Molybdates transition

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

In 1826 J. J. Berzelius found that acidification of solutions containing both molybdate and phosphate produced a yellow crystalline precipitate. This was the first example of a heteropolyanion and it actually contains the phos-phomolybdate ion, [PMoi204o] , which can be used in the quantitative estimation of phosphate. Since its discovery a host of other heteropolyanions have been prepared, mostly with molybdenum and tungsten but with more than 50 different heteroatoms, which include many non-metals and most transition metals — often in more than one oxidation state. Unless the heteroatom contributes to the colour, the heteropoly-molybdates and -tungstates are generally of varying shades of yellow. The free acids and the salts of small cations are extremely soluble in water but the salts of large cations such as Cs, Ba" and Pb" are usually insoluble. The solid salts are noticeably more stable thermally than are the salts of isopolyanions. Heteropoly compounds have been applied extensively as catalysts in the petrochemicals industry, as precipitants for numerous dyes with which they form lakes and, in the case of the Mo compounds, as flame retardants. 

Partially Crystalline Transition Metal Sulphide Catalysts. Chiannelli and coworkers (6, 7, 8) have shown how, by precipitation of metal thio-molybdates from solution and subsequent mild heat-treatment many selective and active hydrodesulphurization catalysts may be produced. We have shown (18) recently that molybdenum sulphide formed in this way is both structurally and compositionally heterogeneous. XRES, which yields directly the variation in Mo/S ratio shows up the compositional nonuniformity of typical preparations and HREM images coupled to SAED (see Figure 2) exhibit considerable spatial variation, there being amorphous regions at one extreme and highly crystalline (18, 19) MoS at the other. 

Heats of formation of certain molybdates and tungstates have been estimated. The Mossbauer parameters for the 100 keV transition of in WO3,... 

Vibrational Spectra of Transition Element Compounds Table 9. IR and Raman data (in cm i) for orthorhombic molybdates and tungstates 84)... 

Exciting closed shell transition metal complexes such as tungstates, molybdates, vanadates, titanites etc. This way of excitation and its transfer to the rare-earth elements has been known since the late fifties. 

Since a polymorphic transition (a/p) of the mixed iron and cobalt molybdate occurs in the temperature range of the catalytic reaction (10,13,14), and since the high temperature form (p) can metastably be maintained at low temperature,... 

Molybdenum is a metal of the second transition series, one of the few heavy elements known to be essential to life. Its most stable oxidation state, Mo(VI), has 4d orbitals available for coordination with anionic ligands. Coordination numbers of 4 and 6 are preferred, but molybdenum can accommodate up to eight ligands. Most of the complexes are formed from the oxycation Mo(VI)022+. If two molecules of water are coordinated with this ion, the protons are so acidic that they dissociate completely to give Mo(VI)042, the molybdate ion. Other oxidation states vary from Mo(III) to Mo(V). 

Although Wolfs indicated that the catalyst particles are covered by a skin of bismuth molybdate, Batist (112) recently found bismuth, molybdenum, and iron in the surface layers of multicomponent catalysts. Additional data are needed to determine if multicomponent catalysts gain their activity as a result of the formation of compounds such as bismuth iron molybdate, or by surface enhancement of an active component such as 7-phase bismuth molybdate, or by creation of low-energy electronic transitions. Of course, due to their complexity, all of these factors may be important. 

Firsova et al. (136) also investigated a cobalt molybdate catalyst containing a small amount of Fe3+, after exposure to a reaction mixture of propylene and oxygen. The authors observed the valence change of Fe3+ to Fe2+ and the formation of a surface complex between the hydrocarbon and the iron (Fe—O—C—). In contrast to pure iron molybdate which also forms a surface Fe—O—C— complexes, the electronic transitions in the cobalt iron molybdate were reversible. The observed valence change showed that iron ions increase the electronic interaction between ions in the catalyst and the components of the reaction mixture. 

Such an effect might be expected when boehmite supported cobalt is being calcined, viz. during the phase transition AIO(OH) - y-Al203. Figure 7 shows spectra of pyridine, adsorbed on the sample CoMo-124 B, which has been prepared in this way. Spectra for MoCo-122, -123 and -124, containing 2, 3 and 4 wt% CoO resp. are shown for comparison. All these catalysts have had a final calcination of 650°C. Comparison of the spectra of CoMo-124 B and MoCo-124 indicates that the intensity of the 1612 cm l band, which is introduced by the interaction of the cobalt ions and the molybdate layer, is lower for CoMo-124 B than for MoCo-124. The spectrum for CoMo-124 B resembles that of CoMo-123, indicating that a part of the cobalt ions does not participate in this interaction. 

Cornish, A.S. and W.J. Page. 2000. Role of molybdate and other transition metals in the accumulation of protochelin by Azotobacter vinelandii. Appl. and Environ. Microbiol. 66 1580-1586. 

When the central atom is not a transition element, a soluble molybdate or tungstate may be dissolved with a soluble salt containing the central atom in the appropriate oxidation state. The mixture is then acidified to an appropriate pH range. Sometimes barium molybdate is mixed with a sulfuric acid solution containing the central atom, or molybdenum trioxide is boiled with a solution containing the atom. 

When the central atom is a transition metal, a simple salt of that element may be mixed hot with a soluble molybdate or tungstate in a solution of appropriate pH. If the central atom must be raised to an unusual oxidation state, persulfate, peroxide or bromine water are often employed electrolytic oxidation may also be used. Alternatively, freshly precipitated hydrous metal oxides may be boiled in acidic molybdate or tungstate solutions, or coordination complexes may be decomposed in hot molybdate solutions. Free acids are prepared in several ways ... 

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