Chromium molybdates

Aluminum molybdate, Al2(MoOi )3 was first prepared by Doyle and Forbes(T2) quickly followed by other workers (Ul,73). DSC measurements by Sleight(52) indicate the structure to be monoclinic below 200°C the structure is isomorphous with chromium molybdate( 1). 

All these molybdates are isostructural with ferric molybdate with an open 3-dimensional network of MO octahedra and M0O4 tetrahedra. A ferroelastic transition exists from the low temperature monoclinic form to the high temperature orthorhombic form. The transition temperature varies from 200 C for pure aluminum molybdate to 385 0 for pure chromium molybdate and 500 C for pure ferric molybdate. For the mixed molybdates, the transition temperature was found to be a linear function of composition as is illustrated in Figure 4 for the mixed iron-aluminum molybdates. 

Coatings, Paints, and Pigments. Various slightly soluble molybdates, such as those of zinc, calcium, and strontium, provide long-term corrosion control as undercoatings on ferrous metals (90—92). The mechanism of action presumably involves the slow release of molybdate ion, which forms an insoluble ferric molybdate protective layer. This layer is insoluble in neutral or basic solution. A primary impetus for the use of molybdenum, generally in place of chromium, is the lower toxicity of the molybdenum compound. 

H. 8-Hydroxyquinaldine (XI). The reactions of 8-hydroxyquinaldine are, in general, similar to 8-hydroxyquinoline described under (C) above, but unlike the latter it does not produce an insoluble complex with aluminium. In acetic acid-acetate solution precipitates are formed with bismuth, cadmium, copper, iron(II) and iron(III), chromium, manganese, nickel, silver, zinc, titanium (Ti02 + ), molybdate, tungstate, and vanadate. The same ions are precipitated in ammoniacal solution with the exception of molybdate, tungstate, and vanadate, but with the addition of lead, calcium, strontium, and magnesium aluminium is not precipitated, but tartrate must be added to prevent the separation of aluminium hydroxide. 

For formation of anticorrosive and adhesion-improving protective layers on metals the cleaned surface is treated with aqueous acidic solution containing molybdate, chromium fluoride, phosphate, acetate, and Zn ions. As dispersant a mixture of 60% alkali salt of a phosphate ester, 20% alkylpolyglucoside, and 20% fatty alcohol ethoxylate was applied. This method passivates the metal surface by formation of an anticorrosive and protective layer that improves adhesion of subsequent coatings. 

Chromium(III) sulfide, CrySs chromium selenide, CrSe chromium(III) telluride, Cr2Tc3 molybdenum(IV) sulfide, M0S2 (molybdenite) molybde-num(IV) selenide, MoSe2 molybdenum(IV) telluride, MoTey tungsten(IV) sulfide,... 

A.K. Minocha, Pankaj Kumar, Jaswinder Singh, L.K. Aggarwal, C.L. Verma, Effect of molybdate (II), chromium (III) and (VI) metal ions on the setting time of ordinary Portland cement. Indian J. Env. Prot., 24, 771-774, 2004. 

Bis(benzene)chromium dichromate, 3851 Calcium chromate, 3926 Copper chromate oxide, 4223 Dibismuth dichromium nonaoxide, 0232 Lead chromate, 4243 Lithium chromate, 4236 Magnesium permanganate, 4691 Potassium dichromate, 4248 Potassium permanganate, 4647 Sodium dichromate, 4250 Sodium molybdate, 4713 Sodium permanganate, 4703 Zinc permanganate, 4710... 

Modification of the metal itself, by alloying for corrosion resistance, or substitution of a more corrosion-resistant metal, is often worth the increased capital cost. Titanium has excellent corrosion resistance, even when not alloyed, because of its tough natural oxide film, but it is presently rather expensive for routine use (e.g., in chemical process equipment), unless the increased capital cost is a secondary consideration. Iron is almost twice as dense as titanium, which may influence the choice of metal on structural grounds, but it can be alloyed with 11% or more chromium for corrosion resistance (stainless steels, Section 16.8) or, for resistance to acid attack, with an element such as silicon or molybdenum that will give a film of an acidic oxide (SiC>2 and M0O3, the anhydrides of silicic and molybdic acids) on the metal surface. Silicon, however, tends to make steel brittle. Nevertheless, the proprietary alloys Duriron (14.5% Si, 0.95% C) and Durichlor (14.5% Si, 3% Mo) are very serviceable for chemical engineering operations involving acids. Molybdenum also confers special acid and chloride resistant properties on type 316 stainless steel. Metals that rely on oxide films for corrosion resistance should, of course, be used only in Eh conditions under which passivity can be maintained. 

Another property of the iron-defective molybdate is the presence of Mo=0 double bonds on the surface. The hydrogen-abstracting capacity of the catalyst is closely related to Mo6 contained in the Mo=0 as is shown in Sect. 3. There the role of iron is also discussed. It is, however, interesting to note here that pure iron oxides accelerate combustion and that a W03—Fe2(W04)3 catalyst is practically inactive [254], Replacement of iron by chromium is possible but leads to a lower activity [253]. Baussart et al. [46] prepared stoichiometric NiMo04 which showed selective behaviour towards formaldehyde in a pulsed column below 375°C. 

Iron oxide is an important component in catalysts used in a number of industrially important processes. Table I shows some notable examples which include iron molybdate catalysts in selective oxidation of methanol to formaldehyde, ferrite catalysts in selective oxidative dehyrogenation of butene to butadiene and of ethylbenzene to styrene, iron antimony oxide in ammoxidation of propene to acrylonitrile, and iron chromium oxide in the high temperature water-gas shift reaction. In some other reactions, iron oxide is added as a promoter to improve the performance of the catalyst. 

Many of the finishes applied to other types of metal products can also be applied to zinc die castings, although some differences in formulation as well as occasional differences in method of application may be desirable. The types of finishes applicable to zinc die castings include mechanical finishes (buffed, polished, brushed, and tumbled) electrodeposited finishes (copper, nickel, chromium, brass, silver, and black nickel) chemical finishes (chromale, phosphate, molybdate and black nickel) and organic finishes (enamel, lacquer, paint and varnish, and plastic finishes). Electrodeposited coatings of virtually any metal capable of electrodeposition can be applied to zinc die castings. 

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