Molybdenum spectrophotometric determination

A reaction of mixed molybdenum polyoxometalates (POMs) with cyanine dye has been used for highly selective and sensitive spectrophotometric determination of phosphorus(V) and arsenic(V). Color of the solution is considerably changed by reaction of Keggin POMs with styrene cyanine dyes. Derivatives of l,3,3-threemethyl-3//-indol - astrazone violet (AV 3R), astrazone rose, astrazone yellow, astrazone red were investigated. 

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. 

Nutaksuka et al. [501] converted molybdenum to its molybdenum-phenyl-fluorone complex, then extracted the complex on a membrane filter prior to spectrophotometric determination on the membrane. 

An adsorbing colloid formation method has been used to separate molybdenum from seawater prior to its spectrophotometric determination by the thiocyanate procedure [517]. 

Extraction and Spectrophotometric Determination of Molybdenum (VI) using 3-Hydroxy-2-[-3-(4-methoxyphenyl)-l-phenyl-4-pyrazolyl]-4-oxo-4H-l-benzopyran as a Chelating Agent... 

The strong absorptions of the complex technetium (IV) hexahalides (Fig. 10) can also be utilized for spectrophotometric determinations. A sensitive method has been developed using hexachlorotechnetate (IV) When pertechnetate is heated for 50- 0 min in cone, hydrochloric acid, it is reduced to the complex [TcClgp . The absorption curve of [TcClgf in cone. HCl has a maximum at 338 nm where technetium can be determined in the presence of microgram amounts of rhenium or molybdemun. The molar extinction coefficient is said to be 32.000 (after Jorgensen and Schwochau it amounts to 10.600). About 0.1 fig Tc/ml can be determined. Rhenium present in quantities up to 30 ng/ml has almost no influence on the determination of technetium. The error in the determination of the latter in the presence of molybdenum at a weight ratio of 1 1 is 1-2%. 

Won, Ck. H. Sensitive Spectrophotometric Determination of Submicrogram Amounts of Orthophosphate in Natural Water by a Modified Molybdenum(V)-thiocyanate Method. J. Chem. Soc. Japan, Pure Chem. Sect. 85, 859 (1964). 

Molybdenum is determined by a spectrophotometric procedure involving the reaction of molybdenum with dithiol and evaluation of the carbon tetrachloride complex at 680 nm. 

D4. David, D. J., Atomic absorption spectrophotometric determination of molybdenum and strontium. Nature 187, 1109 (1960). 

If higher sensitivities are desired then the ammonium phosphomolybdate product may be reduced with stannous chloride or ascorbic acid in order to give soluble molybdenum blue [24]. Spectrophotometric determination of the blue absorbance at 885 nm gives a detection limit of 0.003 mg/L phosphate, stated as phosphorus (3 ppb in freshwater) or 0.0092 mg/L as expressed phosphate [24]. 

For flow analysis incorporating electrolytic dissolution, very small characteristic masses, often below the ng level, are reported for metal determinations. This is a consequence of the analytical sensitivity and the small sample volume required, and is an attractive feature of in-line electrolytic dissolution. As a very small dissolved mass is required, rapid electrolysis (a few seconds) under a moderate current (mA) is sufficient. This was demonstrated in the flow-based spectrophotometric determination of aluminium in steels [29]. The analyte was oxidised and dissolved in a flowing acidic electrolytic solution that also acted as the sample carrier stream of the flow analyser. This innovation was further applied to the spectrophotometric determination of molybdenum in alloys [30]. In both applications, the anode was the polished metallic sample, and the cathode was a gold or silver coated electrode placed at the bottom of the electrolytic chamber (Fig. 8.4). A silicone rubber sheet (adapter) was placed between the solid sample and the chamber walls in order to avoid leakage and to define the sample surface area to be dissolved. This classical geometry is the most commonly used. 

Placement of the mini-column prior to the sample introduction port can also be useful in unsegmented flow analysis, as demonstrated in the flow injection spectrophotometric determination of molybdenum in plant digests [236]. This method relied on the influence of molybdate anions on the rate of iodide oxidation by hydrogen peroxide under acidic conditions, and some potential interfering cations needed to be separated. To this end, a cation-exchange resin mini-column was attached to the central sliding bar of an injector-commutator hence, it could be displaced between two different streams. Initially, the sample solution was pumped... 

H. Bergamin-Filho, F.J. Krug, B.F. Reis, J.A. Nobrega, M. Mesquita, I.G. Souza, On-line electrolytic dissolution of alloys in flow injection analysis. Part 2. Spectrophotometric determination of molybdenum in steels, Anal. Chim. Acta 214 (1988) 397. 

A.P.G. Gervasio, P.R. Fortes, S.R.P. Meneses, C.E.S. Miranda, E.A.G. Zagatto, An improved flow-injection system for spectrophotometric determination of molybdenum and tungsten in tool steels, Talanta 69 (2006) 927. 

Spectrophotometric determination. In the sample of the dust fall-out, silicon dioxide is transformed into a solution by melting with a mixture NaHC03 -f NaCl. The silicic acid formed yields Molybdenum Blue by reaction with ammonium molybdate and the concentration is determined by spectrophotometric measurements. The portion of amorphous silicon dioxide is dissolved by boiling with NaOH solution and the determination is performed in the same way as mentioned above [18]. 

Spectrophotometric determination as a molybdophosphate complex (phosphorus molybdenum blue)... 

Spectrophotometric determination is performed using UV-visible spectrophotometry with formation of yellow saturated silicomolybdate. The method is used normally for determination of 0.002-1 mg of Si02- For greater sensitivity (for 0.0001-0.25 mg of SiOz), the yellow silicomolybdate may be reduced with sodium sulfite or a mixture of citric and ascorbic acids (the solution must contain 5% citric acid and 1% ascorbic acid) to the corresponding silico-molybdenum blue. 

Spectrophotometric determination of molybdenum can be accomplished by reaction with thiocyanate in an acid medium in the presence of tin(II) chloride (465 nm). Toluene-3,4-dithiol, usually referred to as dithiol, can also be used as a spectrophotometric reagent for molybdenum determination. In an acid medium, it forms a green complex that can be extracted using organic solvents. 

Thiophen Derivatives of Analytical Interest.—2-Thenoyltrifluoroacetone has maintained its position as a chelating agent in analytical chemistry. Papers describing its use in the extraction or determination of thorium, copper, europium, thallium, niobium, and molybdenum have appeared. The effect of copper(n) on the formation of monothenoyltri-fluoroacetonatoiron(iii) has been studied. The stability constants of some bivalent metal chelates of di-(2-thenoyl)methane have been determined. 3-Thianaphthenoyltrifluoroacetone has been proposed as a reagent for the spectrophotometric determination of iron(iii) and cerium(iv). The stabilities of metal chelates formed from derivatives of thiophen-2-aldehyde and of rare-earth carboxylates of thiophen-2-carboxylate have been studied. 

Another example is a fully computerized MSFIA system for the spectrophotometric determination of available phosphorus in soil extracts. The molybdenum blue method is chosen for the colorimetric determination, using ascorbic acid as reducing agent, antimony to accelerate the reduction to the blue complex and applying the Egner-Riehm method to extract phosphorus from soil samples. It presents a hnear calibration curve between 0.75 and 15 mg/1. A determination frequency of 15/h may be achieved, with good repeatability for 12 consecutive injections of soil extracts (RSD <1.7%). Results obtained from 12 soil samples were statistically comparable to those attained by the usual batch method [102]. 

SIA system for the spectrophotometric determination of phosphate and silicate in environmental samples using the molybdenum blue reaction. HC holding coil RC reaction coil SV selection valve. 

F. Mas-Torres, J.M. Estela, M. Miro, A. Qadera, V. Cerda, Sequential injection spectrophotometric determination of orthophosphate in beverages, wastewaters and urine samples by electrogeneration of molybdenum blue using tubular flow-through electrodes. Anal. Chim. Acta 510 (2004) 61-68. 

C.X. Galhardo, J.C. Masini, Spectrophotometric determination of phosphate and silicate by sequential injection using molybdenum blue chemistry. Anal. Chim. Acta 417 (2000) 191-200. 

Sugawara, K. and Kanamori, S., Spectrophotometric determination of submicromolar quantities of orthophosphate in natural waters. Bulletin of the Chemical Society of japan 34,526,1961. Sjosten, A. and Blomqvist, S., Influence of phosphate concentration and reaction temperature when using the molybdenum blue method for determination of phosphate in water. Water Research 31,1818,1997. 

Zaugg, W.S. and Knox, R.J., Indirect determination of inorganic phosphate by atomic absorption spectrophotometric determination of molybdenum. Analytical Chemistry 38,1759,1966. 

Spec A = 665 nm of the titanium-methylene blue-ascorbic acid redox reaction Spec A= 420 nm of the yellow Tiron derivative (pH = 5.2 to 5.6) Spectrophotometric determination of tungsten with thiocyanate after both tungsten(VI) and molybdenum(VI) are extracted into chloroform as benzoin a-oxime complexes... 

USE For spectrophotometric determination of various metals copper [7493,7494], molybdenum [7495] or vanadium [7496]. 

Spectrophotometric determination of phosphate by the molybdenum blue method... 

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). 

Phosphorus from organophosphorus compounds, which are combusted to give mainly orthophosphate, can be absorbed by either sulphuric acid or nitric acid and readily determined spectrophotometrically either by the molybdenum blue method or as the phosphovanadomolybdate (Section 17.39). 

The following procedure has been recommended by the Analytical Methods Committee of the Society for Analytical Chemistry for the determination of small amounts of arsenic in organic matter.20 Organic matter is destroyed by wet oxidation, and the arsenic, after extraction with diethylammonium diethyldithiocarbamate in chloroform, is converted into the arsenomolybdate complex the latter is reduced by means of hydrazinium sulphate to a molybdenum blue complex and determined spectrophotometrically at 840 nm and referred to a calibration graph in the usual manner. 

A circular TLC spectrophotometric method for the determination of lanthanum and yttrium at concentration level of 0.01 to 1.0% in molybdenum-based alloys has also been developed. It involves the separation of lanthanum and yttrium on cellulose layers impregnated with 0.2-Mtrioctylamine using aqueous HCl as developer, extraction from sorbent layer, and determination by spectrophotometry [69]. 

A commonly used procedure for the determination of phosphate in seawater and estuarine waters uses the formation of the molybdenum blue complex at 35-40 °C in an autoanalyser and spectrophotometric evaluation of the resulting colour. Unfortunately, when applied to seawater samples, depending on the chloride content of the sample, peak distortion or even negative peaks occur which make it impossible to obtain reliable phosphate values (Fig. 2.7). This effect can be overcome by the replacement of the distilled water-wash solution used in such methods by a solution of sodium chloride of an appropriate concentration related to the chloride concentration of the sample. The chloride content of the wash solution need not be exactly equal to that of the sample. For chloride contents in the sample up to 18 000 mg/1 (i.e., seawater),... 

Johnson and Pilson [229] have described a spectrophotometric molybdenum blue method for the determination of phosphate, arsenate, and arsenite in estuary water and sea water. A reducing reagent is used to lower the oxidation state of any arsenic present to +3, which eliminates any absorbance caused by molybdoarsenate, since arsenite will not form the molybdenum complex. This results in an absorbance value for phosphate only. 

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