Vanadous sulphate

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 —... 

Acid Vanadous Sulphates and double vanadous sulphates.—Electrolytic reduction of solutions of vanadyl sulphate, V0S04, has given two green, crystalline, acid vanadous sulphates, according to the amount of sulphuric acid also added ... 

A compound intermediate in composition between vanadic sulphate and vanadyl sulphate has been obtained by reducing a solution of a vanadic salt in sulphuric acid with sulphur dioxide, or by mixing solutions of the pentoxide and the dioxide in sulphuric acid.1... 

Double Salts of Vanadous Thiocyanate.—When vanadous sulphate, V2(S04)3, in solution, is treated with barium thiocyanate, a green solution8 is obtained which is believed to contain vanadous thiocyanate, V(SCN)g, but attempts to isolate this compound have not met with success. Its double salts with the alkali thiocyanates have, however, been obtained in well-defined crystals when an alkali thiocyanate is substituted for the barium salt. The following are known —... 

Some other ions also react chemically with the negatively charged sites, forming stronger chemical bonds. Such ions as fluoride, phosphate, and molybdate are very strongly retained. Birrell [1961] gave examples of the changes that took place when phosphates, molybdates, chromates, vanadates, sulphates, and fluorides were allowed to react to completion with allophane. In some of these cases, taranakite could be identified after reaction with phosphate. 

An important indusuial interest is in the conosion of metals and ceramics by molten sodium sulphate/vanadate solutions. This is because turbines, which are usually nickel-based alloys, operating in a marine anuosphere, containing... 

Reactions of contaminants in the fuel or air in the combustion zone can result in the formation of compounds which can condense as molten salts onto cooler components in the system. This type of process can occur when fuels containing sulphur or vanadium are burnt. In the case of sulphur contaminants, alkali sulphates form by reactions with sodium which may also be present in the fuel or in the combustion air, and for vanadium-containing fuels low-melting-point sodium vanadates or vanadium pentoxide are produced, particularly when burning residual oils high in vanadium. Attack by molten salts has many features in common which will be illustrated for the alkali-sulphate-induced attack, but which will be subsequently shown to be relevant to the case of vanadate attack. 

B. Wet Processes.—These vary considerably in detail according to the nature and amount of constituents other than vanadium in the ore. An outline of the operations involved in the case of patronite is as follows The ore is roasted with common salt or sodium carbonate and then extracted either (a) with water to give an alkaline solution of sodium vanadate and soluble vanadates of other metals, any lead, zinc, copper, etc., being left in the residue or (b) with sulphuric acid to produce a solution of vanadyl sulphate. Acid extraction is usually employed when the vanadium content of the material is low. The alkaline extract from (a) is treated with excess of sodium carbonate in order to precipitate calcium and aluminium, after removal of which,... 

For the treatment of camotite several methods are available. The method recommended by the United States Bureau of Mines2 is as follows The ore is leached with concentrated nitric acid at 100° C., neutralised with caustic soda, and barium chloride and sulphuric acid added to the solution to precipitate the radium as barium-radium sulphate. The precipitate settles in three or four days, after which time the clear liquid is decanted into tanks and is treated with excess of boiling sodium carbonate solution in order to precipitate any iron, aluminium and chromium present. The solution now contains sodium uranyl carbonate and sodium vanadate. It is nearly neutralised with nitric acid, and caustic soda is added in sufficient quantity to precipitate the uranium as sodium uranate. After filtering, the remaining solution is neutralised with nitric acid and ferrous sulphate added, whereupon iron vanadate is thrown down. By this method it is claimed that 90 per cent, of the radium, all the uranium, and 50 per cent, of the vanadium in the camotite are recovered. 

In some cases, however, the modus operandi is modified. In the oxidation of hydriodic acid with chromic acid, the data indicate that while liberation of iodine takes place, the vanadous or hypovanadic salt employed as the catalyst also undergoes oxidation to vanadate.2 The vanadium compound here belongs to the class of catalysts known as inductors, and the reaction is comparable to the oxidation in aqueous solution of sodium sulphite with sodium arsenite, whereby both sodium sulphate and sodium arsenate are produced. 

Iron Vanadate is, metallurgically, the most important vanadate. Precipitation of a solution of a vanadate with ferrous sulphate gives rise to a precipitate of indefinite composition, ortlio-, pyro-, meta-, and perhaps a poly-vanadate being present, as well as ferric or ferrous oxide. Reduction of the vanadate to a vanadyl salt may also ensue. The precipitate is usually colloidal and carries down with it some sodium vanadate. The dried powder may be either green, yellow, brown, or red the more nearly the precipitate approximates to a red colour the lower is its vanadium content. An iron vanadate has also been prepared by electrolysis of a solution of sodium vanadate between iron poles.1... 

Zinc Polyvanadate, 2Zn0.3Va08.15Ha0, is obtained as well-defined crystals by the action of zinc sulphate on acid barium vanadate. ... 

The estimation of a vanadate solution by direct titration with ferrous sulphate or ferrous ammonium sulphate solution has been worked out, and is found to be specially applicable to the analysis of vanadium alloys. The vanadate is again reduced to tire tetravalent state by the ferrous salt, the end point being obtained by the use of potassium ferricyanide as internal indicator alternatively, a known excess of the ferrous salt solution is added to the vanadate, the amount unused... 

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... 

---