The determination of thiols with diphenylpicrylhydrazyl as a spectrophotometric reagent

Diphenylpicrylhydrazyl (DPPH), a stable, intensely purple free radical, is used as a reagent in the quantitative determination of various aromatic and aliphatic thiols by indirect spectrophotometric analysis. Plots of degree of reaction vs. time show that thiophenol and its derivatives react more quickly than aliphatic thiols with DPPH. Calibration plots are linear over the concentration range 0.05-3.00 x 10(-5)M thiol. The average relative error is in the range 1-2% and the absolute standard deviations range up to 0.50 x 10(-6)M.     

Morin as a spectrophotometric reagent for gold

A reaction of morin with gold(III) in a hydrochloric acid medium has been studied. A redox reaction occurring in the examined system has been identified. The oxidized form of morin (λ_max at 291 nm), being the product of the reaction, has been used as the basis of the spectrophotometric method for the determination of gold. Gold can be determined in the concentration range of 0.2–12 μg mL⁻¹ (RSD in the range of 0.89–2.38%). The molar absorptivity at 291 nm is equal to 2.02 × 10⁴ L mol⁻¹. cm⁻¹. The developed method was applied to the determination of gold (0.04%) in a cosmetic cream. Published in Russian in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 2. pp. 129–133. The text was submitted by the authors in English.     

The spectrophotometric determination of gold with bromopyrogallol red

Optimum conditions were found for the reaction of Au(III) with bromopyrogallol red and a new spectrophotometric determination of Au(III) ions was developed. At a wavelength of 400 nm the Lambert-Beer law is followed in a range of 0.1 to 3.0 μg Au ml^?1 and the absorption coefficient ? = 3 × 10⁴M^?1 cm^?1. The effect of cationic tensides on the studied reaction was also studied; it was found that in their presence the properties of the system are strongly affected by the ionic strength of the solution. The changes observed are a result of the effect of the ionic strength on the dissociation constant of the DG-tenside system.     

Gravimetric and spectrophotometric determination of hexafluoroantimonate with tetraphenylarsonium chloride, nitron and ferroin

Two methods are described for the gravimetric determination of the hexafluoroantimonate anion with tetraphenylarsonium chloride and nitron as precipitants. In addition, a spectrophotometric method for this anion with ferroin as reagent is described. Hydrolysis of the anion is avoided by using stock solutions of KSbF(6) in N,N-dimethylformanude and adding these directly to concentrated aqueous solutions of the analytical reagent. Interference studies are included on a number of anions.     

Indirect spectrophotometric determination of borate using nitron as reagent

An indirect method is outlined for the spectrophotometric determination of small amounts of borate. Borate is quantitatively precipitated as nitron tetrafluoborate in the presence of excess nitron. After separating off the precipitate, the excess of reagent is determined in the supernatant liquid as nitron cobaltothiocyanate.     

Indirect spectrophotometric determination of perchlorate using nitron as reagent

An indirect method is outlined for the spectrophotometric determination of small amounts of perchlorate. Perchlorate is quantitatively precipitated as nitron perchlorate in the presence of excess nitron. After separating off the precipitate, the excess reagent is determined in the supernatant liquid as nitron cobaltothiocyanate. The latter compound is extracted in 30% cyclohexanone in carbon tetrachloride and the absorbance of the extract measured at 625 nm. The method is simple, reproducible, and accurate to ±1%. The interferences of other anions were also investigated.     

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.     

Arsenazo III as a spectrophotometric reagent for determination of lead

Arsenazo III is proposed as a spectrophotometric reagent for the determination of lead. The complex formation begins at pH > 2 and is greatest at pH 4-6. The molar absorptivity of the complex has a mean value of 2.8 x 10(4) 1.mole(-1).cm(-1) at 600 nm and remains nearly constant in the pH range 4-8. The ionic species taking part in the reaction are studied and the equilibrium constants for the different possible reactions are calculated. According to the values obtained, the reaction of PbOH(+) with H(5)L(3-) is predominant. The reaction studied is applied for the determination of micro amounts of lead in technical aluminium.     

Indirect spectrophotometric determination of palladium using 1,10-phenanthroline as reagent

Summary The spectrophotometric method for the determination of palladium is based upon the addition of a standard 1,10-phenanthroline solution to precipitate Pd(phen)Cl₂ and the determination of 1,10-phenanthroline concentration of the supernatant solution. The absorbancy readings were made in the absorption maximum at about 271 nm, in the concentration range of 10^–6 to 10^–5M 1,10-phenanthroline in 0.1 M hydrochloric acid and 0.1% hydroxylamine hydrochloride. For the phenanthroline system Beer's law is valid. Ions which either form with phenanthroline very strong complexes or interfere with the spectrophotometric determination of 1,10-phenanthroline must be absent. The method is simple, rapid, accurate and applicable to the macro and micro-determination of palladium in different systems. Standard deviation was found to be 0.085 ppm (in pure Pd solutions).

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Indirekte spektrophotometrische Bestimmung von Palladium mit 1,10-Phenanthrolin

Zusammenfassung Das Verfahren beruht auf der Fällung von Pd(phen)Cl₂ durch Zusatz einer bestimmten Menge Standard-1,10-Phenanthrolinlösung und spektrophotometrischer Bestimmung des Überschusses.Die Messungen werden bei dem Absorptionsmaximum bei etwa 271 nm und einer Konzentration von 10^–6M bis 10^–5M 1,10-Phenanthrolin in 0,1 M HCl und 0,1% Hydroxylaminhydrochlorid enthaltender Lösung durchgeführt. Das 1,10-Phenanthrolinsystem folgt dem Beerschen Gesetz. Ionen, die entweder mit 1,10-Phenanthrolin starke Komplexe bilden oder die spektrophotometrische Bestimmung von 1,10-Phenanthrolin beeinflussen, müssen abwesend sein. Die Methode ist einfach, rasch und genau und kann für Mikro- und Makrobestimmungen in verschiedenen Systemen angewendet werden. Die Standardabweichung beträgt 0,085 ppm (in reinen Pd-Lösungen).

     

1,2,4,6-Tetraphenylpyridinium perchlorate as a reagent for ion-association complex formation and its use for the spectrophotometric determination of gold

The synthesis, characteristics, and applications of 1,2,4,6-tetraphenylpyridinium perchlorate (TPPP) as an agent that forms ion-association complexes is described. This new spectrophotometric analytical reagent forms with AuCl₄^?1 a 1:1 complex which is slightly soluble in water and can be extracted with isopentyl acetate, with maximum absorbance 313 nm, molar absorptivity 3.44 × 10⁴ liters mol^?1 cm^?1. The variables involved in the formation and extraction of the complex in the mentioned organic solvent are studied. In the selected conditions, 1 M hydrochloric acid medium, the extraction efficiency was 95.3%. The apparent stability constant of the complex is log K = 5.9 ± 0.1 at 20 °C. The extracted complex is useful for the spectrophotometric determination of gold in the range of 0.05 to 0.5 ppm. Standard deviation at 0.2 ppm (10 determinations) was 0.0022 and the relative error was ±0.78%.The interferences of many foreign ions are studied, concluding that the procedure proposed shows a high selectivity.The method has been applied satisfactorily to the determination of gold in ores, leads and other materials.     

Potassium ferrocyanide as a spectrophotometric reagent for the determination of uranium

Potassium ferrocyanide gives a colour reaction with U(VI), which is suitable for its determination. The complex absorbs in the wavelength range of 390–397 nm. The optimum pH range for colour development was 1.5–3.5. The molar absorptivity was found to be 4.65·10³ 1·mol^–1·cm^–1. Most of the anions up to 1000 g did not interfere. The method was made selective by extracting U(VI) first with DOSO from the mixture of interfering cations from 1–2M HNO₃ medium and then determining uranium in the back-extracted solution by developing the colour with ferrocyanide. 20 g/10 ml of U(VI) in the final solution could be satisfactorily determined within an RSD of ±2%.     

Guaiacol as a new reagent for the spectrophotometric determination of uranium

Guiacol, i.e. o-hydroxyanisole, gives a distinct color reaction with U(VI) suitable for spectrophotometric determination of the metal. The complex formed in the reaction has an absorption maximum at 352 nm. Optimum pH for the color development ranges from 6.5 to 8.5. The molar absorptivity and Sandell's sensitivity of the method were found to be 3.75×10³ l·mol^–1·cm^–1 and 0.063 g·cm^–2, respectively. Many anions and cations do not interfere up to 100 ppm. The method has been made very specific by selective extraction of U(VI) with TBP from a mixture of different cations and anions in the presence of 60% NH₄NO₃ as salting out agent followed by developing the color in the non-aqueous phase by adding quaiacol in methanol at pH 6.5 to 8.5 An amount as low as 30 g of uranium (VI) per 10 ml of the solution could be satisfactorily determined with an RSD of ±2.0%. The method was applied to rock samples after U(VI) had been extracted from a sample solution into 25% TBP in hexane. Results obtained by the new method compare very well with those of conventional fluorimetric and radiometric assays. The features of the method include excellent precision, rapidity, good selectivity, and ease of performance.     

Resorcinol as an analytical reagent for the spectrophotometric determination of uranium

A spectrophotometric study of the reaction of uranyl acetate and resorcinol shows that an orange-red coloured resorcinolate of composition 1:2 is formed. This colour reaction can be conveniently used for the spectrophotometric estimation of uranium at PH 4.72.     

5-(4-Carboxylphenylazo)-8-aminoquinoline as an analytical reagent for the spectrophotometric determination of gold

The synthesis and analytical application of 5-(4-carboxylphenylazo)-8-aminoquinoline (CPAQ) are described. A simple, rapid, selective, and sensitive spectrophotometric method for the determination of microgram amounts of gold is developed, based on the colour reaction between the metal ion and CPAQ in the presence of cetyltrimethyl ammonium bromide. Gold (III) reacts with the reagent in the ratio 1 3 (metal to ligand) in alkaline solution to form a blue-green complex with an absorption maximum at 608 nm. Beer's law is obeyed over the concentration range 0–1.8 g · ml^–1 (ppm) of gold. The molar absorptivity and Sandell's sensitivity of the method are 9.11 × 10⁴ l · mole^–1 · cm^–1 and 0.00216 g · cm^–2, respectively. The interference of various ions has been studied and conditions were developed for the determination of gold in an ore and anode slimes.     

Sensitized extraction spectrophotometric determination of Hg(II) with dithizone after its flotation as ion-associate using iodide and ferroin

This paper describes a simple and highly selective method for the separation, preconcentration and spectrophotometric determination of extremely low concentration of mercury. The method is based on the flotation of an ion-associate of HgI₄²⁻ and ferroin between aqueous and n-heptane interface at pH 5. The ion-associate was then separated and treated with ammonia and dithizone solutions to extract only the mercury chelate with CH₂Cl₂. The measurement is feasible when the volume of the water sample containing Hg(II) was varied over 50-800 ml. Beer's law was obeyed over the concentration range of 8 × 10⁻⁹ to 1.6 × 10⁻⁷ mol l⁻¹ with an apparent molar absorptivity of 6.53 × 10⁶ l mol⁻¹ cm⁻¹ for a 500 ml aliquot of the water sample. The detection limit (n = 7) was 5.0 × 10⁻¹⁰ mol l⁻¹ and the R.S.D. (n = 5) for 8.0 × 10⁻⁷ mol l⁻¹ of Hg(II) was 3.7%. A notable advantage of the method is that the determination of Hg(II) is free from the interference of almost all cations and anions found in the environmental and waste water samples. The determination of Hg(II) in tap, synthetic sea water and human hair samples was carried out by the present method and cold vapor atomic absorption spectrometry (CV-AAS). The results were satisfactorily comparable so that the applicability of the proposed method was confirmed to the real samples.     

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 determination of hexafluoroarsenate with ferroin

A spectrophotometric method for the hexafluoroarsenate anion is described. The determination involves selective extraction of the tris(1,10-phenanthroline)iron(II) salt of the anion into n-butyronitrile, followed by measurement of the absorbance of the organic layer. The extracts give good Beer's law plots over a wide range of concentrations and more than 98% of the hexafluoroarsenate is removed in a single extraction. Interference studies were made on a number of anions.     

Simple spectrophotometric and titrimetric methods for the determination of sulfur dioxide.

The proposed work describes a simple spectrophotmetric as well as a titrimetric method to determine sulfur dioxide. The spectrophotometric method is based on a redox reaction between sulfur dioxide and iodine monochloride obtained from iodine with chloramine-T in acetic acid. The reagent iodine monochloride oxidizes sulfur dioxide to sulfate, thereby reducing itself to iodine. Thus liberated iodine will also oxidize sulfur dioxide and reduce itself to iodide. The obtained iodide is expected to combine with iodine to form a brown-colored homoatomictriiodide anion (460 nm), which forms an ion-pair with the sulfonamide cation, providing exceptional color stability to the system under an acidic condition, and is quantitatively relatd to sulfur dioxide. The system obeys Beer's law in the range 5 - 100 microg of sulfur dioxide in a final volume of 10 ml. The molar absorptivity is 5.03 x 10(3) l mol(-1)cm(-1), with a relative standard deviation of 3.2% for 50 microg of sulfur dioxide (n = 10). In the titrimetric method, the reagent iodine monochloride was reduced with potassium iodide (10%) to iodine, which oxidized sulfur dioxide to sulfate, and excess iodine was determined with a thiosulfate solution. The volume difference of thiosulfate with the reagent and with the sulfur dioxide determined the sulfur dioxide. Reproducible and accurate results were obtained in the range of 0.1 - 1.5 mg of sulfur dioxide with a relative standard deviation of 1.2% for 0.8 mg of sulfur dioxide (n = 10).     

Indirect spectrophotometric determination of some reducing agents,using phenolphthalin as reagent

Summary An indirect method for the spectrophotometric determination of microgram amounts of hydroquinone, hydroxylamine and hydrazine is outlined. A known excess of potassium ferricyanide solution is added to the sample solution to oxidise the compound to be determined; the excess of ferricyanide is then determined spectrophotometrically with phenolphthalin. The method is simple, reproducible and accurate to ±2%.

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Zusammenfassung Ein indirekles Verfahren für die spektrophotometrische Bestimmung von Mikromengen Hydrochinon, Hydroxylamin und Hydrazin wurde beschrieben. Eine gemessene überschüssige Menge Kaliumcyanoferrat(III) wird der Probenlösung zugesetzt, um die Verbindung zu oxydieren. Der Überschuß wird dann spektrophotometrisch mit Phenolphthalin gemessen. Das Verfahren ist einfach und auf ±2% genau.