Molybdenum in acids

Table 2. Aqueous Ions of Molybdenum in Acid Solutions...

Table 7.17 The oxidation states of molybdenum in acid solution...

M. Bojinov, I. Betova, and R. Raicheff, A model for the transpassivity of molybdenum in acidic sulphate solutions based on ac impedance measrrrements, Electrochim. Acta 1173 (1996). 

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). 

Molecular examples of trivalent molybdenum are known in mononuclear, dinuclear, and tetranuclear complexes, as illustrated in Figure 5. The hexachloride ion, MoCk (Fig- 5a) is generated by the electrolysis of Mo(VI) in concentrated HCl. Hydrolysis of MoCP in acid gives the hexaaquamolybdenum(III) ion, Mo(H20) g, which is obtainable in solution of poorly coordinating acids, such as triflic acid (17). Several molybdenum(III) organometaUic compounds are known. These contain a single cyclopentadienyl ligand (Cp) attached to Mo (Fig. 5d) (27). 

Aqueous Chemistry. Molybdenum has weU-characterized aqueous chemistry in the five oxidation states, VI, V, IV, III, and II. A listing of aqua ions is given in Table 2. Except for the Mo(VI) species all of the aqua ions are only soluble or stable in acidic media (17). The range of aqueous ions known for molybdenum is far broader than that of other elements. 

Soil Nutrient. Molybdenum has been widely used to increase crop productivity in many soils woddwide (see Fertilizers). It is the heaviest element needed for plant productivity and stimulates both nitrogen fixation and nitrate reduction (51,52). The effects are particularly significant in leguminous crops, where symbiotic bacteria responsible for nitrogen fixation provide the principal nitrogen input to the plant. Molybdenum deficiency is usually more prominent in acidic soils, where Mo(VI) is less soluble and more easily reduced to insoluble, and hence unavailable, forms. Above pH 7, the soluble anionic, and hence available, molybdate ion is the principal species. 

Volcanic Deposits. Uranium deposits of volcanic deposits type are strata-bound and stmcture-bound concentrations in acid volcanic rocks. Uranium is commonly associated with molybdenum, fluorine, etc. Examples are the uranium deposits in Michelin, Canada Nopal I in Chihualiua, Mexico Macusani in Pern and numerous deposits in China and the CIS (16). 

The catalysts are prepared by impregnating the support with aqueous salts of molybdenum and the promoter. In acidic solutions, molybdate ions are present largely in the form of heptamers, [Mo2024] , and the resulting surface species are beHeved to be present in islands, perhaps containing only seven Mo ions (100). Before use, the catalyst is treated with H2 and some sulfur-containing compounds, and the surface oxides are converted into the sulfides that are the catalyticaHy active species. 

The Krupp work had shown interesting improvements in acid resistance resulting from molybdenum and copper additions, and the use of 2-3% Mo for more difficult acid conditions was soon established. Other early additions were made to overcome susceptibility to intercrystalline corrosion, culminating in the general use, by the early thirties, of titanium additions for carbide stabilisation, followed shortly after by the alternative use of niobium. 

The alloying elements molybdenum and copper do not, by themselves, enhance passivity of nickel in acid solutions, but instead ennoble the metal. This means that, in practice, these alloying elements confer benefit in precisely those circumstances where chromium does not, viz. hydrogen-evolving acidic solutions, by reducing the rate of anodic dissolution. In more oxidising media the anodic activity increases, and, since binary Ni-Mo and Ni-Cu alloys do not passivate in acidic solutions, they are generally unsuitable in such media. 

The US Bureau of Mines found the chemical and galvanic corrosion behaviour of both the TZM and Mo-30W alloy to be generally equal or superior to that of unalloyed molybdenum in many aqueous solutions of acids, bases and salts. Notable exceptions occurred in 6-1 % nitric acid where both alloys corroded appreciably faster than molybdenum. In mercuric chloride solutions the TZM alloy was susceptible to a type of crevice corrosion which was not due to differential aeration. The alloys were usually not adversely affected by contact with dissimilar metals in galvanic couple experiments, but the dissimilar metals sometimes corroded galvanically. Both alloys were resistant to synthetic sea water spray at 60°C. 

Masing, G. and Roth, C., Behaviour of Molybdenum and Nickel and Some Molybdenum-nickel Alloys in Acid Electrolytes , Werkstqffe and Korrosion, 3, 176-186, 253-263 (1952)... 

Discussion. Molybdenum(VI) in acid solution when treated with tin(II) chloride [best in the presence of a little iron(II) ion] is converted largely into molybdenum(V) this forms a complex with thiocyanate ion, probably largely Mo(SCN)5, which is red in colour. The latter may be extracted with solvents possessing donor oxygen atoms (3-methylbutanol is preferred). The colour depends upon the acid concentration (optimum concentration 1M) and the concentration of the thiocyanate ion (1 per cent, but colour intensity is constant in the range 2-10 per cent) it is little influenced by excess of tin(II) chloride. The molybdenum complex has maximum absorption at 465 nm. 

The above procedure may be adapted to the determination of molybdenum in steel. Dissolve a 1.00 g sample of the steel (accurately weighed) in 5 mL of 1 1 hydrochloric acid and 15 mL of 70 per cent perchloric acid. Heat the solution until dense fumes are evolved and then for 6-7 minutes longer. Cool, add 20 mL of water, and warm to dissolve all salts. Dilute the resulting cooled solution to volume in a 1 L flask. Pipette 10.0 mL of the diluted solution into a 50 mL separatory funnel, add 3 mL of the tin(II) chloride solution, and continue as detailed above. Measure the absorbance of the extract at 465 rnn with a spectrophotometer, and compare this value with that obtained with known amounts of molybdenum. Use the calibration curve prepared with equal amounts of iron and varying quantities of molybdenum. If preferred, a mixture of 3-methylbutanol and carbon tetrachloride, which is heavier than water, can be used as extractant. 

Molybdenum(VI), vanadium(V), mercury, and iron interfere permanganates, if present, may be removed by boiling with a little ethanol. If the ratio of vanadium to chromium does not exceed 10 1, nearly correct results may be obtained by allowing the solution to stand for 10-15 minutes after the addition of the reagent, since the vanadium-diphenylcarbazide colour fades fairly rapidly. Vanadate can be separated from chromate by adding oxine to the solution and extracting at a pH of about 4 with chloroform chromate remains in the aqueous solution. Vanadium as well as iron can be precipitated in acid solution with cupferron and thus separated from chromium (III). 

Discussion. In acid solution, toluene-3,4-dithiol (dithiol) forms a red compound when warmed with tin(II) salts (compare molybdenum, Section 17.30). Tin(IV) also reacts, but more slowly than tin(II) thioglycollic acid may be employed to reduce tin(IV) to tin(II). The reagent is not stable, being easily reduced, and hence should be prepared as required. A dispersant is generally added to the solution under test. 

A. Molybdenum blue method Discussion. Orthophosphate and molybdate ions condense in acidic solution to give molybdophosphoric acid (phosphomolybdic acid), which upon selective reduction (say, with hydrazinium sulphate) produces a blue colour, due to molybdenum blue of uncertain composition. The intensity of the blue colour is proportional to the amount of phosphate initially incorporated in the heteropoly acid. If the acidity at the time of reduction is 0.5M in sulphuric acid and hydrazinium sulphate is the reductant, the resulting blue complex exhibits maximum absorption at 820-830 nm. 

Molybdenum Trioxide (Molybdenum Anhydride, Moiybdic Oxide, Moiybdic Acid Anhydride). Mo03, mw 143.95, white powd, mp 795°, bp 1155°, d 4.696g/cc at 26/4°, SI sol in w, sol in acids, alk sulfates and amm hydroxide. Prepn is by first boiling coned nitric acid with NH4... 

On account of the fact that the electrode potential of molybdenum is more negative than the discharge potential of hydrogen, principle difficulties arise to cathodically electrodeposit molybdenum chalcogenide films from aqueous solutions. Theoretically, the deposition of pure molybdenum by electrolytic reduction of molybdates in acidic aqueous solutions is possible according to the reaction... 

Gladyshev VN, SV Khangulov, TC Stadtmann (1994) Nicotinic acid hydrolase from Clostridium barkeri electron paramagnetic studies show that selenium is coordinated with molybdenum in the catalytically active selenium-dependent enzyme. Proc Natl Acad USA 91 232-236. 

In the first family, the metal is coordinated by one molecule of the pterin cofactor, while in the second, it is coordinated to two pterin molecules (both in the guanine dinucleotide form, with the two dinucleotides extending from the active site in opposite directions). Some enzymes also contain FejSj clusters (one or more), which do not seem to be directly linked to the Mo centers. The molybdenum hydroxylases invariably possess redox-active sites in addition to the molybdenum center and are found with two basic types of polypeptide architecture. The enzymes metabolizing quinoline-related compounds, and derivatives of nicotinic acid form a separate groups, in which each of the redox active centers are found in separate subunits. Those enzymes possessing flavin subunits are organized as a2jS2A2, with a pair of 2Fe-2S centers in the (3 subunit, the flavin in the (3 subunit, and the molybdenum in the y subunit. 

Section 2.17). We shall find that it dominates much of life s organic chemistry too. There is also the rather unusual insolubility of VS4. We need to explain the presence of some V, Co, Ni and Zn in early life, but note that their sulfides are relatively soluble in somewhat acid solutions, pH < 7, which may have prevailed at least locally some 4 x 109 years ago. Molybdenum and heavy metals of Groups 13 to 16 are also insoluble as sulfides but tungsten does not precipitate so easily and is known to be more available than molybdenum in sulfide-rich seas. 

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