Molybdate, determination

Description of Method. The FIA determination of phosphate is an adaptation of a standard spectrophotometric analysis for phosphate. In the presence of add, phosphate reacts with molybdate to form a yellow-colored complex in which molybdenum is present as Mo(VI). 

The total phosphoms content of the sample is determined by method AOCS Ja 5-55. Analysis of phosphoUpid in lecithin concentrates (AOCS Ja 7-86) is performed by fractionation with two-dimensional thin-layer chromatography (tic) followed by acid digestion and reaction with molybdate to measure total phosphorous for each fraction at 310 nm. It is a semiquantitative method for PC, PE, PI, PA, LPC, and LPE. Method AOCS Ja 7b-91 is for the direct deterrnination of single phosphoHpids PE, PA, PI, PC in lecithin by high performance Hquid chromatography (hplc). The method is appHcable to oil-containing lecithins, deoiled lecithins, lecithin fractions, but not appHcable to lyso-PC and lyso-PE. 

Analytical Methods. Molybdenum contents in ore concentrates and technical oxide are most accurately deterrnined gravimetricaHy by precipitating lead molybdate. Molybdenum content is usually not determined on pure compounds or metal. Instead, spectrographic methods are used to measure impurity elements that must be controlled. Carbon and oxygen in metal products are measured by standard gas analysis methods. 

Polarimetric analysis of sorbitol and mannitol in the presence of each other and of sugars is possible because of their enhanced optical rotation when molybdate complexes are formed and the higher rotation of the mannitol molybdate complex under conditions of low acidity (194). The concentration of a pure solution of sorbitol may be determined by means of the refractometer (195). Mass spectra of trimethylsilyl ethers of sugar alcohols provide unambiguous identification of tetritols, pentitols, and hexitols and permit determination of molecular weight (196). 

First procedure consists of several stages. 11-molybdo-bismuthphosphate (MBP) is formed and extracted with butyl acetate, stripped with ammonia or acetate buffer solution and determined in aqueous solution using reaction of MBP with Astro Floxine (AF) or other polymethine dyes. Full separation from molybdate excess is not necessary in this procedure as spectiaim of lA differs considerable from dye spectiaim. Therefore sepai ation is simplified and used only as preconcentration step. Concentration factor 50 and good reproducibility make possible determination of low P(V) concentrations at 10 mol/1 level and lower. 

SPECTROPHOTOMETRIC DETERMINATION OF RARE EARTH ELEMENTS IN MONO CRYSTALS AND STARTING LEAD MOLYBDATE RAW MATERIAL... 

Phosphorus and Silicon in Waters, Effluents and Sludges [e.g. Phosphorus in Waters, Effluents and Sludges by Spectrophotometry-phosphomolybdenum blue method. Phosphorus in Waters and Acidic Digests by Spectrophotometry-phosphovanadomolybdate method. Ion Chromatographic Methods for the Determination of Phosphorus Compound, Pretreatment Methods for Phosphorus Determinations, Determination of silicon by Spectrophotometric Determination of Molybdate Reactive Silicon-1 -amino-2-naphthol-4, sulphonic acid (ANSA) or Metol reduction methods or ascorbic acid reduction method. Pretreatment Methods to Convert Other Eorms of Silicon to Soluble Molybdate Reactive Silicon, Determination of Phosphorus and Silicon Emission Spectrophotometry], 1992... 

Mild and reversible reduction of 1 12 and 2 18 heteropoly-molybdates and -tungstates produces characteristic and very intense blue colours ( heteropoly blues ) which find application in the quantitative determinations of Si, Ge, P and As, and commercially as dyes and pigments. The reductions are most commonly of 2 electron equivalents but may be of 1 and up to 6 electron equivalents. Many of the reduced anions can be isolated as solid salts in which the unreduced structure remains essentially unchanged and... 

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. 

Arsenites may also be determined by this procedure but must first be oxidised by treatment with nitric acid. Small amounts of antimony and tin do not interfere, but chromates, phosphates, molybdates, tungstates, and vanadates, which precipitate as the silver salts, should be absent. An excessive amount of ammonium salts has a solvent action on the silver arsenate. 

Molybdates yield sparingly soluble orange-yellow molybdyl oxinate with oxine solution the pH of the solution should be between the limits 3.3-7.6. The complex differs from other oxinates in being insoluble in organic solvents and in many concentrated inorganic acids. The freshly precipitated compound dissolves only in concentrated sulphuric acid and in hot solutions of caustic alkalis. This determination is of particular interest, as it allows a complete separation of molybdenum from rhenium. 

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. 

Molybdenum blue method. When arsenic, as arsenate, is treated with ammonium molybdate solution and the resulting heteropolymolybdoarsenate (arseno-molybdate) is reduced with hydrazinium sulphate or with tin(II) chloride, a blue soluble complex molybdenum blue is formed. The constitution is uncertain, but it is evident that the molybdenum is present in a lower oxidation state. The stable blue colour has a maximum absorption at about 840 nm and shows no appreciable change in 24 hours. Various techniques for carrying out the determination are available, but only one can be given here. Phosphate reacts in the same manner as arsenate (and with about the same sensitivity) and must be absent. 

Fluoride, in the absence of interfering anions (including phosphate, molybdate, citrate, and tartrate) and interfering cations (including cadmium, tin, strontium, iron, and particularly zirconium, cobalt, lead, nickel, zinc, copper, and aluminium), may be determined with thorium chloranilate in aqueous 2-methoxyethanol at pH 4.5 the absorbance is measured at 540 nm or, for small concentrations 0-2.0 mg L 1 at 330 nm. 

B. Phosphovanadomolybdate method Discussion. This second method is considered to be slightly less sensitive than the previous molybdenum blue method, but it has been particularly useful for phosphorus determinations carried out by means of the Schoniger oxygen flask method (Section 3.31). The phosphovanadomolybdate complex formed between the phosphate, ammonium vanadate, and ammonium molybdate is bright yellow in colour and its absorbance can be measured between 460 and 480 nm. 

Discussion. Small quantities of dissolved silicic acid react with a solution of a molybdate in an acid medium to give an intense yellow coloration, due probably to the complex molybdosilicic acid H4[SiMo12O40]. The latter may be employed as a basis for the colorimetric determination of silicate (absorbance measurements at 400 nm). It is usually better to reduce the complex acid to molybdenum blue (the composition is uncertain) a solution of a mixture of l-amino-2-naphthol-4-sulphonic acid and sodium hydrogensulphite solution is a satisfactory reducing agent. 

There also exists interference from diphosphoric acid, other more highly condensed phosphoric acids, and their organic derivatives. The free phosphoric acid can be determined as a heteropolyacid complex of phosphoric acid and ammonium molybdate. Afterward the complex is reduced by stannum II chloride to molybdenum blue. The amount of this dye can be measured photometricly at 625 nm. Organic derivatives of phosphoric acid and condensed phosphoric acids do not interfere with this method. 

Schieffer, G. W., Preliminary examination of a new post-column photolysis-molybdate reaction detection system for the determination of organophos-phorus compounds by high performance liquid chromatography, Instr. Sci. Technol., 23, 255, 1995. 

S2Og2- has been used to oxidize Ni2+(aq) in the presence of molybdate ion. The NiIV product obtained was crystallized as (NH4)6[NiMo9032]-6II20 and its crystal structure (determined independently by two groups) revealed a severely distorted octahedral 06 environment for the Ni atom, with an average Ni—O bond length of 1.876(5)A or 1.872(2)A.177,178... 

Isaeva [181] described a phosphomolybdate method for the determination of phosphate in turbid seawater. Molybdenum titration methods are subject to extensive interferences and are not considered to be reliable when compared with more recently developed methods based on solvent extraction [182-187], such as solvent-extraction spectrophotometric determination of phosphate using molybdate and malachite green [188]. In this method the ion pair formed between malachite green and phosphomolybdate is extracted from the seawater sample with an organic solvent. This extraction achieves a useful 20-fold increase in the concentration of the phosphate in the extract. The detection limit is about 0.1 ig/l, standard deviation 0.05 ng-1 (4.3 xg/l in tap water), and relative standard deviation 1.1%. Most cations and anions found in non-saline waters do not interfere, but arsenic (V) causes large positive errors. 

Yoshimura et al. [193] carried out microdeterminations of phosphate by gel-phase colorimetry with molybdenum blue. In this method phosphate reacted with molybdate in acidic conditions to produce 12-phosphomolybdate. The blue species of phosphomolybdate were reduced by ascorbic acid in the presence of antimonyl ions and adsorbed on to Sephadex G-25 gel beads. Attenuation at 836 and 416 nm (adsorption maximum and minimum wavelengths) was measured, and the difference was used to determine trace levels of phosphate. The effect of nitrate, sulfate, silicic acid, arsenate, aluminium, titanium, iron, manganese, copper, and humic acid on the determination were examined. 

Cambella and Antia [385] determined phosphonates in seawater by fractionation of the total phosphorus. The seawater sample was divided into two aliquots. The first was analysed for total phosphorus by the nitrate oxidation method capable of breaking down phosphonates, phosphate esters, nucleotides, and polyphosphates. The second aliquot was added to a suspension of bacterial (Escherichia coli) alkaline phosphatase enzyme, incubated for 2h at 37 °C and subjected to hot acid hydrolysis for 1 h. The resultant hot acid-enzyme sample was assayed for molybdate reactive phosphate which was estimated as the sum of enzyme hydrolysable phosphate and acid hydrolysable... 

Cembella et al. [40] have described a method for the determination of total phosphorus in seawater. The procedure used magnesium nitrate to oxidise organic compounds before standard molybdate colorimetric determination of ortho-phosphate. The method was applied to several pure organic phosphorus compounds and gave 93-100% recovery of phosphorus. 

Fujiwara et al. [94] found that, when present as a heteropolyacid complex, molybdenum(VI), germanium(IV), and silicon(IV) produced CL emission from the oxidation of luminol, and similar CL oxidation of luminol was observed for arsenic(V) and phosphorus(V) but with the addition of the metavanadate ion to the acid solution of molybdate. A hyphenated method was therefore proposed for the sensitive determination of arsenate, germanate, phosphate, and silicate, after separation by ion chromatography. The minimum detectable concentrations of arsenic(V), germanium(IV), phosphate, and silicon(IV) were 10, 50, 1, and 10... 

Because the preceding chromogenic assay rely on choline quantitation, the hydrolysis of substrates with headgroups other than choline cannot be followed. To circumvent this problem, another useful protocol was devised whereby the phosphorylated headgroup produced by the PLCBc hydrolysis is treated with APase, and the inorganic phosphate (Pi) that is thus generated is quantitated by the formation of a blue complex with ammonium molybdate/ascorbic acid 5 nmol of phosphate may be easily detected. This assay, which may also be performed in a 96-well format, has been utilized to determine the kinetic parameters for the hydrolysis of a number of substrates by PLCBc [37,38]. 

An excellent example of this type of analysis involves the determination of phosphate in soil extracts. Soil is extracted with an appropriate extractant and added to a solution of acid molybdate, with which the phosphate reacts to produce a purple- or blue-colored solution of phosphomolybdate. Standard phosphate solutions are prepared, reacted with acid molybdate, and the intensity of the phosphomolybdate color produced is measured. A standard curve (also called a calibration curve) is prepared (see Section 14.10) from which the intensity of the color is directly related to the concentration of phosphate in the extract. 

Thermochemical investigations of molybdate solutions have been carried out and reaction heats were measured (108,109). As the interpretation of calorimetric data depends heavily on the correct reaction model, progress in determining reliable enthalpy and entropy changes for condensation reactions have been hampered. However, since there is little doubt that [M07O24]6 is the first polyanion which forms on acidification, the enthalpy and entropy changes obtained for its formation should be meaningful. The values for Eq. (30) are AH° =... 

The veiy large Mo36 polyanion is crystallized at very low pH (Z —1.8 to 2) (116). The structure of the potassium salt Kg[Mo360112(H20)16] 36H20 has been determined by X-ray crystallography. It actually consists of two 18-molybdate subunits which combine via four common oxygen atoms (116b). 

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