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).     

Analytical Applications of 2,6‐Diacetylpyridine‐bis‐4‐phenyl‐3‐thiosemicarbazone (2,6‐DAPBPTSC): Determination of Cd(II) in Foods and Water Samples

To the determination of trace amount of Cd(II) present in food and water samples, a selective and extractive spectrophotometric method were developed with 2,6‐diacetylpyridine‐bis‐4‐phenyl‐3‐thiosemicarbazone as a complexing agent. The yellowish orange colored metal complex, Cd(II)‐2,6‐DAPBPTSC with 1:1 (M:L) composition was extracted in to cyclohexanol at pH 9.5 and was shows maximum absorbance at λ_max 390 nm. This method obeys Beer's law in the range of 1.12‐11.25 ppm with 0.972 correlation coefficient of Cd(II)‐2,6‐DAPBPTSC complex, which is indicates linearity between the two variables. The molar absorptivity and sandell's sensitivity were found to be 6.088 × 10⁴ L mol^?1 cm^?1 and 0.0018 μg cm^?2, respectively. The instability constant calculated from Asmus' method (1.447 × 10^?4)at room temperature. The precision and accuracy of the method were checked by relative standard deviation (n = 5), 0.929 and its detection limit, 0.0060 μg mL^?1. The interfering effects of various cations and anions were also studied. The proposed method was successfully applied to the determination of Cd(II) in foods and water samples, and was evaluated its performance in terms of Student ‘t’ test and Variance ‘f’ test, which indicates the significance of present method. The inter comparison of the experimental values, using atomic absorption spectrometer (AAS), was also repoted.     

Solvent extraction and spectrophotometric determination of iron(II) with 2,2′-dipyridyl-2-quinolylhydrazone

2,2′-Dipyridyl-2-quinolylhydrazone (DPQH) was used for the spectrophotometric determination of trace amount of iron(II) after the extraction process. Iron(II) reacts with DPQH at pH 3.4–4.5 to form a water-insoluble 1:2 complex, which can be extracted with many kinds of organic solvent. The extracted species with benzene has absorption maxima at 473, 504, and 644 nm and obeyed Beer's law over the range 0–14 μg of iron at 504 nm and 0–33 μg at 644 nm. The molar absorptivities at 504 and 644 nm are 3.14 × 10⁴ and 1.30 × 10⁴M^?1 cm^?1, respectively. DPQH is one of the most sensitive reagents for iron(II) and trace amount of iron(II) can be determined in the presence of fairly large amounts of other ions. Possible equilibria involved in the extraction process were also studied.     

Color Reaction Between 4-(2-Pyridylazo)Resorcinol and Mercury (II) in the Presence of Surfactant,and Improved Spectrophotometric Determinations of Mercury(II) and Cyanide Ion with its Coloring

Abstract

The reactions among 4-(2-pyridylazo)resorcinol (PAR), mercury(II) and/or cyanide ion in the presence of water soluble surfactants alone or combination were systematically investigated at about pH 9. The spectrophotometric determinations of mercury(II) and cyanide ion were investigated by using the PAR-mercury(II)-HPC complex (3:2:2 molar ratio) in the presence of N-hexadecylpyridinium chloride (HPC) alone; calibration graphs were rectilinear in the ranges of 0 – 40 μg mercury(II) and 0 –10 μg cyanide ion in a final 10 ml with the apparent molar absorptivities of 5.9 × 10⁴ for mercury(II) and 2.5 × 10⁴ 1 mol^?1 cm^?1 for cyanide ion at 590 nm. The proposed method had advantages—rapidity, simplicity without solvent extraction, and sensitivity in comparison with reported solvent extraction methods. The interference of foreign ions decreased 1/2–l//4-fold compared with that in the presence of non-ionic surfactant alone.     

Spectrophotometric Determination of Palladium(II) with n-Hydroxy-N,N-Diphenylbenzamidine and 1 -(2-Pyridylazo)-2-Naphthol

A spectrophotometric method to determine palladium(II) at trace levels is based on the extraction of palladium(II) as a binary complex with N-hydroxy-N,N′-diphenylbenzamidine (HDPBA) in chloroform at pH 5.0 ± 0.2. The complex shows maximum absorbance at 400 nm with molar absorptivity 6.4 × 10³ L mol^?1 cm^?1. The sensitivity of the Pd(II)-HDPBA complex was enhanced by the addition of l-(2-pyridylazo)-2-naphthol (PAN). The green coloured complex shows maximum absorbance at 620 nm with molar absorptivity 1.58 × 10⁴ L mol^?1 cm^?1. Sandell's sensitivity and the detection limit of the method are 0.0067 μg cm^?2and 0.1 μg Pd(II) mL^?1, respectively. Most common metal ions associated with palladium metal do not interfere. The effects of various analytical parameters on the extraction of the metal are discussed.     

Isonitroso-4-Methyl-2-Pentanone for Solvent Extraction and Spectrophotometric Determination of Palladium (II) at Trace Level

Abstract

Isonitroso-4-methyl-2-pentanone (HIMP) is proposed as a new reagent for extraction and photometric determination of Pd(II). The reagent forms a yellow complex with palladium in the pH range 4.0-5.0. The complex extracted into chloroform was measured at 330 nm. The molar absorptivity was found to be 5.37 × 10³ 1 mol^?1 cm^?1 and Sandell's sensitivity 20 ng cm^?2 Beer's law was obeyed over the concentration range 0.1-10.0 μg/ml of palladium. The method is applicable for palladium estimation in Ores and catalysts.     

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.     

Benzothiazole-2-aldehyde-2-quinolylhydrazone as a reagent for the extractive spectrophotometric determination of copper (II)

Benzothiazole-2-aldehyde-2-quinolylhydrazone (BTAQH) was used for the spectrophotometric determination of trace amounts of copper(II) after the extraction process. Copper(II) reacts with BTAQH at pH 8.3–12.6 to form a water-insoluble 1:2 complex, which can be extracted with many kinds of organic solvent. The extracted species with benzene has an absorption maximum at 523 nm and obeyed Beer's law over the range 0.09 to 0.75 ppm of copper. The molar absorptivity is 7.50 × 10⁴M^?1 cm^?1 at 523 nm. The spectral properties of the copper(II) complexes with some tridentate hydrazones containing benzothiazole ring as a functional group were also discussed.     

Spectrophotometric Determination of Lead by Extraction of the Mixed-Metal Complex Pb(II)-Ca-Purpurin (1,2,4-Trihydroxyanthraquinone)

Abstract

Mixtures of Lead(II) and Ca(II) form with purpurin (P; 1,2,4-Trihydroxyanthraquinone) the mixed-metal-complex PbCaP₃, which is extracted with isobutyl methyl ketone (IBMK) at pH 7.8. The molar absorptivity of the complex is 2.8 × 10⁴ l.mol^?1.cm^?1 at 575 nm and its conditional extraction constant 2.5 × 10¹⁷ 1⁴.mole^?4. The use of this complex for the spectrophotometric determination of lead up to 40 μg has been investigated. The proposed procedure has been successfully applied to the analysis of this metal in different samples.     

Nanostructured Cobalt(II) Tetracarboxyphthalocyanine Complex Supported Within the MWCNT Frameworks: Electron Transport and Charge Storage Capabilities

The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm^?1), which is more than an order of magnitude greater than that of the MWCNT‐SO₃H (527 µS cm^?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm^?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (k_app≈19.73×10^?3 cm s^?1)>MWCNT‐SO₃H (k_app≈11.63×10^?3 cm s^?1)>nanoCoTCPc (k_app≈1.09×10^?3 cm s^?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm^?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10^?4 F cm^?2)>nanoCoTCPc (2.57×10^?4 F cm^?2)>MWCNT‐SO₃H (2.28×10^?4 F cm^?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.     

Extractive Spectrophotometric Determination of Cobalt (II) as Ion Association Complex with Thiocyanate and Ephedrine

Abstract

A new spectrophotometric method to determine cobalt(II), based on extraction into methyl-isobutyl—ketone at pH 4.0 of its Ephedrine-Co (II)-SCN^? association ionic compound, is proposed. the organic extract shows an absorption band at 620 nm, having a molar absortivity coefficient of 4.3. 10³ L. mol^?1. cm^?1. Beer's law is obeyed in the 0.5–19.5 μg Co (II)/mL concentration range. the variation coefficient is 0.32 % for ten determinations at the concentration level of 8.8 ppm of cobalt (II).     

Study on the Solid Phase Extraction of Hg(II)‐ABR Chelate with C18 Disks and its Application to the Determination of Mercury in Tobacco and Tobacco Additives

A highly sensitive, selective and rapid method for the determination of mercury based on the rapid reaction of mercury(II) with 5‐(p‐aminobenzylidene)‐rhodanine (ABR) and the solid phase extraction of the colored chelate with C₁₈ disks has been developed. In the presence of pH = 3.5 sodium acetate‐acetic acid buffer solution and Emulsifier‐OP medium, ABR reacts with mercury(II) to form a red chelate of a molar ratio 1:2 (mercury to ABR). This chelate was enriched by the solid phase extraction with C₁₈ disks and eluted the retained chelate from the disks with dimethyl formamide (DMF). The enrichment factor of 50 was achieved. In the DMF medium, the molar absorptivity of the chelate is 1.16 × 10⁵ L.mol^?1.cm^?1 at 540 nm. Beer's law is obeyed in the range of 0.01?3 μg/mL in the measured solution. The relative standard deviation for eleven replicated samples of 0.01 μg/mL level is 1.83%. This method was applied to the determination of mercury in tobacco and tobacco additives with good results.     

A rapid method for the spectrophotometric determination of palladium(II) and osmium(VIII)

Propionyl promazine phosphate is proposed as a new reagent for the rapid spectrophotometric determination of microgram amounts of Pd(II) and Os(VII). PPP instantaneously forms an orange-red 1:1 complex with Pd(II) in sodium acetate-hydrochloric acid buffer of pH 0.8 to 4.0 at room temperature. The reagent also forms an orange-red radical cation with Os(VIII) in 0.5 to 2.0 M hydrochloric acid. The Pd-PPP complex exhibits an absorption maximum at 490–500 nm with molar absorptivity of 7.1 × 10³ liter mol^?1 cm^?1. The Os-PPP radical cation has an absorption maximum at 505–515 nm with molar absorptivity of 2.21 × 10⁴ liters mol^?1 cm^?1. The Sandell sensitivity is 0.022 μg/cm² (Pd) and 0.008 μg/ cm² (Os). Beer's law is valid over the concentration range 0.2 to 21 ppm (Pd) and 0.2 to 4.2 ppm (Os). The proposed method offers the advantages of simplicity, rapidity, and without the need for heating or extraction. The reagent is used for the determination of Pd in the synthetic mixtures corresponding to Pd alloys used in jewelery and Os in osmiridium alloy.     

Spectrophotometric determination of cobalt(II) in the presence of large amounts of iron with salicylaldehyde thiosemicarbazone

Cobalt(II) reacts instantaneously with the reagent at pH 5.0. The yellow complex has a molar absorptivity of 1.1 × 10⁴ 1 mol^?1 cm^?1. The method is applied to the determination of cobalt in steels after removal of iron with phosphate.     

Spectrophotometric determination of copper(II) and its application to a plant sample containing zinc,iron, and manganese

Salicylaldehyde thiosemicarbazone instantaneously forms a green complex with copper(II) in the optimum pH range 5–7. A fivefold molar excess of the reagent is sufficient for the full development of the color. Beer's law is obeyed in the range 0.5–6.0 ppm of copper. The optimum concentration range as evaluated by Ringbom's method is 1.4–5.8 ppm. At 375 nm the sensitivity of the reaction and the molar absorptivity are 0.006 μg cm^?2 and 9.2 × 10³ liters mol^?1 cm^?1, respectively. The effects of pH, reagent concentration, time, order of addition of the solutions, and the interference of various ions were investigated. Copper in plant samples, containing zinc, iron, and manganese, was determined.     

Cyclohexane-1, 3-Dione bis (4-Methylthiosemicarbazone) as a Spectrophotometric Reagent for the Determination of Zn (II)

Abstract

The spectrophotometric study of reddish cyclohexane-1, 3-dione bis (4-methylthiosemicarbazone)-Zn(II) was made in dimethylformamide-water solution (λ_max= 475 nm, ∑ = 3.3×10⁴ 1.mole^?1. cm^?1. Sandell sensitivity = 2×10^?2 μg Zn(II).cm^?2, stoichiometry 1:1, and apparent stability constant 6.1×10⁴). A new method for the spectrophotometric determination of Zn(II) is proposed for concentrations between 0.1 and 2.5 ppm. The relative error (95% confidence level) is 0.7% for 1.0 pprn of Zn(II).

The extraction with ethylacetate of the reddish complex was also studied spectrophotometrically (λ_max = 493 nm, ∑ in organic phase = 4.8×10⁴ 1.mole^?1.cm. Sandell sensitivity = 3.4×10^?4 μg Zn(II).cm^?2, stoichiometry 1:1, apparent extraction constant 1.4×10⁴). A new method for the extraction-spectrophotometric determination of Zn(II) is proposed for concentrations, in aqueous phase, between 0.02 and 0.30 ppm. The relative error (95% confidence level) is 1.0% for 0.15 pprn of Zn(II).     

Simple and Sensitive Extractive Spectrophotometeric Method for the Assay of Mebeverine Hydrochloride in Pure and Pharmaceutical Formulations

Simple, sensitive, rapid and cost effective extraction spectrophotometric methods are described for the assay of mebeverine hydrochloride (MBH) in bulk samples and pharmaceutical formulations. These two methods (Bromophenol blue and Erichrome Black‐T) are based on the formation of chloroform soluble ion‐pair complexes of MBH with Bromophenol blue (BPB) and with Erichrome Black‐T (EBT), to form yellow and pink colored chromogen in a Glycine‐HCl buffer of pH 2.4 (BPB) and in a KCl‐HCl buffer of pH 1.4 (EBT) with absorbance maximum at 416 nm and at 524 nm for BPB and EBT respectively. The calibration graph is found to linear over 0.2–20 μg/mL (BPB) and 0.2–20 μg/mL (EBT), with molar absorptivity values of 1.8295 × 10⁴ 1 moL^?1 cm^?1 and 1.5896 × 10⁴ 1 moL^?1 cm^?1, respectively. The LOD (Limit of Detection) were found to be 0.090 μg/mL and 0.084 μg/mL and LOQ (Limit of Quantification) were 0.2997 μg/mL and 0.2730 μg/mL for the BPB and EBT method, respectively. The results of analysis for the two methods have been validated statistically and by recovery studies. The results are compared with those obtained with reported method. The proposed methods are simple, sensitive, accurate and suitable for quality control applications.     

Spectrophotometry Determination of Cobalt after Extraction of its Ternary Complex with 3-(4-Phenyl-2-Pyridyl)-5,6-Diphenyl-1,2,4-Triazine and Tetraphenylborate into Molten Naphthalene

The reaction of 3-(4-phenyl-2-pyridyl)-5,6-diphenyl-1,2,4-triazine (PPDT) and tetraphenylborate (TPB) with cobalt (II) has been studied to determine the optimum conditions for the extraction and quantitative spectrophotometry determination of this metal. The ternary complex is extracted into molten naphthalene at pH 3.6–7.4. The solid naphthalene containing the cobalt associated complex is separated by filtration and dissolved in acetonitrile. Beer's law is obeyed in the concentration range 8–140 μg cobalt in 10 ml of acetonitrile solution. The molar absorptivity and sensitivity are 4.2×10³ l·mol^?1·cm^?1 and 0.01408 μg/cm², respectively. The other factors such as pH, amounts of reagents and naphthalene, shaking and standing times, and the effect of diverse ions are studied. The method has been applied to the determination of cobalt in iron steel alloys.     

Synthesis of New Reagent Benzyloxybenzaldehydethiosemicarbazone (BBTSC): Selective,Sensitive and Extractive Spectrophotometric Determination of Pd(II) in Water Samples and Synthetic Mixtures

A new reagent, benzyloxybenzaldehydethiosemicarbazone (BBTSC) was synthesized and a new method was developed for the simple, highly selective and extractive spectrophotometric determination of palladium(II) with BBTSC at wave length 365 nm. The metal ion formed a yellow colored complex with BBTSC in acetate buffer of pH 5.0, which was easily extractable into cyclohexanol with 1:1 (Metal: Ligand) composition. The method obeys Beer's law in the range of 5–60 ppm. The molar absorptivity and Sandell's sensitivity were found to be 0.4 × 10⁴ Lt. mol^?1 cm^?1 and 0.02661 μg cm^?2, respectively. The correlation co‐efficient of the Pd(II)‐BBTSC complex was 0.9657, which indicated an excellent linearity between the two variables. The repeatability of the method was checked by finding the relative standard deviation (RSD) (n = 10), which was 0.321% and its detection limit 0.016875 μg.mL^?1. The instability constant of the method was calculated by Asmus' method as 3.5714 × 10^?4. The interfering effect of various cations and anions were also studied. The proposed method was successfully applied for the determination of palladium(II) in synthetic and water samples. The results were compared with those obtained using an atomic absorption spectrophotometer, testing the validity of the method.     

Extraction of gold(III) from low-grade ores with amidines followed by its spectrophotometric determination with methylene blue

A procedure is described in which gold(III) is quantitatively extracted with an amidine into chloroform over the acidity range pH 3.0–11.0 M HCl, followed by its selective spectrophotometric determination by interaction of the extract with methylene blue in the pH range 3.0–9.0. The molar absorptivity of the coloured complex formed by extraction with ten different amidines and methylene blue reaction lie in the range 1.1 × 10⁴?6.5 × 10⁴ 1 mol^?1 cm^?1 at λ_max (650 nm) in chloroform. The simplest compound, N, N′-diphenylbenzamidine, was chosen for detailed study. The limit of detection is 5 μg Au l^?1. The method is free from interferences from the metals that are generally associated with gold. The method is simple, reproducible and applicable to the accurate recovery of gold from low-grade ores containing the metal at levels of > 1.5 μg g^?1.