Heteropoly vanadates

All the foregoing heteropoly-eompounds contain vanadium pent-oxide. A large number of other compounds have been prepared which, from their analytical data, appear to contain one of the lower oxides in varying proportions together with the pentoxide, e.g. vanadous-vanadophosphates,3 vanadous-vanadoarsenaies,4 vanadous-vanadomolyb-dales 3 vanadous-vanadotungstates.6 The constitutions of these have not been established. 

Olefin oxidation with an aqueous palladium chloride solution according to eqs. (2)-(4) occurs stoichiometrically. A catalytic reaction is only possible if the metallic palladium can be reoxidized immediately. With gaseous oxygen, conditions to oxidize even finely divided palladium black are not optimal. However, metal salts such as cupric and ferric chlorides, chromates, heteropoly acids of phosphoric acid with molybdic and vanadic acids, or other oxidants - e. g., ben-zoquinone is used in kinetic investigations [10] - are suitable for reoxidation of the palladium metal. This fact explains the increase of the yield of acetaldehyde in the first experiments of the Consortium carried out in the presence of cupric and ferric chlorides, as mentioned above. 

Vanadium (V, at. mass 50.94) occurs in the V, IV, III, and II oxidation states, vanadium(V) compounds being the most stable. In alkaline medium, the colourless vanadate VOs ions exist, whereas in strongly aeidic media, the yellow V02 cations are present. Within the intermediate pH range polymerized orange-yellow anionic forms occur. Vanadium(V) forms heteropoly acids with P(V), Mo(VI), and W(VI), and also peroxide complexes. Vanadium(IV) occurs as the blue vanadyl ion V02", stable in acid solutions and readily oxidized to vanadium(V) in alkaline solution. The VO cation is amphoteric. At pH 4, V0(0H)2 precipitates and at pH 9 it dissolves. Vanadium(IV) forms fluoride-, oxalate-, and... 

Heteropoly compounds are composed not only of the weak, oxygen-containing metallic acids (tungstic, molybdic and vanadic), but also of moderately strong to weak acids of nonmetals, e.g., boric, silicic, phosphoric, arsenic, telluric, etc., acids. Stable heteropoly compounds very frequently show nonmetallic to metallic acid ratios of 1 12, 1 6 or 1 9. Since the heteropoly compounds form under conditions similar to those in which isopoly compounds are obtained, that is, only in solutions containing H+ ions, it is assumed that the building blocks of the heteropolyanions are isopoly anions [1]. 

Oxidation of ethylene according to Eq. (9.2) occurs stoichiometrically. A catalytic oxidation is possible if palladium(O) is reoxidized immediately. This happens in the presence of oxidizing agents such as cupric and ferric chlorides ferric sulfate chromates heteropoly acids of phosphoric, molybdic, and vanadic acids peroxides and others. Benzoquinone is used by Moiseev et al. for their kinetic investigations [11]. Gaseous oxygen does not oxidize palladium black in a sufficiently short time. 

Spectrophotometric methods are usually preferred for routine analysis of this parameter, most of them relying on the reaction between orthophosphate ions and molybdate in acidic medium in order to form a heteropoly acid. Color formation can be enhanced by adding vanadate to obtain the yellow vanadomolybdate complex (vanadomolybdophosphoric acid method) or by reducing the molybdo-phosphoric acid to yield strongly colored phosphomolybdenum blue species. 

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