Molybdophosphates

A comparatively large number of molybdenum derivatives with the empirical formula A Mo P O, where A is usually a Group 1 or Group II metal, have been studied and characterised by crystal structure determination. These include [46-50] 

The complex oxide K4MogPi2052 contains pentavalent molybdenum and is built from MoOg octahedra and PO4 tetrahedra which share corner O atoms. The structure contains one-dimensional 

FIG U RE 5.45 Tunnel structure of K4M08P12O52. Built from [MoOJ octahedara nd [PO4] tetrahedra sharing corner O atoms. K in channels. (Adapted from K.H. Lii and R.C. Haushalter, JSStC, 69, 320, 1988.) 

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Sensitivity of the proposed method correlates with molai absorptivity of the cyanine dye. Mixed POMs PMeMo O j (Me=TP+, Sb +, BP+) were chosen as analytical form because of its higher stability as compared with 12-molybdophosphate. Only 2-3T0 concentration of molybdate is enough for complete formation of POM avoiding in this way formation of lA with polymolybdate ions. In addition, mixed POMs are stable in wider interval of pH. Increasing of anion chai ge from 3 to 5(6) is also favorable. Constant absorbance of lA is observed in the acidity range of 0.12-0.28 M. 

Procedure has been proposed for the P(V) and As(V) determination based on the selective extraction of ionic associate of Crystal Violet with reduced molybdophosphate with mixture of inert (toluene) and active (methyl isobutyl ketone) solvents. Extraction of reagent is negligible. After concentration determination lower than 10 mol/1 of P(V) and As(V) is possible. 

Spectrophotometric methods based on an enhancement of the blue color produced on reduction of 12-molybdophosphate (arsenate) in the presence of antimony(III) are widely used for the determination of phosphoms(V) or arsenic(V). However, nature of heteropoly blue, their spectra, mechanism of the reaction are obscure. In addition, mixed POMs were shown as very efficient analytical forms for the determination of P(V) and As(V). 

It is shown that both Sb(III) and Bi(III) can speed reduction of 12-molybdophosphate (12-MPC) to the corresponding heteropoly blue (12-MPB) by ascorbic acid (AA). It is found that mixed polyoxometalates can be formed in solution which reduce considerably more rapidly than 12-MPC. Complete formation of mixed POM is observed only if significant excess of Me(III) ions is used in the reaction. POM responsible for blue color was synthesized by selective extraction. Chemical analysis of tetrabutyl-ammonium salt is in accordance with formula of (TBAl PMeflllfMo O j (Me = Sb, Bi). IR spectmm of mixed POM is identical to 12-MPC. 

The application of ammonium molybdophosphate and other unsoluble in water salts of heteropolyacids for preconcentration of heavy metals of first group elements Cs(I), Ag(I), Cu(I) and also T1(I), Hg(I) (M(I)) is described. The shortcomings of ammonium molybdophosphate as ionexchanger are ... 

We achieved, that by contact of polyurethane foam with water solution of molybdophosphate, contain by pH 1-2,5 mixture of saturated (5 NMR P=-3.20 p.p.m. apply to 85 % H PO ) and unsaturated monovacant (x=0-t-4) (5 NMR P = -0,96 p.p.m.) heteropolycomplexes Keggin staicture, equilibrium discharge in the direction produced of saturated heteropolycomplex of Dowson stmcture and on the surface of polyurethan foam formed 18-molybdo-2-phosphate acid ( P = -2,40 p.p.m. in ether extract). The formed surfaces heteropolycomplex is stable for action 1 M solution of strong acids and basics and have ion exchanged properties in static and dynamic conditions to relation to macro and micro amount of M(I) ... 

Discussion. When a solution of an orthophosphate is treated with a large excess of ammonium molybdate solution in the presence of nitric acid at a temperature of 20-45 °C, a precipitate is obtained, which after washing is converted into ammonium molybdophosphate with the composition (NH4)3[P04,12Mo03]. This may be titrated with standard sodium hydroxide solution using phenolph-thalein as indicator, but the end point is rather poor due to the liberation of ammonia. If, however, the ammonium molybdate is replaced by a reagent containing sodium molybdate and quinoline, then quinoline molybdophosphate is precipitated which can be isolated and titrated with standard sodium hydroxide ... 

The main advantages over the ammonium molybdophosphate method are (1) quinoline molybdophosphate is less soluble and has a constant composition, and (2) quinoline is a sufficiently weak base not to interfere in the titration. 

The method may be standardised, if desired, with pure potassium dihydrogen-orthophosphate (see below) sufficient 1 1 hydrochloric acid must be present to prevent precipitation of quinoline molybdate the molybdophosphate complex is readily formed at a concentration of 20 mL of concentrated hydrochloric acid per 100 mL of solution especially when warm, and precipitation of the quinoline salt should take place slowly from boiling solution. A blank determination should always be made it is mostly due to silica. 

Determination of phosphate as ammonium molybdophosphate. This may be readily effected by precipitation with excess of ammonium molybdate in warm nitric acid solution arsenic, vanadium, titanium, zirconium, silica and excessive amounts of ammonium salts interfere. The yellow precipitate obtained may be weighed as either ammonium molybdophosphate, (NH4)3[PMo12O40], after drying at 200-400 °C, or as P205,24Mo03, after heating at 800-825 °C for about 30 minutes. 

Discussion. Phosphate ion is determined nephelometrically following the formation of strychnine molybdophosphate. This turbidity is white in colour and consists of extremely fine particles (compare ammonium molybdophosphate, which is yellow and is composed of rather large grains). The precipitate must not be agitated, as it tends to agglomerate easily it is somewhat sensitive to temperature changes. 

Epoxides have been found to cleanly react with acetic anhydride to provide the diacetate under solvent-free conditions <06TL6865>. Treatment of epoxides with ammonium-12-molybdophosphate and a slight excess of acetic anhydride (1.2 equivalents) provides the corresponding diacetate in excellent yields. A number of epoxides were examined and all worked quite well. It was also found that /V-losyl aziridines participate in this reaction providing the corresponding acetoxysulfonamides. 

Theory The underlying principle for the assay of P043- ion by nephelometry is the formation of strychnine-molybdophosphate complex (I). 

The AOAC alkalimetric ammonium molybdophosphate and photometric molybdovanadate methods for animal feed are described by Padmore (1990, pp. 87-88), and for plants by Isaac (1 990, p. 56). A spectrophotometric molybdovanadate procedure is also described in MAFF/ADAS (1986, pp. 181-182). The official Bran-rLuebbe AutoAnalyzer method for phosphate in soil, plant and fertilizer extracts is reproduced with permission in Appendix 6. 

Indeed, other electrocatalytic processes were studied, including the pioneering work on chlorate reduction by the six-electron reduction product of 12-molybdophosphate in water-dioxane solutions [169]. This process, extended to bromate, has become a classical test of the electrocatalytic abilities of several POMs [see Table 13]. 

Instead of being determined volumetrically, however, the ammonium or quinoline molybdophosphates are usually reduced to another molybdenum complex, molybdenum blue (heteropoly blue), which is then analysed spectrophotometrically (see Section II.B.2.C). 

The fact that twelve molybdate ions are bound to each phosphate unit in molybdophosphate has been exploited as an amplifying factor. The molybdophosphoric acid is extracted from the original solution into a mixture of diethyl ether or chloroform with butanol, in order to eliminate the excess of molybdate reagent it is then re-extracted into an aqueous phase and broken down with alkali. The molybdate ions are reacted with ammonium rhodanide90 or aminochlorobenzenethiol76 to give coloured products with absorption maxima at 470 and 710 nm, respectively. One phosphate ion thus yields twelve molybdate units, the optical absorbance is amplified with respect to that of the heteropoly phosphate complex and its measurement provides a sensitive determination procedure. 

The heteropoly molybdophosphates are much more reducible than the corresponding tungstates, but the latter exhibit one-electron transfer steps at high pH whereas the molybdophosphates did not (12). Otherwise, the electronic structures and behavior of the two are very similar (13), and perhaps the F-C reagent operates well, partly because one-electron transfers are possible, yet the reagent is a good oxidant. 

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