Vanadium oxidising agent

With the exception of iron(II) and uranium(IV), the reduced solutions are extremely unstable and readily re-oxidise upon exposure to air. They are best stabilised in a five-fold excess of a solution of 150g of ammonium iron(III) sulphate and 150 mL of concentrated sulphuric acid per litre [approximately 0.3M with respect to iron] contained in the filter flask. The iron(II) formed is then titrated with a standard solution of a suitable oxidising agent. Titanium and chromium are completely oxidised and produce an equivalent amount of iron(II) sulphate molybdenum is re-oxidised to the Mo(V) (red) stage, which is fairly stable in air, and complete oxidation is effected by the permanganate, but the net result is the same, viz. Mo(III)- Mo(VI) vanadium is re-oxidised to the V(IV), condition, which is stable in air, and the final oxidation is completed by slow titration with potassium permanganate solution or with cerium(IV) sulphate solution. 

All the vanadates are powerful oxidising agents and undergo reduction in add solution in the manner already described for vanadium pentoxide. The alkali vanadates are usually easily soluble in water, and are white or pale yellow, crystalline compounds, and frequently... 

Detection.—Apart from naturally occurring ores of vanadium, vanadium steels, and ferrovanadium, the commonest compounds of vanadium are those which contain the element in the pentavalent state, viz. the pentoxide and the various vanadates. The analytical reactions usually employed are, therefore, those which apply to vanadates. Most vanadium ores can be prepared for the application of these reactions by digesting with mineral acids or by alkaline fusion with the addition of an oxidising agent. When the silica content is high, preliminary treatment with hydrofluoric acid is recommended. Vanadium steels and bronzes, and ferrovanadium, are decomposed by the methods used for other steels the drillings are, for instance, dissolved in sulphuric acid and any insoluble carbides then taken up in nitric acid, or they are filtered off and submitted to an alkaline fusion. Compounds of lower valency are readily converted into vanadates by oxidation with bromine water, sodium peroxide, or potassium permanganate. 

Electrometric Methods have been applied for the estimation of vanadium alone and alloyed with other metals, e.g. iron, chromium, uranium. The reduced solution is either gradually oxidised by means of a suitable oxidising agent (potassium permanganate, ammonium persulphate, nitric acid), or the vanadate solution is gradually reduced with ferrous sulphate solution the changes in the E.M.F. of a suitable cell indicate the end point.8... 

Colorimetric Methods are used only for the estimation of very small percentages of vanadium, e.g. in vanadium steels and alloys. The most important depend on the intensity of the reddish-brown colour produced by the action of hydrogen peroxide on an acid vanadate solution.3 If chromium is present, an equal amount must be introduced into the standard vanadium solution under the same conditions of temperature, acid concentration, etc. Phosphoric acid is added to destroy any yellow colour due to ferric iron, and either hydrofluoric acid or ammonium fluoride to destroy any colour produced by titanium.4 A colorimetric method for the simultaneous estimation of small quantities of titanium and vanadium has also been worked out.5 Other colorimetric processes are based on (a) the formation of a yellow to black coloration, due to aniline black, in the presence of aniline hydrochloride and potassium chlorate or other oxidising agent,6 and (b) the orange coloration finally produced when an acid solution of a vanadate is brought into contact with strychnine sulphate.7... 

Of striking brevity is the direct addition of acetic acid to 1,1 -dichloro-4-methyl-penta-1,3-diene by means of one-electron oxidising agents like manganese (111) acetate [98], cerium(IV) [99] or vanadium(V) salts. [100,101] The further... 

Vanadium(V) is utilised extensively as an oxidising agent. The oxide, V205(s), exists naturally as the extremely rare mineral shcherbinaite and also as a hydrated phase V205 3H20(s) (which possibly is equivalent to V020H-H20(s)) known as navajoite. The oxide is used extensively as an industrial catalyst and is the main component used in the production of vanadium alloys. 

Estimation of Vanadium.1—Volumetric Methods.—The most convenient and the usual method for the estimation of vanadium is a volumetric process. The vanadium is first obtained in acid solution as vanadate, and reduced to the tetravalent state by one of several reducing agents which are available. The solution is then titrated in the presence of sulphuric acid with hot potassium permanganate solution, which quantitatively oxidises the lower vanadium salt to the vanadate. Using sulphur dioxide to effect the reduction, the following reactions take place —... 

Vanadium compounds can be oxidised or reduced by suitable reagents. For a redox reaction to work, the value must be positive. A list of F values for the half reactions of vanadium in its various oxidation states and for some oxidising and reducing agents is given below. These values show, for instance, that vanadium(V) will be reduced only to vanadium (IV) by Fe ions, whereas Sn ions will reduce it first to vanadium (IV) and then to vanadium (III). 

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