogen peroxide. Transient peroxoarsenic compounds are beheved to be iavolved ia these systems. Compounds that act as effective epoxidation catalysts iaclude arsenic trioxide, arsenic pentoxide, arsenious acid, arsenic acid, arsenic trichloride, arsenic oxychloride, triphenyl arsiae, phenylarsonic acid, and the arsenates of sodium, ammonium, and bismuth (56). To avoid having to dispose of the toxic residues of these reactions, the arsenic can be immobi1i2ed on a polystyrene resia (57). 

In an alternative industrial process, resorcinol [108-46-3] is autoclaved with ammonia for 2—6 h at 200—230°C under a pressurized nitrogen atmosphere, 2.2—3.5 MPa (22—35 atm). Diammonium phosphate, ammonium molybdate, ammonium sulfite, or arsenic pentoxide maybe used as a catalyst to give yields of 60—94% with 85—90% selectivity for 3-aminophenol (67,68). A vapor-phase system operating at 320°C using a siUcon dioxide catalyst impregnated with gallium sesquioxide gives a 26—31% conversion of resorcinol with a 96—99% selectivity for 3-aminophenol (69). 

Most commercial methanator catalysts contain nickel, supported on alumina, kaolin, or calcium aluminate cement. Sulfur and arsenic are poisons to the catalyst, which can also be fouled by carry-over of solvent from the CO2 removal system. 

A novel interface to connect a ce system with an inductively coupled plasma mass spectrometric (icpms) detector has been developed (88). The interface was built using a direct injection nebulizer (din) system. The ce/din/icpms system was evaluated using samples containing selected alkah, alkaline earths, and heavy-metal ions, as well as selenium (Se(IV) and Se(VI)), and various inorganic and organic arsenic species. The preliminary results show that the system can be used to determine metal species at ppt to ppb level. 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

Metafile arsenic can be obtained by the direct smelting of the minerals arsenopyrite or loeUingite. The arsenic vapor is sublimed when these minerals are heated to about 650—700°C in the absence of air. The metal can also be prepared commercially by the reduction of arsenic trioxide with charcoal. The oxide and charcoal are mixed and placed into a horizontal steel retort jacketed with fire-brick which is then gas-fired. The reduced arsenic vapor is collected in a water-cooled condenser (5). In a process used by Bofiden Aktiebolag (6), the steel retort, heated to 700—800°C in an electric furnace, is equipped with a demountable air-cooled condenser. The off-gases are cleaned in a sembber system. The yield of metallic arsenic from the reduction of arsenic trioxide with carbon and carbon monoxide has been studied (7) and a process has been patented describing the gaseous reduction of arsenic trioxide to metal (8). 

The cmde oxide is pressure-leached in a steam-heated autoclave using water or circulating mother hquor. The arsenic trioxide dissolves, leaving behind a residue containing a high concentration of heavy metal impurities and sihca. The solution is vacuum-cooled and the crystallisation is controUed so that a coarse oxide is obtained which is removed by centrifuging. The mother hquor is recycled. The oxide (at least 99% purity) is dried and packaged in a closed system. 

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