Vanadium divalent

Aqueous pentavalent vanadium is readily reduced to the tetravalent state by iron powder or by S02 gas. A stronger reducing agent, eg, zinc amalgam, is needed to yield divalent vanadium. Divalent and tfivalent vanadium compounds are reducing agents and require storage under an inert atmosphere to avoid oxidation by air. 

It is also becoming increasingly apparent that the specific chemical form of a metal is a factor in its toxicity. Water-lipid partitioning, cell-wall permeability, and metabolic transport are just a few of the factors influenced by chemical form which, in turn, influence toxicity. Hexavalent chromium, pentavalent vanadium, divalent manganese, arsine, and methylmercury are more toxic than other forms of the corresponding metal. ... 

For vanadium solvent extraction, Hon powder can be added to reduce pentavalent vanadium to quadrivalent and trivalent Hon to divalent at a redox potential of —150 mV. The pH is adjusted to 2 by addition of NH, and an oxyvanadium cation is extracted in four countercurrent stages of mixer—settlers by a diesel oil solution of EHPA. Vanadium is stripped from the organic solvent with a 15 wt % sulfuric acid solution in four countercurrent stages. Addition of NH, steam, and sodium chlorate to the strip Hquor results in the precipitation of vanadium oxides, which are filtered, dried, fused, and flaked (22). Vanadium can also be extracted from oxidized uranium raffinate by solvent extraction with a tertiary amine, and ammonium metavanadate is produced from the soda-ash strip Hquor. Fused and flaked pentoxide is made from the ammonium metavanadate (23). 

The electrolyte is made by in situ chlorination of vanadium to vanadium dichloride in a molten salt bath. Higher valent chlorides are difficult to retain in the bath and thus are not preferred. The molten bath, which is formed by sodium chloride or an equimolar mixture of potassium chloride-sodium chloride or of potassium chloride-lithium chloride or of sodium chloride-calcium chloride, is contained in a graphite crucible. The crucible also serves as an anode. Electrolysis is conducted at a temperature about 50 °C above the melting point of the salt bath, using an iron or a molybdenum cathode and a cathode current density of 25 to 75 A dnT2. The overall electrochemical deposition reaction involves the formation and the discharge of the divalent ionic species, V2+ ... 

There are a few features relative to POMs that are necessary for obtaining the best performance. In all cases. Vanadium is present in the structure of the P/Mo Keggin anion, while the cations include different components, that is, protons, divalent transition metal ions (preferably either Fe " " or Cu " "), and alkali metal ions (preferably Cs" "). The role of Cu ions is to catalyze the reduction of molybdenum, thus increasing the activity of the catalyst it also affects the surface acidity. 

Divalent vanadium belongs to 3d ions and is isoelectronic with Cr. Hence all energy levels and spectral characteristics are similar. The difference between them lies in the lower crystal field strength for V in comparison with Cr. ... 

In the sodium chloride structure, the symmetry enables three of the five d orbitals on different atoms to overlap. Because the atoms are not nearest neighbours, the overlap is not as large as in pure metals and the bands are thus narrow. The other two d orbitals overlap with orbitals on the adjacent oxygens. Thus, two narrow 3c/ bands exist. The lower one, labelled 2g. can take up to 67Velectrons, and the upper one, labelled 6g, up to 47V electrons. Divalent titanium has two d electrons, therefore, 27V electrons fill the 37V levels of the lower band. Similarly, divalent vanadium has three d electrons and so the lower band is half full. As in the case of pure metals, a partly filled band leads to metallic conductivity. For FeO, the /2g band would be full, so it is not surprising to find that it is a semiconductor but MnO with only five electrons per manganese is also a semiconductor. 

Vanadyl salts are salts of tetravalent vanadium, and contain the divalent [VO]- radical. Many vanadium compounds are known which appear to contain a [VO] group, but the vanadium is either trivalent or pentavalent. Throughout this book the term vanadyl is restricted to compounds of tetravalent vanadium, that is, to salts of the oxide V02. Hence, for example, the compound VOCI3, which contains pentavalent vanadium, is called vanadium oxytrichloride, and not by the more usual but less logical name vanadyl chloride. ... 

Vanadium predpitates the metal from solutions of salts of gold, silver, platinum, and iridium, and reduces solutions of mercuric chloride, cupric chloride and ferric chloride to mercurous chloride, cuprous chloride, and ferrous chloride, respectively. In these reactions the vanadium passes into solution as the tetravalent ion. No precipitation or reduction ensues, however, when vanadium is added to solutions of divalent salts of zinc, cadmium, nickel, and lead. From these reactions it has been estimated that the electrolytic potential of the change, vanadium (metal)—>-tetravalent ions, is about —0 3 to —0 4 volt, which is approximately equal to the electrolytic solution pressure of copper. This figure is a little uncertain through the difficulty of securing pure vanadium.5... 

In 1898, Cowper-Coles 2 claimed to have successfully effected the electrolytic reduction of an acid solution of vanadium pentoxide to metallic vanadium, but the product was subsequently shown by Fischer 3 to have been a deposit of platinum hydride. Fischer, in a series of over three hundred experiments, varied the temperature, current density, cathode material, concentration, electrolyte, addition agent, and construction of cell, but in not one instance was the formation of any metallic vanadium observed. In most cases reduction ceased at the tetravalent state (blue). At temperatures above 90° C. reduction appeared to proceed to the divalent state (lavender). The use of carbon electrodes led to the trivalent state (green), but only lead electrodes produced the trivalent state at temperatures below 90° C. Platinum electrodes reduced the electrolyte to the blue vanadyl salt below 90° C. using a divided cell and temperatures above 90° C. the lavender salt was obtained. 

Hypovanadous oxide resembles the metal in many of its properties. It is insoluble in water, but dissolves in acids without evolution of hydrogen to yield the lavender-coloured solutions which are characteristic of solutions of hypovanadous salts. These salts are, however, most conveniently prepared in solution by electrolytic reduction in an inert atmosphere of solutions of vanadium pentoxide in the various acids.7 Hypovanadous salts are isomorphous with salts of divalent iron, chromium, and manganese. On being treated with caustic alkalis, a brown precipitate of hypovanadous hydroxide, V(OH)a, is obtained, which rapidly oxidises to the greyish-green vanadous hydroxide, V(OH)s. 

Reduction of add solutions of vanadium pentoxide to the tetravalent state also takes place with bismuth amalgam 5 magnesium gives the trivalent salts of vanadium, while by using zinc, zinc coated with cadmium, electrolytically deposited cadmium, or sodium amalgam in the absence of air, divalent vanadium salts are obtained in solution.7 Vanadous salts and hypovanadous salts are, however, much more conveniently prepared by electrolytic reduction of acid solutions of vanadium pentoxide in an atmosphere of carbon dioxide.8... 

Additionally, Aykan et al. (98) reported the results for scheelite-type systems in which A sites are occupied by divalent elements and bismuth, and M sites contain vanadium and molybdenum. The tolerance for vacancies in this system was reported to be 15% of the A cation sites. Good yields of acrolein were obained when bismuth and defects were present in the scheelite-structured catalysts. 

Vanadate transport in the erythrocyte was shown to occur via facilitated diffusion in erythrocyte membranes and was inhibited by 4,4 -diisothiocyanostilbene-2,2 -disulfonic acid (DIDS), a specific inhibitor of the band 3 anion transport protein [23], Vanadium is also believed to enter cells as the vanadyl ion, presumably through cationic facilitated diffusion systems. The divalent metal transporter 1 protein (called DMT1, and also known as Nramp2), which carries iron into cells in the gastrointestinal system and out of endosomes in the transferrin cycle [24], has been proposed to also transport the vanadyl cation. In animal systems, specific transport protein systems facilitate the transport of vanadium across membranes into the cell and between cellular compartments, whereas the transport of vanadium through fluids in the organism occurs via binding to proteins that may not be specific to vanadium. 

Polymerization activity was obtained with a variety of catalyst compositions. The best stereospecific catalyst was the split pretreated type (357) in which one mole of VC14 was reduced by a stoichiometric amount of an alkyl metal (0.34 mole AlEt3) in heptane at room temperature and heated 16 hours at 90° C. to obtain the purple crystalline VC13-1/3 A1C13. This reduced transition metal component was then treated with two moles of (i-Bu)3Al tetrahydrofuran complex for 20 hours at room temperature to obtain a chocolate-brown catalyst consisting predominantly of divalent vanadium with 0.21 Al/V and 1.4 i-Bu/Al. Polymerizations at 30° C. gave crystalline polymers from methyl, ethyl, isopropyl, isobutyl, tert.-butyl, and neopentyl vinyl ethers. 

It is highly probable that an alkylated vanadium complex is the site at which polymerization occurs. In the case of coarsely powdered VCh the amount of alkylation as judged by divalent vanadium in the catalyst is very small... 

The X-ray structures of vanadium bromoperoxidases from the red seaweeds Corallina pilulifera and C. officinalis have also been determined and their structures are almost identical. The native structure of these enzymes is dodecameric and the structure is made up of 6 homo-dimers. The secondary stmcture of the chloroperoxidase from the ftmgus Curvularia inaequalis that will be discussed later can be superimposed with the Corallina hromoperoxidase dimer. Many of the a helices of each chloroperoxidase domain are structurally equivalent to the a helices in the Corallina hromoperoxidase dimer. This is in line with the evolutionary relationship between the haloperoxidases that will be discussed later. The disulfide bridges in the enzyme from A. nodosum are not found in the enzyme from Corallina and the two remaining cysteine residues are not involved in disulfide bonds. Additionally, in this enzyme binding sites are present for divalent cations that seem to be necessary to maintain the stmcture of the active site cleft. All the residues directly involved in the binding of vanadate are conserved in the algal bromoperoxidases. ... 

The chromous salts, derived from the oxide CrO, arc analogous to the salts of divalent vanadium, manganese, and iron. This is seen in the isomorphism of the sulphates of the type R" SOj-THgO. The stability of such salts increases in the order of the atomic number of the metal. The chief basic oxide of chromium is the sesquioxidc CraO, which is closely allied to ferric oxide, and, like the latter, resembles aluminium oxide. The hydroxide, Cr(OH)3, with bases yields chromites analogous to, but less stable than, the aluminates. Chromic sulphate enters into the formation of alums. The chromic salts are very stable, but in the trivaJent condition the metal shows a marked tendency to form complex ions, both anions and cations thus it resembles iron in producing complex cyanides, whilst it also yields compounds similar to the cobaltamines. 

New important information about the structure of the intermediate complex was obtained from the X-ray studies of V complex with di-ferf-butylcatecholate [18]. The complex, the structure of which is presented in Figure 4, contains four vanadium ions two are divalent and two trivalent, but they are indistinguishable, thus their oxidation state is 2.5 and the complex can be regarded as existing in a semi-reduced state, similar to the s-r state of FeMoco in the presence of dithionite, which is not sufficiently reduced to activate dinitrogen. 

In these experiments, vanadyl sulfate was reduced with amalgamated zinc to produce a divalent vanadium solution. Portions of this solution were then added to the unreduced Pd-PVA catalyst contained in an atmosphere of purified nitrogen. The nitrogen was then displaced by hydrogen or carbon monoxide and the substance to be hydrogenated introduced. In some cases the divalent vanadium solution was added after the catalyst had been reduced by hydrogen. 

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