Determination of molybdate

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... 

For many scientists involved in the analysis of phosphorus in water, sediment and soil, the only available techniques depend on the colorimetric determination of molybdate-reactive phosphorus, and that which can be made reactive during a digestion step. Molybdate-reactive phosphorus in filtered samples is generally equated to inor-... 

Table 1 Specification scheme for phosphorus (P) based on determination of molybdate reactive (R), phosphorus in total (T), filterable (F), and particulate (P) forms O and C designate organic and condensed forms, respectively...

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). 

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... 

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... 

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. 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. 

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. 

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... 

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 automated spectrophotometric procedure [47] for the determination of total nitrogen in soils discussed in section 12.5.1.2 has also been applied to the determination of 0-0.75% phosphorus in soils. The method is based on the formation of the yellow molybdate-vanadate complex which has an absorption maximum at 420nm. 

Olsen et al. [62] have described a method for the determination of pH8.5 sodium bicarbonate extractable phosphorus in soils. The concentration of the blue complex produced by the reduction, with ascorbic acid, of the phosphomolybdate formed when acid ammonium molybdate reacts with phosphate is measured spectrophotometrically at 880 nm [63]. 

The determination of the orthophosphate was carried out by using the automated systems described by the Technicon Instruments Corporation. The manifolds used are shown in Fig. 12.3. The procedures referred to below as methods I and II are Technicon industrial methods Nos. 94-70W and 155-71W, respectively. Method I includes ascorbic acid alone for the reduction of the molybdophosphoric acid whereas in method II the mixed reagents ascorbic acid, sulphuric acid, ammonium molybdate and antimony potassium tartrate are used. Method I is intended for use for high levels of phosphorus (up to lOpg ml4) and method II for low levels (less than 0.5pg ml4). The wetting agent (Levor IV) used in order to obtain a smooth bubble pattern, is present in the ascorbic acid reagent line for method I whereas it is added externally Fig. 12.3) in the water line (0.5pg ml4 of Levor) in method II. 

Solyom has conducted an intercalibration of methods used for the determination of phosphorus in sludges [37]. The methods used to determine phosphorus were that of Koroleff [83] in which the sample is digested with potassium peroxydisulphate and phosphate determined spectro-photometrically. Alternatively a reducing Kjeldahl digestion was used followed by determination of phosphate using molybdate and ascorbic acid. The former method gives somewhat low results. The reducing Kjeldahl method is therefore recommended. 

Allen, R. J. L. (1940). Micro-determination of phosphorus. (Colorimetric estimation molybdate blue.) Biochem. J. 34, 858. Bellamy, L. J. (1954). Infra-red Spectra of Complex Molecules. Methuen and Co. 

Astheimer and Schwochau have applied the voltametry method to the determination of low technetium concentrations in the presence of molybdate and perrhenate ions. Using a Kemula electrode technetium is concentrated on a mercury drop from alkaline solution of 6.0 x 10 M KTcO by electrolysis at a potential of — 1.0 V vs. SCE. Anodic stripping in 1 M NaOH yields a characteristic stripping curve (Fig. 14). The height of the peak at —0.33 V is proportional to the concentration of technetium in the range of 10 to 3 x 10 M. Technetium can be detected with an accuracy of +4%. The determination of 0.5 ng of technetium in a 10 fold molar excess of ReO or MoO is possible. 

Procedure (determination of inorganic phosphate (a) in the acetic acid extract). The 8-hydroxyquinoline forms a precipitate in acidic ammonium molybdate solution, which will interfere unless the aliquot is <5 ml. It should therefore be removed by ignition as follows. Transfer 10 ml acetic acid extract to a 45-ml silica basin, add 0.5 ml 1 M magnesium acetate and evaporate to dryness on a water-bath. (Note do not use magnesium nitrate, which reacts adversely on heating with 8-hydroxyquinoline.)... 

Reactions based on the presence of the 21-hydroxy-20-keto functionality (ketol group) are much more specifie for corticosteroids, and these methods have been used for the determination of corticosteroids in pharmaceutical formulations or in biological fluids [72]. For instance, only 21-unesterified corticosteroids react with sodium molybdate in acetic acid medium [81]. The blue color obtained by reducing the ketol group allows the determination of 40-200 pg of these steroids. 

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