Preconcentration extractive separation, speciation and spectrometric determination of iron(III) in environmental samples

Preconcentration, speciation and separation with solvent extraction of Fe(III) from samples of different origin, using methyl isobutyl ketone (MIBK) as a solvent and the sodium salt of 2-carboethoxy-1,3-indandione (CEIDNa) as a complexing agent for Fe(III), were studied. CEIDNa reacts with Fe(III) in the pH range 1.5–3.5 to produce a red colored complex of Fe(III)–CEIDNa (1:3 molar ratio) soluble in MIBK. The investigation includes a study of the characteristics that are essential for solvent extraction, spectrophotometric and flame atomic absorption spectrometric determination (AAS) of iron. A highly sensitive, selective and rapid spectrometric method is described for the trace analysis of iron(III) by CEIDNa. The complex formed obeys Beer's law from 0.06 to 1.8 mg l⁻¹ with an optimum range. A single step extraction was efficiently used with a distribution ratio (D)=10^3.6. The extracted red colored (1:3) Fe–CEIDNa was measured spectrophotometrically at 500 nm with a molar absorptivity of 1.2×10⁴ l mol⁻¹ cm⁻¹. In addition, the organic phase was directly aspirated to the flame for AAS determination and the signals related to Fe(III) concentration were recorded at 243.3 nm. The complexation of iron(III) with CEIDNa allows the separation of the analyte from alkali, alkaline earth and other elements, which are not complexed. The proposed preconcentration procedure was applied successfully to the determination of trace Fe(III) in soil, milk and natural water samples.     

Structural,spectral, and theoretical investigations of 5-methyl-1-phenyl-1H-pyrazole-4-carboxylic acid

Research on Chemical Intermediates - The present research work has focused on combined experimental and theoretical studies of one of the biologically important pyrazole-4-carboxylic acid...     

Selective extraction and determination of Au(III) by first-derivative spectrophotometry

The selective extraction of Au(III) in the presence of Zn(II) by salting-out of 2-propanol was investigated. The salting-out effect increased partitioning between water and 2-propanol in the presence of sodium chloride in aqueous–organic mixtures. This is observed through the distribution coefficient, which increases with salt addition. First-derivative spectrophotometry, which eliminates interference from overlapping spectral bands, was used for the determination of trace Au(III) in the presence of Zn(II). Absorption spectra were recorded and the first-derivative spectra were obtained using Δλ?=?10?nm. The calibration graph was linear for 0.857–5.142?µg?mL^?1 and the detection limit was 0.038–8?µg?mL^?1. The proposed method has been successfully applied to the determination of trace Au(III) in synthetic mixtures and Algerian low gold ore solutions. The results agree with those obtained by atomic absorption spectroscopy and the recoveries were >98%. The relative standard deviations were in all instances less than 3%.     

Multi-pumping flow system for the determination, solid-phase extraction and speciation analysis of iron

A multi-pumping flow system (MPFS) for the spectrophotometric determination, solid-phase extraction (SPE) and speciation analysis of iron at a wide range of concentrations is proposed. Chelating (iminodiacetic groups) disks have been used as solid phase. A solenoid valve allows the deviation of the flow towards the chelating disk to carry out SPE procedures. The possibility to combine solenoid micro-pumps with solenoid valves increases the versatility of MPFS. Ammonium thiocyanate has been chosen as chromogenic reagent for Fe(III). The determination of total iron is achieved by the on-line oxidation of iron(II) to iron(III) with a hydrogen peroxide stream.

A mass calibration was run within the range 0.01–1.75 μg. The detection limit (3s_b/S) was 0.01 μg. The repeatability (R.S.D.) was estimated as 1.6% after 10-fold processing of 2 ml of 0.5 mg l⁻¹ Fe solution. When SPE was not required, two linear calibration graph within the ranges 0.05–10 and 0.2–15 mg l⁻¹ for the determination of iron(III) and total iron, respectively, were obtained. The proposed procedure was validated by analysis of certified reference materials. The analytical features were compared with those obtained exploiting MSFIA.     

Selective solid-phase extraction of trace Fe(III) from biological and natural water samples using nanometer SiO2 modified with acetylsalicylic acid

A new method using acetylsalicylic acid (aspirin) modified SiO₂ nanoparticles (nanometer SiO₂-aspirin) as a solid-phase extractant (SPE) has been developed for the preconcentration of trace amounts of Fe(III) prior to their determination by inductively coupled plasma optical emission spectrometry. The preconcentration conditions of analytes were investigated, including the pH value, the shaking time, the mass of sorbent, the sample flow rate and volume, the elution condition and the interfering ions. At pH 4, the sorption capacity of nanometer SiO₂-aspirin was found to be 1.28 mmol g⁻¹. The preconcentration factor is 50. The detection limit (3σ) for Fe(III) was 0.49 ng mL⁻¹. The method was validated by analyzing two certified reference materials (GBW 08301, river sediment and GBW 08303, polluted farming soil), and the results obtained are in good agreement with standard values. The method was also applied to the determination of trace Fe(III) in biological and water samples with satisfactory results. Correspondence: Xiangbing Zhu, Department of Chemistry, Lanzhou University, Lanzhou 730000, P.R. China     

Effect of aniline derivatives on the extraction of cobalt with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one in toluene

Summary The effect of aniline derivatives [4-methylaniline=4-toluidine, 3,4-dimethylaniline=3,4-xylidine, N,N-dimethylaniline and tribenzylamine (Am)] on the extraction of cobalt from sulphate, nitrate and perchlorate aqueous media of 1.0M ionic strength with 1-phenyl-3-methyl-4-benzoylpyrazol-5-one (HL) in toluene, has been quantitatively studied. With both primary amines a synergic effect was found owing to theAmH·CoL ₃ ion pair extraction. TheAmH·CoL ₃ average formation constant, from CoL ₂ andAmH·CoL, was logK _s =3.7 and 3.8 forAm=4-toluidine and 3,4-xylidine respectively. With N,N-dimethylaniline and tribenzylamine which are poorly protonated in the cobalt extractionpH range (4–6), no noticeable synergism was observed.On leave from: Department of Inorganic Chemistry, Chemical Faculty, Ignacy Lukasiewicz Technical University, PL-35-959 Rzeszow, Poland     

Synthesis of 5-substituted 1-aryl-1H-pyrazole-4-acetonitriles, 4-methyl-1-phenyl-1H-pyrazole-3-carbonitriles and pharmacologically active 1-aryl-1H-pyrazole-4-acetic acids

Lithium aluminum hydride reduction of 5-substituted or unsubstituted ethyl or methyl 1-aryl-1H-pyrazole-4-carboxylates gave, generally in excellent yields, 5-substituted or unsubstituted 1-aryl-1H-pyrazole-4-methanols which afforded the corresponding 1-aryl-4-(bromomethyl)-1H-pyrazoles with hydrobromic acid in acetic acid solution. These crude intermediates gave by reaction with potassium cyanide in dimethylsulfoxide solution 1-aryl-1H-pyrazole-4-acetonitriles only in the case of 5-unsubstituted compounds, otherwise mixtures of 5-substituted 1-aryl-1H-pyrazole-4-acetonitriles and 4-methyl-1-phenyl-1H-pyrazole-3-carbonitriles were generally obtained. Acetonitriles IIIa,b,i,l gave in excellent yields the corresponding 1-aryl-1H-pyrazole-4-acetic acids Va,b,i,l by alkaline hydrolysis. Compounds Vb,i,l showed in the writhing test appreciable analgesic properties, associated with low acute toxicity; moreover, compound VI exhibited a statistically significant antiinflammatory activity in the carrageenan-induced edema assay.     

Selective preconcentration, separation and speciation of ferric iron in different samples using N,N'-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane

The synthesis and analytical applications of N,N'-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane (HBDAP) are described. This compound reacts with Fe(III) in the range of pH 3-6 to produce a red complex (2:3 mol ratio of Fe(III)/HBDAP) soluble in chloroform. The investigation included a study of the characteristics that are essential for solvent extraction and for spectrophotometric determination and speciation of iron. A highly sensitive, selective and rapid spectrophotometric method is described for the determination of trace amounts of iron(III) by HBDAP. The complex obeys Beer's law from 0.056 to 1.68 mg l(-1) with an optimum range. The detection limit (taken as three times the standard deviation of the reagent blank) is approximately 1.23x10(-7) M Fe(III) and the limit of quantitation (taken as ten times the standard deviation of the reagent blank) is about 4.11x10(-7) M Fe(III). A single extraction gave a good separation of iron(III) from iron(II). Good separation of Fe(III) from Ni(II), Fe(II), Co(II), Cd(II), Mn(II), Zn(II), Pb(II) was also achieved at pH 3-5.     

Liquid-liquid extraction separation of zinc and cadmium with 1-phenyl-3-methyl-4-acyl-5-pyrazolones and tri-n-octylphosphine oxide

The extraction of zinc and cadmium with a mixture of a 1-phenyl-3-methyl-4-acyl-5-pyrazolone and trioctylphosphine oxide (TOPO) in various solvents is described. The extraction constants for systems based on eight 4-acyl compounds (C₃C₁₈) are reported. The 1-phenyl-3-methyl-4-stearoyl-5-pyrazolone/benzene system is most effective for the mutual separation of zinc and cadmium at pH 4.5; 20 μg of zinc can be separated efficiently from 20 mg of cadmium.     

Extraction chromatographic separation of platinum(IV) from real samples and associated elements

 The extraction behavior of platinum(IV) was studied with N-n-octylaniline as a function of different parameters, such as pH, concentrations of weak acids, mineral acids, reagents and elution time. A selective method was developed for the extraction chromatographic studies of platinum(IV) and its separation from several metal ions with N-n-octylaniline (liquid anion exchanger) as a stationary phase on silica gel. The quantitative extraction of platinum(IV) was observed with 0.067 mol/L N-n-octylaniline and 0.015 mol/L ascorbic acid at pH 1.0. Metal ion was stripped from the column with water and determined spectrophotometrically with stannous chloride method. The proposed method is free from the interference of a large number of cations and anions. Platinum(IV) was separated from pharmaceutical preparations, alloys and synthetic mixtures. Mutual separation scheme was developed for platinum(IV), palladium(II) and gold(III). The log-log plot of N-n-octylaniline concentration versus the distribution ratio indicates that the probable extracted species is ［RR′NH+2 ］· Pt(C6H7O6)－3.     

Second derivative spectrophotometric method for simultaneous determination of cobalt, nickel and iron using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol

A simple, sensitive and rapid derivative spectrophotometric method using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) has been developed for simultaneous determination of Co(II), Ni(II) and Fe(II) which have very similar chemical behavior and appear together in many real samples. The complexes of all these metal ions with 5-Br-PADAP were formed immediately at pH 7.0 ammonium acetate buffered solution and were stable for at least 24 h. Second derivative spectra were selected for evaluation, because working wavelength determination was more precise and spectral overlap was less than in the ordinary and first derivative spectra. Three wavelengths at which the complexes exhibit extremum ²D values for Co(II), Ni(II) and Fe(II) were selected as analytical wavelengths, i.e., 640, 600 and 740 nm, respectively. Calibration curves drawn with zero-to-peak values at mentioned wavelengths were linear between 80 and 2000 ng ml⁻¹ for each metal ion. Concentrations of Co(II) and Ni(II) were calculated from the total ²D values and the sum of the linear equations for these three cations at 640 and 600 nm, after Fe(II) assay by making use of the ²D value at 740 nm. Limits of detection (LOD) for Co(II), Ni(II) and Fe(II) were 2.7, 13.9 and 3.0 ng ml⁻¹, respectively. The method has been applied to tool steel and heater resistance wire samples successfully.     

Preconcentration and separation of copper (II) with solvent extraction using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane

Preconcentration and separation with solvent extraction of Cu(II) from aqueous solution using N,N′-bis(2-hydroxy-5-bromo-benzyl)1,2 diaminopropane (H₂L) as the new extractant has been studied. Separation of Cu(II) from other metal ions such as Cd(II), Ni(II), Zn(II), Pb(II), Cr(III), Co(II) and Mn(II) at aqueous solutions of various pH values and complexing agent H₂L, has been described. The possible extraction mechanism and the compositions of the extracted species have been determined. The separation factors for these metals using this reagent are reported while efficient methods for the separation of Cu(II) from other metal ions are proposed. From the loaded organic phase, Cu(II) stripping was carried out in one stage with different mineral acid solutions. The stripping efficiency was found to be quantitative in case of HNO₃ and HCl. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complex extracted is the simple 1:1 chelate, CuL. The extraction constant has a value of logK_ex=−4.05±0.04.     

Synergistic extraction of copper(II) from sulfate medium with capric acid and tri-n-octylphosphine oxide in chloroform

The synergistic solvent extraction of copper(II) from 0.33?mol?dm^?3 Na₂SO₄ aqueous solutions with capric acid (HL) in the absence and presence of tri-n-octylphosphine oxide (TOPO) in chloroform at 25°C has been studied. The extracted species when capric acid was used alone is CuL₂(HL)₂. In the presence of TOPO, the extracted complex is CuL₂(HL)₂(TOPO). The TOPO–HL interaction strongly influences the synergistic extraction efficiency. The extraction constants were calculated.     

HPLC determination of copper(II), cobalt(II) and iron(II) in pharmaceutical preparations using 2-acetylpyridine-4-phenyl-3-thiosemicarbazone derivatizing agent

Summary Cu(II) Co(II) and Fe(II) in pharmaceutical preparations were determined using precolumn derivatization and solvent extraction with 2-acetylpyridine-4-phenyl-3-thiosemicarbazone (APPT) as complexing reagent. Liquid chromatography (LC) was carried out on a reversed phase C-18, column. The complexes were eluted isocratically with acetonitrile-water containing sodium acetate and tetrabutyl ammonium bromide as ion-pairing agents. The results obtained were compared with those using atomic absorption.     

On-line separation and preconcentration of inorganic arsenic and selenium species in natural water samples with CTAB-modified alkyl silica microcolumn and determination by inductively coupled plasma-optical emission spectrometry

A new, simple, and selective method has been presented for the separation and preconcentration of inorganic arsenic (As(III)/As(V)) and selenium (Se(IV)/Se(VI)) species by a microcolumn on-line coupled with inductively coupled plasma-optical emission spectrometry (ICP-OES). Trace amounts of As(V) and Se(VI) species were separated and preconcentrated from total As and Se at desired pH values by a conical microcolumn packed with cetyltrimethylammonium bromide (CTAB)-modified alkyl silica sorbent in the absence of chelating reagent. The species adsorbed by CTAB-modified alkyl silica sorbent were quantitatively desorbed with 0.10 ml of 1.0 mol l⁻¹ HNO₃. Total inorganic arsenic and selenium were similarly extracted after oxidation of As(III) and Se(IV) to As(V) and Se(VI) with KMnO₄ (50.0 μmol l⁻¹). The assay of As(III) and Se(IV) were based on subtracting As(V) and Se(VI) from total As and total Se, respectively. All parameters affecting the separation/preconcentration of As(V) and Se(VI) including pH, sample flow rate and volume, eluent solution and volume have been studied. With a sample volume of 3.0 ml, the sample throughput was 24 h⁻¹ and the enrichment factors for As(V) and Se(VI) were 26.7 and 27.6, respectively. The limits of detection (LODs) were 0.15 μg l⁻¹ for As(V) and 0.10 μg l⁻¹ for Se(VI). The relative standard deviations (RSDs) for nine replicate determinations at 5.0 μg l⁻¹ level of As(V) and Se(VI) were 4.0% and 3.6%, respectively. The calibration graphs of the method for As(V) and Se(VI) were linear in the range of 0.5–1000.0 μg l⁻¹ with a correlation coefficient of 0.9936 and 0.9992, respectively. The developed method was successfully applied to the speciation analysis of inorganic arsenic and selenium in natural water samples with satisfactory results.     

HPLC determination of copper(II), cobalt(II) and iron(II) in pharmaceutical preparations using 2-acetylpyridine-4-phenyl-3-thiosemicarbazone derivatizing agent

Summary Cu(II) Co(II) and Fe(II) in pharmaceutical preparations were determined using precolumn derivatization and solvent extraction with 2-acetylpyridine-4-phenyl-3-thiosemicarbazone (APPT) as complexing reagent. Liquid chromatography (LC) was carried out on a reversed phase C-18, column. The complexes were eluted isocratically with acetonitrile-water containing sodium acetate and tetrabutyl ammonium bromide as ion-pairing agents. The results obtained were compared with those using atomic absorption.     

Coupling of flow injection wetting-film extraction without segmentation and phase separation to flame atomic absorption spectrometry for the determination of trace copper in water samples

A flow injection wetting-film extraction system without segmentor and phase separator has been coupled to flame atomic absorption spectrometry for the determination of trace copper. Isobutyl methyl ketone (MIBK) was selected as coating solvent and 8-hydroxyquinoline (oxine) as the chelating reagent. By switching of a 8-channel valve and alternative initiation of two peristaltic pumps, MIBK, sample solution containing copper chelate of oxine, and air-segment sandwiched eluting solution (1.0 mol l⁻¹ nitric acid) were sequentially aspirated into an extraction coil made of PTFE tubing of 360 cm length and 0.5 mm i.d. The formation of organic film in the wall of the extraction coil, extraction of the copper chelate into the organic film and back-extraction of the analyte into the eluting solution occurred consecutively when these zones aspirated into the extraction coil were propelled down the extraction coil by a carrier solution at a flow rate of 2 ml min⁻¹. After leaving the extraction coil, the concentrated zone was transported to the nebulizer at its free uptake rate for atomization. Under the optimized conditions, an enrichment factor of 43 and a detection limit of 0.2 μg l⁻¹ copper were achieved at a sample throughput rate of 30 h⁻¹. Eleven determinations of a standard copper solution of 60 μg l⁻¹ gave a relative standard deviation of 1.5%. Foreign ions possibly present in tap water and natural water did not interfere with the copper determination. The developed method has been successfully used to the determination of copper content of tap water and river water.     

Selective solid phase extraction and preconcentration of iron(III) based on silica gel-chemically immobilized purpurogallin

The immobilization of purpurogallin on the surface of amino group containing silica gel phase for the formation of a newly synthesized silica gel-bound purpurogallin (SGBP) is described. The surface modification was studied and evaluated by determination of the surface coverage value by both the elemental analysis and metal probe testing method, which was found to be 0.485 and 0.460 mmol g⁻¹, respectively. The metal sorption properties of SGBP were examined by a series of di- and tri-valent metal ions. The metal capacity values (mmol g⁻¹) for this series of metal ions were also determined under different buffer solutions (pH 1.0–6.0) as well as shaking times by the batch equilibrium technique. The results of this study confirmed the strong affinity and selectivity as well as the fast equilibration and interaction processes of SGBP and Fe(III) compared to the other tested metal ions. The reduction–oxidation process of iron(II)/iron(III) by SGBP was also studied and the results indicated only 2.1% reduction of iron(III) into iron(II). The selectivity incorporated into silica gel phase via the immobilization of purpurogallin was intensively studied for a several binary mixtures containing iron(III)—another interfering metal ion. The determined percentage extraction values of iron(III) from these mixtures were found to be in the range of 94–100%. The potential applications of SGBP as a selective solid extractor for iron(III) from natural tap water samples and real matrices were also studied and the results revealed good percentage extraction values of iron(III) (93.5−94.9±4.6−5.3%) of the spiked iron(III) in the acidified tap water samples as well as a high preconcentration factor of 500 was also established when SGBP was used as a selective solid phase extractor and preconcentration of iron(III) from acidified soft drink samples with percentage recovery values of (98.0−97.4±4.7−5.3%) of the spiked iron(III).     

Lanthanide complex of 1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldehyde-(isonicotinoyl) hydrazone: crystal structure and DNA-binding properties

A Schiff-base ligand derived from 1-phenyl-3-methyl-4-formyl-2-pyrazolin-5-one (PMFP) and isoniazid was prepared and its La(III) complex was characterized by X-ray single crystal diffraction. The La(III) is nine-coordinate in a space group P2₁/n. DNA-binding was investigated by UV-Vis, fluorescence titration, ethidium bromide displacement experiments, and viscosity measurements, which indicated that the ligand and La(III) complex strongly binds to calf thymus DNA presumably via groove binding and intercalation. The intrinsic binding constants of the ligand and La(III) complex were 0.86?×?10⁵ and 2.46?×?10^5?mol?L^?1, respectively. Antioxidant data from hydroxyl radical scavenging experiments in vitro suggest that the La(III) complex possesses higher scavenging ratio than the free ligand, metallic salt, and some standard antioxidants like mannitol.     

Synergistic extraction of lanthanum(III) from chloride medium by mixtures of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 and triisobutylphosphine sulphide

The synergistic effect of 1-phenyl-3-methyl-4-benzoyl-pyrazalone-5 (HPMBP) and triisobutylphosphine sulphide (TIBPS, B) is investigated in the extraction of lanthanum(III) from chloride solution. Lanthanum(III) is extracted by the mixture as LaCl₂·PMBP·B_0.5 instead of La(PMBP)₃·(HPMBP) which is extracted by HPMBP alone. The equilibrium constants and thermodynamic functions such as ΔG, ΔH and ΔS are determined. The extraction of other rare earth ions by mixtures of HPMBP and TIBPS is also studied and the possibility of separating rare earth ions is discussed.