Spectrophotometric Determination of Cobalt,Nickel and Palladium after Extraction with Thioxanthate into Molten Naphthalene

Cobalt, nickel and palladium have been extracted with thioxanthate into molten naphthalene (85–90°C). Various parameters involved in the extraction have been studied and composition of the extracted complex established in each case. Cobalt. nickel and palladium thioxanthates are extracted in the pH range, Co: 5.0–9.5. Ni: 3.9–7.4 and Pd: 2.0–9.5 and can be determined spectrophotometrically at 390. 500 and 345 nm respectively. The molar absorptivities are calculated to be Co: 6.187×10³ ? mol^?1 cm^?1, Ni: 8.8×10³ ? mol^?1 cm^?1 and Pd: 1.16×10⁴ ? mol^?1 cm^?1 with sensitivities in terms of Sandell's defication are; 0.0095 μg Co/cm² at 390 nm, 0.0060 μg Ni/cm² at 500 nm and 0.0091 μg Pd/cm² at 345 nm respectively. These conditions have been utilized for the determination of these metals in alloys and also for the simultaneous determination of cobalt and nickel in an alloy.     

Tetradecyldimethylbenzylammonium thiocyanate adsorbent supported on naphthalene for the preconcentration and determination of cobalt in aluminium alloys and steels using atomic absorption spectrometry

A solid ion-pair material produced from tetradecyldimethylbenzylammonium chloride (TDBA) and ammonium thiocyanate on naphthalene provides a simple, rapid and selective technique of preconcentrating cobalt from up to 200 ml of aqueous solution. Cobalt reacts with sodium 1-nitroso-2-naphthol-3,6-disulphonate (nitroso-R salt) to form a brown, water-soluble chelate anion. The chelate anion forms a water-insoluble Co-nitroso-R salt-TDBA complex on naphthalene packed in a column and trace cobalt is quantitatively retained on the naphthalene in the pH range 2.7–11.0 at a flow-rate of 2 ml min^?1. The solid mass is stripped from the column with 5 ml of dimethylformamide (DMF) and cobalt is measured by atomic absorption spectrometry (AAS) at 241 nm. The calibration graph is linear over the concentration range 0.5–15μg Co in 5 ml of dimethylformamide solution. Seven replicate determinations of 9 μg of cobalt gave a mean absorbance of 0.095 with a relative standard deviation of 1.7%. The sensitivity for 1% absorption was 0.0834μg ml^?1 (0.240 μg ml^?1 for direct AAS on the aqueous solution). The proposed method was utilized for the determination of cobalt in standard aluminium alloys and steel samples.     

Spectrophotometric Determination of Iron (III) Using 3-Hydroxy-2-Methyl-1,4-Naphthoquinone Monoxime (HMNQM)

Iron (III) forms brown coloured complex with 3-hydroxy-2-methyl-1,4-naphthoquinone monoxime. The iron (III)-HMNQM complex is found to be soluble in DMF and exhibits maximum absorption at 470 nm in the pH range 4.5–5.5. Beer's law is obeyed upto 5.58 ppm of iron (III) and sensitivity of the reaction is 0.0046 μg/cm², with molar absorptivity of 1.21×10⁴ ? mole^?1 cm^?1. The method has been used for the determination of iron (III) in alloys.     

2-Methyl-1, 4-Naphthoquinone Thiosemicarbazone as a Sensitive and Selective Chromogenic Reagent for Microdetermination of Palladium (II)

A simple, sensitive and selective procedure has been developed for the spectrophotometric determination of palladium. Palladium (II) reacts with 2-methyl-1,4-naphthoquinone thiosemicarbazone to form an orange brown complex in the pH range 8.2–9.5. The sensitivity, in terms of Sandell's definition, is 0.0025 μg Pd/cm² at 500 nm. The system adheres to Beer's law upto 2.66 ppm of palladium and optimum concentration range for the determination of the metal is 0.3–2.29 ppm with molar absorbtivity of 4.2×10⁴ ? mole^?1 cm^?1. The complex has 1:1 molar composition, as deduced by Job's method. The determination of palladium has been carried out in presence of foreign ions especially in presence of eighth group metals.     

The Extractive-Spectrophotometric Determination of Iron(III) As a Mixed-Ligand Complex with N-Hydroxy-N,N′DI-p-Tolyl-p-Toluamidine and Thiocyanate

The extractive-photometric determination or iron(III) as a mixed-ligand complex with N -hydroxy-N, N′ -di-p -tolyl-p -toluamidine (HDTTA) and thiocyanate is described. The orange-red Waterinsoluble 1:1:2 (metal: HDTTA: SCN^?) ternary complex formed in 0.1–0.6 M hydrochloric acid solutions is quantitatively extractable into benzene. The wavelength of maximum absorption, molar absorptivity and sensitivity of the colour system are 460nm, 12000 l. mole^?1 cm^?1 and 0.0046 μg Fe/cm ²respectively. The influence or foreign ions on the determination of iron has been studied. This method has also been applied to determine the iron content of several alloys.     

Rapid spectrophotometric determination of ruthenium(III) with prochlorperazine maleate

A rapid, simple spectrophotometric method for the determination of μg amounts of ruthenium, based on the formation of a pink complex between the metal and prochlorperazine maleate (PCPM) in sulphuric or hydrochloric acid solution, is described. The complex has an absorption maximum at 530 nm and its molar absorptivity is 6.733·10³ l mol^?1 cm^?1. The sensitivity is 0.0151 μg Ru cm^?2 for log I_o/I = 0.001. Beer's law is valid over the range 0.2–10 μg Ru ml^?1 ; the optimal range for spectrophotometric determination is 0.8–8.0 μg Ru ml^?1. Job's method of continuous variation, the mole ratio method and the slope ratio method indicate a 1:1 composition for the complex. The effects of acidity, time, temperature, order of addition of reagents, reagent concentration, and the interferences from various ions are reported.     

Spectrophotometric Determination of Diphenadione Via its Metal Complexes

Abstract

Spectrophotometric procedure is described for the quantitative determination of diphenadione [2-(diphenylacetyl)-1,3-indandione], based on direct spectrophotometric measurements of the absorbances of its iron (III), iron (II) and cobalt (II), metal complexes at 488 nm, 505 nm and (334 nm, 372 nm), respectively. The drug reacts with metals in the ratio of 3:1 and 2:1 for iron (III) and for both iron (II) and cobalt (II) respectively. The obtained complexes have apparent molar absorptivities of 1.48 × 10³ 1 mol^?1 cm^?1, 0.714 × 10³ 1 mol^?1cm^?1 and (1.70 × 10³ 1 mol^?1cm^?1, 1.93 × 10³ 1 mol^?1cm^?1) for iron (III), iron (II) and cobalt (II) complexes, respectively. The procedure is suggested for the determination of 51–400 μg.ml^?1 diphenadione via the iron (II) complex and 35–170 μg.ml^?1 diphenadione via both cobalt (II) and iron (III) complexes. The suggested procedure has accuracies of 99.79 ± 0.67%, 99.64 ± 0.37% and (100.09 ± 0.53%, 99.99 ± 0.42%) for the metal complexes of iron (III), iron (II) and cobalt (II), respectively.     

Spectrophotometric Determination of Albendazole Drug in Tablets: Spectroscopic Characterization of the Charge-transfer Solid Complexes

Simple, rapid and reliable method for the determination of albendazole (ABZ) was described. This includes the utility of some Π‐acceptors such as 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) and 3,6‐dichloro‐2,5‐dihy‐ droxy‐p‐benzoquinone (p‐CLA) for estimation of ABZ drug (act as donor). The experimental conditions were optimized and the system obeys Beer's law for 7.50–80 and 10.00–85.00 µg·mL^?1 of ABZ using DDQ and p‐CLA, respectively. The molar absorptivity and Sandell sensitivity were calculated to be 1.83×10³ and 1.12×10³ L·mol^?1·cm^?1, and 2.60 and 3.40 ng·cm^?2 using DDQ and p‐CLA, respectively. The limits of detection and quantification were calculated to be (7.42 and 6.73) and (9.94 and 4.13) µg·mL^?1 using DDQ and p‐CLA, respectively. The proposed methods were successfully applied to the determination of ABZ in commercially available dosage forms. The reliability of the assays was established by parallel determination by the official method and recovery studies. The chemical structures of the solid charge‐transfer (CT) complexes formed via reaction between ABZ under study and Π‐acceptors, have been elucidated using elemental analyses (C, H and N), IR, ¹H NMR and mass spectra.     

Spectrophotometric determination of osmium with phthalimide dithiosemicarbazone by means of complex formation and catalytic reactions

Phthalimide dithiosemicarbazone forms a 1:1 complex with osmium at pH 3.3–4.5 (?₄₅₀ = 1.3 · 10⁴ l mol^?1 cm^?1 ) which is applied to the photometric determination of osmium; Beer's law is obeyed for the range 1–12 μg Os ml^?1. The oxidation of the reagent with cerium(IV) is catalyzed by osmium(VIII), and this reaction allows a more sensitive procedure for the determination of osmium; the calibration curve is linear over the range 0.05–0.4 μg Os ml^?1. The interferences in both procedures are described.     

2‐Aminocyclopentene‐1‐Dithiocarboxylic Acid‐Naphthalene Adsorbent for the Preconcentration and Determination of a Trace Copper in Real Samples by Spectrophotometric Method

A solid uncharged complex produced from 2‐aminocyclopentene‐1‐dithiocarboxylic acid (synthetic reagent) on naphthalene provides a very sensitive, selective and economical method for the preconcentration and determination of trace amounts of copper in drug and alloy samples. The 2‐aminocyclopentene‐1‐dithiocarboxylate of copper is retained quantitatively on microcrystalline naphthalene in the pH range 2.8–3.3. After filtration the solid mass consisting of copper complex‐naphthalene is dissolved with 4 mL of dimethylformamide (DMF). The absorbance is measured at 462 nm with a spectrophotometer against the reagent blank and molar absorptivity found to be 2.8 × 10⁵ liter mol^?1 cm^?1. Beer's law is obeyed over the concentration range of 0.1–16.0 μg of copper in 4 mL of the dimethylformamide solution. Detection limit is 3 ng mL^?1 [signal to noise ratio = 2]. Ten replicate determinations on a sample containing 1 μg of copper gave a relative standard deviation of 0.76%. The interference of a large number of anions and cations have been studied and the optimized conditions developed were utilized for determination of copper in various real samples.     

Column Chromatographic Preconcentration of Copper in Alloys and Complex Materials Using 9,10 Phenanthrenequinone Monoxime Supported on Naphthalene

Abstract

A solid chelating compound phenanthrenequinone monoxime PQM) supported on naphthalene provides a rapid and economical means of preconcentration and separation of copper from the aqueous samples. Copper forms a complex with PC:: supported on naphthalene in the column at pH 6.1–8.4 with a flow rate of 1 ml/min. The metal complex and naphthalene are dissolved out from the column with 5 ml of DMF and the absorbance is measured at 470 nm against reacent blank. Beer's law is obeyed in the concentration range 0.6 9.6 μg of copper in 5 ml of DMF. The molar absorptivity and sensitivity are 6.3×10⁴ L mol^?1 cm^?1 and 0.001 μg cm^?2 respectively.     

Synthesis of New Reagent 2,6‐Diacetylpyridine Bis‐4‐Phenyl‐3‐Thiosemicarbazone (2,6‐DAPBPTSC): Selective,Sensitive and Extractive Spectrophotometric Determination of Co(II) in Vegetable,Soil, Pharmaceutical and Alloy Samples

New synthesized reagent 2,6‐diacetylpyridine bis‐4‐phenyl‐3‐thiosemicarbazone (2,6‐DAPBPTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a reddish brown colored complex with 2,6‐DAPBPTSC, which is extracted into isoamylalcohol, under optimum conditions. The maximum absorption of the isoamylalcohol extract is measured at 400 nm. Beer's law is applied in the range 0.6‐6.0 ppm of cobalt(II). The molar absorptivity and Sandell's sensitivity of the complex is calculated as 2.2 × 10⁴ L mol^?1 cm^?1 and 2.68 × 10^?3 μg cm^?2, respectively. An adequate linearity with a correlation coefficient value of 0.969 is obtained for the Co(II)‐2,6‐DAPBPTSC complex. The instability constant of the complex, calculated from Asmus' method is 3.75 × 10^?4 The precision and accuracy of the method is checked with calculation of relative standard deviation (n = 5), 0.388 and the detection limit a value is 0.0028 μg mL^?1. The method is successfully employed for the determination of cobalt(II) in real samples, such as vegetables, soil, water samples, standard alloy samples, and the performance of the present method was evaluated in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of the present method is an inter comparison of the experimental values, using atomic absorption spectrometer (AAS).     

Extraction-spectrophotometric determination of nickel as Ni-(PAR)2-(CTAB)2 complex in polymetallic sea-bed nodules and steels

A red, water-soluble complex of nickel with PAR can be extracted into chloroform with CTAB at pH 7.0. The system obeys Beer's law upto 0.5 μg/ml with a molar absorptivity of 45 200 L·mol^?1·cm^?1 at 540 nm. Job's method of continuous variations revealed that the composition of the extracting species is 1:2:2 for nickel:PAR:CTAB. Based on this extraction, a highly sensitive and selective spectrophotometric method for the determination of nickel in polymetallic sea-bed nodules and in steels, after prior separation of iron and manganese, was developed. The standard deviation was 0.04–0.127 μg for 5–25 μg of nickel.     

Spectrophotometric studies on complexation reactions of some water-soluble 5-nitro-2-pyridylhydrazones with cobalt. Spectrophotometric and derivative spectrophotometric determination of trace cobalt with 2-benzimidazolyl-3-sulphophenylmethanone 5-nitro-2-pyridylhydrazone

The complexation reactions of four water-soluble hydrazones, 2-quinolyl-3-sulphophenylmethanone 5-nitro-2-pyridylhydrazone, 3-sulphophenyl-2-thiazolylmethanone 5-nitro-2-pyridylhydrazone (STNPH), 2-benzothiazolyl-3-sulphophenylmethanone 5-nitro-2-pyridylhydrazone and 2-benzimidazolyl-3-sulphophenylmethanone 5-nitro-2-pyridylhydrazone (BISNPH), with cobalt(II) were studied spectrophotometrically. These hydrazones react with cobalt(II) to form stable 1:2 (metal:ligand) complexes, except for STNPH, which forms a 1:1 complex, with high molar absorptivities. A sensitive and selective spectrophotometric method for the determination of cobalt with BISNPH has been developed. The cobalt(II)-BISNPH complex is formed quantitatively in the pH range 2.7–9.4 and oxidized rapidly to give the corresponding cobalt(III) complex with an absorption maximum at 517 nm. Beer's law is obeyed over the range 0.02–1.0 μg ml^?1 and the apparent molar absorptivity of the cobalt(III) complex is 6.65 × 10⁴ l mol^?1 cm^?1 at 517 nm. The method was applied to the determination of cobalt in iron and steel samples with satisfactory results. The sensitivity is increased 11-fold by use of second-derivative spectrophotometry.     

Spectrophotometric determination of platinum with substituted pyrimidine-2-thiol

The yellow complex of Pt(IV) with 1-pyridyl-4,4,6-trimethyl-1H,4H-pyrimidine-2-thiol (PyTPT) which has maximum absorbance at 430 nm, is studied for the spectrophotometric determination of the metal. Molar absorptivity is 5000 liters mol^?1 cm^?1 and Sandell's sensitivity is 0.039 μg/cm². The determination of Pt(IV) (2.8–8.4 ppm) in the presence of diverse ions is described.     

Spectrophotometric determination of cobalt(II) based on the ion-pair of tetrathiocyanatocobaltate(II) with neotetrazolium chloride

The ion-pair formed between tetrathiocyanatocobaltate(II) and [3,3′-(4,4′- biphenylene)bis(2,5-diphenyl)]-2H-tetrazolium chloride (neotetrazolium chloride) can be extracted into 4-methylpentan-2-one and used for the spectrophotometric determination of cobalt (2.5–9.8 μg ml^?1) at pH 3.5–5.0. The Sandell sensitivity of the method is 0.02 μg Co cm^?2. With suitabte masking, the method is quite selective and is applicable to nickel wire alloys.     

Electrochemical Interrogation and Sensor Applications of Nanostructured Polypyrroles

The polymerization of pyrrole in β‐naphthalene sulfonic acid (NSA) gave nanotubules, nanomicelles or nanosheets of polypyrrole (PPy) depending on the amount of NSA in the polymer and the temperature of the reaction. Scanning electron microscopy (SEM) measurements showed that the diameters of the nanostructured polypyrrole‐β‐naphthalene sulfonic acid (PPyNSA) composites were 150–3000 nm for the tubules, 100–150 nm for the micelles and 20 nm for the sheets. A red shift in the UV‐vis absorption spectra of PPy was observed for PPyNSA which indicates the involvement of bulky β‐naphthalene sulfonate ion in the polymerization process. The UV‐vis also showed the existence of polaron and bi‐polaron in the polymer which may be responsible for the improved solubility of PPyNSA compared to PPy. All the characteristic IR bands of polypyrrole were observed in the FTIR spectra of PPyNSA, with slight variation in the absolute values. However, the absence of N? H stretching at 3400 cm^?1 and 1450 cm^?1 usually associated with neutral polypyrrole confirms that the polymer is not in the aromatic state but in the excited polaron and bipolaron defect state. Electrochemical analysis of PPyNSA reveals two redox couples: a/a′ – partly oxidized polypyrrole‐naphthalene sulfonate radical cation/neutral polypyrrole naphthalene sulfonate; b/b′ – fully oxidized naphthalene sulfonate radical cation/partly reduced polypyrrole‐naphthalene sulfonate radical anion. The corresponding formal potentials measured at 5 mV/s, E°′_{(5 mV/s)}, are 181 mV and 291 mV, respectively. Amperometric phenol sensor constructed with PPyNSA on a glassy carbon electrode (GCE) gave a sensitivity of 3.1 mA M^?1 and a dynamic linear range of 0.65–139.5 μM. The data for the determination of phenol on the GCE/PPyNSA electrode was consistent with the electrocatalytic Michaelis‐Menten model, giving an apparent Michaelis‐Menten constant (K_M′) value of 160 μM.     

O. Carboxyphenylhydrazoethylacetoacetate as an Analytical Reagent for the Determination of Cu(II) and Co(II) in Complex Materials

An extraction‐spectrophotometric method for the determination of trace amounts of copper and cobalt based on their extraction into n‐pentanol with 0. carboxyphenylhydrazoethylacetoacetate (O.CPHEAA) was per formed. Copper was extracted from pH 6.0 – 8.0 and ionic strength 0.5 M – KCl. The maximum absorption of the extracted Cu(II) ‐ O.CPHEAA complex (1:1 & 1:2 species) occurs at 415 nm. The proposed method succeeded in as saying a concentration of 3–63 μg per 10 mL of n‐pentanol (? = 1.25 × 10⁴L mol^?1 cm^?1). The method failed to ex tract cobalt ion into various organic sol vents over a pH range of 2–11. The suggested method is highly selective and sensitive according to a wide scheme of interference studied. Copper in some plant samples was accurately estimated using the suggested method. The obtained results and the results of the AAS method were consistent. The reproducibility test shows a relative standard deviation of 1%. Sandell sensitivity for A = 0.001 is 5 × 10^?3 μg cm^?2.     

Selective Spectrophotometric Determination of Copper in Milk with Phenanthraquinone Monothiosemicarbazone

The red complex formed by copper (II) and phenanthraquinone monothiosemicarbazone has an absorption maximum at 530 nm with a molar absorptivity of 14000 cm^?1 mole^?1. The pH range for the determination is 1.1–6.6. Optimum range of concentration for accurate determination is 0.50–3.47 ppm of copper (II) in 50% methanol medium. The limits of interference due to foreign ions have been studied. The method has been successfully employed for the determination of copper in various samples of milk.     

Spectrophotometric determination of magnesium through adsorption of its oxinate complex on microcrystalline naphthalene

An analytical procedure for spectrophotometric determination of magnesium has been developed. The method is based on adsorption of its oxinate complex under controlled experimental conditions on microcrystalline naphthalene at room temperature. The adsorbed species is then dissolved in dimethylformamide and magnesium is quantified spectrophotometrically at 382 nm. The oxine complex in DMFO has molar absorptivity of 4.1 × 10³ liter mol^?1 cm^?1, while its sensitivity is 5.9 × 10^?3 μg/cm² for 0.001 absorbance. The analytical precision is good, since for 10 replicate analyses at 30 μg of Mg, the relative standard deviation did not exceed 2.5%. The method has been applied toward Mg analysis in reference materials and environmental samples.