Vanadium hydroxides

A reaction of particular relevance with respect to applied catalysis is the oxidative dehydrogenation (ODH) of hydrocarbon by VmOn ions according to reaction 2, which involves a two-electron reduction of the cluster. By means of a systematic study of the reactions of various YmOn ions as well as the related oxo-vanadium hydroxides VmO H+ ions with a set of C4-hydrocarbons, it was demonstrated recently that the ODH activity of the cluster ions shows a clear correlation with the formal valence of vanadium in the cluster ions with a maximum reactivity for formal vanadium (V) (Fig. 3) [84]. In such a kind of reactivity screening, it is essential to include more than a single reagent as a probe for the reactivity of the different ions in order to reduce interferences by kinetic barriers of one particular combination of neutral and ionic reactants [85]. Accordingly, the sums of the relative rate constants for the ODH reactions of the four different butenes are considered and normalized to the most reactive ion studied, which turns out to be the formally pure vanadium (V) compoimd In addition to isomeric... 

Reduction via protonalion is also reported by Shilov [7]. The reaction proceeds in those systems w hich are known to reduce Nj to hydrazine and ammonia, e.g., under the action of bivalent vanadium hydroxids show n in Equation (5). 

The last option is the most restrictive, while the first alternative is the most relaxed. For example, when V and O are included in the list, then Exclusive AND limits the search only to oxides of vanadium, while compounds containing other elements (e.g. vanadium hydroxides, vanadates, etc.) will not be considered and analyzed, On the other hand, Inclusive AND searches among all compounds containing both V and O in combination with any other chemical elements. The latter option may be useful, for example, when intercalates of vanadium oxides are suspected or studied. 

With sulfuric acid a vanadium hydroxide is precipitated that can be redissolved in soda to a pure soluhon of sodium vanadate. Addition of ammonium chloride precipitates white crystalline ammonium vanadate NH VO. This can be calcined to give orange vanadium pentoxide, suitable for production of pure vanadium and of fer-rovanadium. 

Examples FeO(OH), iron(lll) hydroxide oxide V0(S04), vanadium(lV) oxide sulfate. 

Amino-4-nitropheno1 is produced commercially by the partial reduction of 2,4-dinitrophenol This reduction may be achieved electrolyticaHy using vanadium (159) or chemically with polysulftde, sodium hydrosulftde, or hydrazine and copper (160). Alternatively, 2-acetamidophenol or 2-methylbenzoxazole may be nitrated in sulfuric acid to yield a mixture of 4- and 5-nitro derivatives that are then separated and hydrolyzed with sodium hydroxide (161). 

For solvent extraction of pentavalent vanadium as a decavanadate anion, the leach solution is acidified to ca pH 3 by addition of sulfuric acid. Vanadium is extracted in about four countercurrent mixer—settler stages by a 3—5 wt % solution of a tertiary alkyl amine in kerosene. The organic solvent is stripped by a soda-ash or ammonium hydroxide solution, and addition of ammoniacal salts to the rich vanadium strip Hquor yields ammonium metavanadate. A small part of the metavanadate is marketed in that form and some is decomposed at a carefully controlled low temperature to make air-dried or fine granular pentoxide, but most is converted to fused pentoxide by thermal decomposition at ca 450°C, melting at 900°C, then chilling and flaking. 

In this method, a metal oxide or hydroxide is slurried in an organic solvent, neodecanoic acid is slowly added, and the mixture is refluxed to remove the water. Salts that are basic can be prepared by using less than stoichiometric amounts of acid. This method has been used in the preparation of metal salts of silver (80) and vanadium (81). The third method of preparation is similar to the fusion process, the difference is the use of finely divided metal as the starting material instead of the metal oxide or hydroxide. This method has been appHed to the preparation of cobalt neodecanoate (82). Salts of tin (83) and antimony (84) have been prepared by the fusion method, starting with lower carboxyHc acids, then replacing these acids with neodecanoic acid. 

The active phase, which is soHd at room temperature, is comprised of mixed potassium and sodium vanadates and pyrosulfates, whereas the support is macroporous siUca, usually in the form of 6—12 mm diameter rings or pellets. The patent Hterature describes a number of ways to prepare the catalyst a typical example contains 7 wt % vanadium pentoxide, 8% potassium added as potassium hydroxide or carbonate, 1% sodium, and 78 wt % siUca, added as diatomaceous earth or siUca gel, formed into rings, and calcined in the presence of sulfur dioxide or sulfur trioxide to convert a portion of the alkah metal salts into various pyrosulfates (81,82). 

Ammonium hydrogen fluoride (NH4HF2) is useful for converting pure oxides or hydroxides to the corresponding fluorides. The reaction occurs through the formation of a double fluoride. For example, with vanadium sesquioxide the following reactions occur ... 

Vanadium Co-precipitation with ferric hydroxide, cobalt ammonium pyrrolidine dithio carbarn ate or ammonium pyrrolidine dithiocarbamate Miscellaneous [920]... 

Merox [Mercaptan oxidation] A process for removing mercaptans from petroleum fractions by extracting them into aqueous sodium hydroxide and then catalytically oxidizing them to disulfides using air. The catalyst is an organometallic compound, either a vanadium phthalocyanine supported on charcoal, or a sulfonated cobalt phthalocyanine. Developed by UOP in 1958 and widely licensed by 1994, more than 1,500 units had been built, worldwide. Unzelman, G. H. and Wolf, C. J., in Petroleum Processing Handbook, Bland, W. F. and Davidson, R. L., Eds., McGraw-Hill, New York, 1967, 3-128. 

The residue after the water wash is leached at an elevated temperature by sulfuric acid, part of which is the recycled raffinate from the vanadium extraction. The leaching yield of vanadium (mainly IV-valent) is about 55% and of nickel about 95%. A final (post) leach with sodium hydroxide dissolves the remaining vanadium (mainly V-valent). The resulting leach solution, containing practically all the vanadium ( 25gdm ) and nickel ( 12gdm ) is fed to the solvent extraction circuit. 

Enzymes requiring vanadium for catalytic activity. Perhaps the best studied of these are the vanadium-dependent nitrogenases [EC 1.18.6.1]. Other vanadium-dependent enzymes include vanadium haloperoxidase, vanadium chloroperoxidase, and vanadium bromoper-oxidase. In the vanadium chloroperoxidase and bromo-peroxidase reactions, the vanadium(V) is coordinated in a trigonal bipyramidal site to a histidyl residue, three nonprotein oxygens, and, presumably, to a hydroxide. 

The purification of the alkali hydroxides.—Numerous impurities have been reported in commercial sodium and potassium hydroxides. Several have commented on the presence of peroxide, particularly in caustic potash.19 Various salts—carbonate, sulphate, nitrate, nitrite, chloride, and phosphate—as well as alumina, silica, organic matters, and metal oxides—e.g. arsenic, vanadium, iron, etc., have been reported. More or less of the other alkalies may also be present. 

Rapidly add a 10% sodium hydroxide solution to one series of solutions containing compounds of vanadium in different oxidation states. What do you observe See how the obtained hydroxides react with acids and alkalies. Add a potassium permanganate solutioq... 

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