Vanadium trivalent

Gandeboeuf, J. and Souchay, P. (1959) tude des solutions de vanadium trivalent. J. Chim. Phys., 56, 358-371. 

Vanadium (IV) Chloride. Vanadium(IV) chloride (vanadium tetrachloride, VCy is a red-brown hquid, is readily hydrolyzed, forms addition compounds with donor solvents such as pyridine, and is reduced by such molecules to trivalent vanadium compounds. Vanadium tetrachloride dissociates slowly at room temperature and rapidly at higher temperatures, yielding VCl and CI2. Decomposition also is induced catalyticahy and photochemically. This instabihty reflects the difficulty in storing and transporting it for industrial use. 

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). 

In studies of the concentrations of arsenic, bromine, chromium, copper, mercury, lead and zinc in south-eastern Lake Michigan, it was shown that these elements concentrated near the sediment water interface of the fine-grained sediments. The concentration of these elements was related to the amount of organic carbon present in the sediments (161). However, it was not possible to correlate the concentration of boron, berylium, copper, lanthanum, nickel, scandium and vanadium with organic carbon levels. The difficulty in predicting the behaviour of cations in freshwater is exemplified in this study for there is no apparent reason immediately obvious why chromium and copper on the one hand and cobalt and nickel on the other exhibit such variations. However, it must be presumed that lanthanium might typify the behaviour of the trivalent actinides and tetravalent plutonium. 

The most widely studied transition metal is titanium. At various times, all oxidation states of titanium (II, III, IV) have been proposed for the active site of titanium-based initiators. Most of the evidence points to titanium (HI) as the most stereoselective oxidation state, although not necessarily the most active nor the only one [Chien et al., 1982]. (Data for vanadium systems indicate that trivalent vanadium sites are the syndioselective sites [Lehr, 1968].) Initiators based on the a-, y-, and 8-titanium trihalides are much more stereoselective (iso-selective) than those based on the tetrahalide or dihalide. By itself, TiCl2 is inactive as an initiator but is activated by ball milling due to disproportionation to TiCl3 and Ti [Werber et al., 1968]. The overall stereoselectivity is usually a-, y-, 8-TiCl , > TiCL > TiCLj P-TiCl3 [Natta et al., 1957b,c],... 

Although titanium retards the transformation of ferrihydrite (pH 6-11), it enhances the formation of goethite over hematite (Fitzpatrick Le Roux, 1976 Fitzpatrick et al., 1978). The opposite was found for trivalent chromium (Schwertmann et al., 1989) and vanadium (Schwertmann Pfab, 1994) besides retarding the transformation, higher concentrations of both ions led to enhanced hematite formation. 

Alum, KAl(S0i)i-l2H20.—Ammonium, rubidium, cesium, univalent thallium, and in some cases sodium may replace potassium, while the aluminum may be replaced by trivalent iron, chromium, indium, gallium, titanium, vanadium but not by the rare-earth metals. 

Vanadium pentoxide can be reduced to the metal by the action of hydrogen at high temperatures and pressures niobium pentoxide is more stable, and yields the trivalent oxide Nb203, whereas tantalum pentoxide has not hitherto been reduced by hydrogen. 

Trivalent Compounds.—In trivalent vanadium compounds the basic character of the element is well developed, and both normal and oxy-salts of the sesquioxide V203 are well defined, e.g. vanadous sulphate, V2(S04)3, and vanadium oxymonochloride, VOC1. It has been previously mentioned that resemblances between the elements of the A and B Subdivisions of Group V. are mainly restricted to the pentavalent compounds it is of interest to note that the oxychloride has analogues in the trivalent antimony and bismuth basic chlorides, SbOCl and BiOCl. Trivalent vanadium also displays considerable analogy, however, with other trivalent transitional elements, as shown by the following —... 

Double cyanides of trivalent vanadium have been prepared which show the properties of co-ordinated compounds, e.g. Ks[V(CN)g] compare with K3[Cr(CN)6] and K3[Fe(CN)6]. 

Hypovanadic Oxide, V02, is amphoteric, and dissolves both in alkalis and acids. In passing from trivalent to tetravalent vanadium, however, the basic character of the oxide becomes less pronounced and... 

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. ... 

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. 

Hydrated Vanadium Tri-iodide, VT3.6H20, is prepared by reducing, electrolytically, a solution of vanadium pentoxide, V2Os, in hydriodic add, until the product becomes green more hydriodic add is then added and the whole allowed to stand over lime and concentrated sulphuric add at 0° C. Small green needles separate, which have the same crystalline form as the hydrated trivalent halides of titanium, iron, and chromium. These crystals are extremely hygroscopic and deliquesce in air to a brown liquid8 which is extremely unstable. 

Hydrogen also reduces pentavalent and tetravalent vanadium salts to the trivalent state in the presence of spongy platinum.1... 

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... 

Vanadyl Selenite, V02.Se02.2H20, is obtained in blue, microscopic crystals when the hydrate of hypovanadic oxide, V02.2Ha0, is dissolved in an aqueous solution of selenous acid and the solution evaporated.3 Efforts to prepare normal selenates and selenate alums of trivalent vanadium were unsuccessful, but several hydrated aceto-selenates of trivalent vanadium have been isolated.4... 

The change in the oxidation state of the vanadium ion has also been observed in the ESR spectra of the soluble V(acac)3/A1(C2H5)2C1 catalyst at various temperatures. At temperatures below —40 °C no ESR signal could be detected, which suggests that the vanadium ions exsist in the trivalent state. A broad ESR signal (AH 20 mT) apperared at g — 1.98 at temperatures above —30 °C, and its intensity increased with temperature to reach a constant value at 20 °C. Thus, these spectral data indicate that the vanadium species active for the living polymerization of propylene are in the trivalent state. 

Maritidine. It was observed that a variety of alkoxyl or silyloxy phenols 340 (Scheme 51), on oxidation with the non-toxic pheny 1 iodo-tos-trifluoroacetate, instead of customary heavy metal reagents such as trivalent thallium or pentavalent vanadium salts, in the weakly nucleophilic solvent, trifluoroethanol at low temperature, furnished consistently improved yields of cyclisation products 341 [89],... 

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