Extraction and spectrophotometric determination of vanadium as a mixed ligand complex of oxine and azide

Summary Vanadium, oxine and azide react at pH 3.5–4.5 to give a dark green solid which extracts into benzene giving dark green solution. The extract has absorption maxima at 415 nm and 620 nm with molar absorptivities 8650 and 6040 respectively. Spectrophotometric investigations reveal that the extracting species has V, HOx and N₃ ^– in the ratio 122. Beer's law is obeyed upto 8.10g and 10.50g of vanadium per ml at 415 nm and 620 nm respectively. The formation constant and the free energy of formation are 8.5 ± 0.2×10⁶ and –9.61±0.30 Cal respectively at 30°. The interference of various foreign ions are studied and methods are proposed for the elimination of the interference of some of those substances. Infrared and magnetic data of the solid complex are given.

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Zusammenfassung Vanadin, Oxin und Azid reagieren bei pH 3,5–4,5 zu einem dunkelgrünen Feststoff, der sich mit Benzol als dunkelgrüne Lösung extrahieren läßt. Deren Absorptionsmaxima liegen bei 415 und 620 nm mit den molaren Extinktionen von 8650 bzw. 6040. Spektrophotometrisch ergibt sich das Verhältnis V:HOx: N₃ ^–=122. Bis 8,10 bzw. 10,5g V hat das Beersche Gesetz Gültigkeit. Die Komplexkonstante beträgt 8,5 ± 0,2×10⁶, die Bildungswärme –9,61±0,3 Kcal bei 30° C. Die Störung durch verschiedene Fremdionen wurde geprüft und in einigen Fällen beseitigt. IR- und magnetische Daten für die feste Komplexverbindung werden angegeben.

     

2-Oximinodimedone monoguanylhydrazone as spectrophotometric reagent for determination of iron

The synthesis, properties and analytical possibilities of 2-oximinodimedone monoguanylhydrazone as spectrophotometric reagent have been examined. A new method for the determination of iron has been developed in a concentration range varying from 0·2–5·0 ppm of iron; the molar absorptivity is 1·1×10⁴ litres mol⁻¹ cm⁻¹ at 600 nm and the relative error is ±0·3%. The method has been applied satisfactorily to the determination of iron in different inorganic samples.     

Flow procedure for ion-exchange preconcentration and on-line spectrophotometric determination of iron(III) as its thiocyanate complex

On-line ion-exchange preconcentration of iron(III) on a conventional cation exchange resin with spectrophotometric detection based on thiocyanate complexation is described. The calibration graph is linear over the range 0.01–0.2 g ml^–1 and the detection limit (3 ) is 6 ng ml^–1 for a 6-ml sample. No interference effects were detected. The recovery of iron from the resin is 95%. 12 samples h^–1 can be analysed.     

Extraction—spectrophotometric determination of traces of antimony as the ferroin—hexachloroantimonate(V) complex

The sparingly soluble scarlet precipitate formed by the interaction of ferroin and antimony(V) in strong hydrochloric acid medium is soluble in nitrobenzene. The composition of the complex is [Fe(phen)₃] [SbCl₆]₂. The percentage extraction into nitrobenzene, determined by tracer techniques, reaches a maximum (98%) at 8–9 M hydrochloric acid. The advantages of this procedure over those employing dyes as reagents are discussed. Antimony(V) can be determined in the range 2.5–24μg ml^-1. Interferences are described.     

Spectrophotometric and derivative spectrophotometric determination of iron by extraction of the iron(II)-TPYZ-picrate ion-association complex

A solvent extraction-spectrophotometric determination of microamounts of iron has been developed, based on the formation of an ion-association complex of iron(II) with 2,4,6-tris(2'-pyridyl)-1,3,5-triazine as primary ligand and picrate as counter-ion, which is extracted into 1,2-dichloroethane. The complex is formed at pH 4.0-7.0 and the iron concentration can be determined by measuring the absorbance directly in the organic phase. The apparent molar absorptivity is 2.2 x 10(5) l.mole(-1).cm(-1). As the method is practically free from interferences it was applied to the determination of iron in different biological and inorganic samples. Although the proposed method is very sensitive it can be further sensitized by employing the derivative spectrophotometric technique.     

Indirect spectrophotometric determination of thiocyanate by extraction as bisthiocyanatobisquinolinemercury(II) complex and its ligand substitution reaction with dithizone

Thiocyanate forms with mercury(II) in the presence of quinoline a mixed-ligand mercury(II) complex, bisthiocyanatobisquinolinemercury(II), and is extracted into chloroform. This mixed-ligand complex is treated with dithizone and forms the bisdithizonatomercury(II) complex. Maximum and constant absorbance of the dithizone complex is obtained when thiocyanate is extracted at pH 5.1-6.5, and Beer's law is obeyed at 498 nm, where the difference in absorbance between the dithizone complex and dithizone is largest. Chloride, bromide, iodide, cyanide and large amounts of ammonium and copper(II) ions interfere.     

Extractive spectrophotometric determination of molybdenum as a thiocyanate-2-acetylpyridinethiosemicarbazone complex

A new spectrophotometric method for the determination of molybdenum is based on the extraction of the orange red molybdenum thiocyanate-2-acetylpyridinethiosemicarbazone complex into chloroform from hydrochloric acid. The complex has an absorption maximum at 470 nm with a molar absorptivity of 1.7 × 10⁴ liters mol^?1 cm^?1. Beer's law is valid from 0.1 to 6.5 ppm of molybdenum. The equilibrium shift method indicated a 1:4:2 complex. The method has been used successfully for the determination of molybdenum in molybdenum steels.     

Extraction and spectrophotometric determination of cobalt with dithizone

Cobalt(II) in acetate-tartrate buffer (pH 6.0-7.3) is extracted quantitatively as cobalt(III) dithizonate with excess of dithizone in CCl(4). The molar absorptivity in the CCl(4) phase is 4.6 x 10(4) 1.mole(-1).cm(-1) at the absorption maximum 550 nm. The calibration graph is linear for 1-10 mug of cobalt in 10 ml of CCl(4) when excess of dithizone is removed by back-extraction with 0.01M aqueous ammonia. Most interferences can be overcome by (a) initial extraction with dithizone at pH 1.3, (b) selective back-extraction into hydrochloric acid (pH 1 to 2), (c) oxidation of iron and tin to iron(III) and tin(IV) and addition of fluoride to complex the former, and (d) selective reaction of nickel dithizonate with 1,10-phenanthroline in the CCl(4) phase followed by back-extraction of nickel into 0.1M acid. The method has been applied to determination of cobalt in a copper-nickel-zinc alloy and a nimonic alloy.     

Extraction—spectrophotometric determination of trace amounts of iron in waters with pyrogallol red and zephiramine

The simple removal of excess of co-extracted reagent in the solvent extraction of metal complex anions with a quaternary ammonium salt greatly improves the determination of iron(II) with pyrogallol red and zephiramine. The method with pyrogallol red is suitable for the determination of trace amounts of iron in natural waters. The apparent molar absorptivities of the iron(II) complex in chloroform are 7.5×10⁴ and 10.3×10⁴ 1 mol^-1 cm^-1 at 560 and 298 nm, respectively. A large excess of reagent can be added, and the ternary complex can be completely extracted over the pH range 8.5–10. Masking agents allow most interferences to be suppressed. The method is suitable for the analysis of potable, river and sea waters.     

Diformylhydrazine as analytical reagent for spectrophotometric determination of iron(II) and iron(III)

The bidentate ligand diformylhydrazine (OHC-HN-NH-CHO), DFH, combines with iron(II) and iron(III) in alkaline media in the pH range 7.3-9.3 to form an intensely colored red-purple iron(III) complex with an absorption maximum at 470 nm. Beer's law is obeyed for iron concentrations from 0.25 to 13 microg mL(-1). The molar absorptivity was in the range 0.3258x10(4)-0.3351x10(4) L mol(-1) cm(-1) and Sandell's sensitivity was found to be 0.0168 microg cm(-2). The method has been applied to the determination of iron in industrial waste, ground water, and pharmaceutical samples.     

Extraction and flame spectrophotometric determination of palladium and rhodium

Solvent extraction methods involving toluene, chloroform, 4-methyl-2-pentanone and pentyl acetate were studied for palladium and rhodium chelates. The palladiurn-salicylaldoxime chelate was extracted quantitatively into 4-methyl-2-pentanone at pH 3. The rhodium-diethyldithiocarbamate chelate was completely extracted into 4-methyl-2-pentanone at pH 8. The optimum combustion conditions for each of the organic extracts were then studied. The position of maximum emission intensity in the flame mantle was determined for each chelate and solvent system ; readings were taken at 363.5 mμ for palladium, and 369.2 mμ for rhodium. For palla-dium, when 4-methyl-2-pentanone was used instead of water as solvent, the emission intensity increased 21-fold. For rhodium, this kctone increased the sensitivity 27 times compared with water. A method is suggested for the separation and determination of palladium and rhodium in the same sample.     

The spectrophotometric determination of iron(III) in a flow-injection system with a mixed solvent

A fast and sensitive flow-injection procedure is described for the determination of iron(III). The complexing agent is ammonium diisopropyldithiophosphate in a 1:1 (v/v) isopropanol/water carrier stream. The linear range is 0.05–15 mg 1^?1 iron(III) with a detection limit of 0.01 mg 1^?1 and the injection rate is about 400 h^?1.     

Simple and rapid spectrophotometric determination of iron after preconcentration as its 1,10-phenanthroline complex on the natural polymer "chitin"

Preconcentration by collection of metal complexes on chitin has been applied to the spectrophotometric determination of iron in water. The iron is collected as its 1,10-phenanthroline (phen) complex on a column of chitin in the presence of tetraphenylborate as counter-ion. The iron(II)-phen complex retained on the chitin is eluted with an acetone-1M acetic acid mixture (8:2 v/v), and the absorbance of the eluate is measured at 512 nm. Beer's law is obeyed over the concentration range 1.1-11.2 mug of iron in 10 ml of eluate. In the presence of EDTA as masking agent, Ca, Mg, Al, Mn, Zn, Cd and Pb do not interfere in concentrations up to 100 times that of iron(II) and Co, Ni and Cu do not interfere in concentrations up to 20 times that of iron(II). Common inorganic anions do not interfere in concentrations up to 10,000 times that of iron(II). The proposed method has been applied to determination of iron in tap water.     

Direct spectrophotometric determination of iron in non-ferrous alloys

Disodium 3-(2-pyridyl)-1,2,4-triazine-5,6-di(4'-phenylsulphonate) is used for determination of iron in metal analysis. High selectivity is achieved by using a ligand buffer and substoichiometric masking. Interference from 0.9 mg of Cu(II) can be completely eliminated by combined reduction and masking with ascorbic acid and thiosemicarbazide. Beer's law is obeyed over the range 0.4-1.6 mug/ml iron in the final solution, with a standard deviation of 0.02 mug/ml. The method has been successfully applied to determination of iron (without preseparation) in a number of non-ferrous metals and alloys, with a coefficient of variation of 1.2-5.0%.