The simultaneous determination of copper and nickel by liquid-liquid extraction and gas-liquid chromatography with (acetylpivalylmethane)-(trifluoroacetylacetone)ethylenediimine as reagent

The unsymmetrical tetradentate ligand, 1,1,1-trifluoro-1′,1′,1′-trimethyl-4,4′-(ethane-1,2-diyldiimino)bis(pent-3-en-2-one), derived from the condensation of trifluoroacetylacetone and acetylpivalylmethane and trivially named (acetylpivalylmethane)(trifluoroacetylacetone)ethylenediimine has been isolated and its copper(II) and nickel chelates have been prepared. These chelates are readily separated by gas chromatography and a method is proposed for the simultaneous determination of copper and nickel by liquid-liquid extraction of their chelates with the new reagent followed by gas chromatography on a column of OV-1 supported on Gas Chromb Q at 230°C. The method is applied to the determination of the composition of cupro-nickel coinage metal.     

High performance liquid chromatographic determination of copper(II) and nickel(II) by using solvent extraction and bis(acetylpivalylmethane)ethylenediimine as complexing reagent

The reagent bis(acetylpivalylmethane)ethylenediimine has been examined for the HPLC separation of copper(II), nickel(II), palladium(II) and oxovanadium(IV) chelates on reversed phase HPLC columns (250 x 4 mm) packed with Hypersil ODS, 5 mu and (150 x 3.9 mm) Nova Pak C(18) with guard column. The complexes are eluted with a binary mixture of methanol and water or methanol, acetonitrile and water. Detection is achieved with a UV detector. The solvent extraction procedure is used for the determination of copper and nickel simultaneously at microgram levels, corresponding to ng levels and pg levels respectively, per injection. The method has been applied to the determination of copper and nickel in a coin, nickel-aluminum alloy and water samples.     

Simultaneous high performance liquid chromatographic determination of vanadium, nickel, iron and copper in crude petroleum oils using bis(acetylpivalylmethane)ethylenediimine as a complexing reagent

A method is described for the simultaneous high performance liquid chromatographic (HPLC) determination of copper, iron, nickel and vanadium, based on complexation of analytes by bis(acetylpivalylmethane)ethylenediimine (H(2)APM(2)en) followed by solvent extraction and HPLC separation on a reversed-phase. C-18, 5 microm column with UV detection at 260 nm. The method has been applied to the determination of metals in crude petroleum oils collected from the South Indus Basin oil fields. The results obtained are compared with those obtained by flame atomic absorption spectrometry.     

High-performance liquid chromatographic determination of uranium using solvent extraction and bis(salicylaldehyde) tetramethylethylenediimine as complexing reagent

The reagent bis(salicylaldehyde)tetramethylethylenediimine has been used for the determination of dioxouranium(VI), based on complexation in aqueous solution at pH 6, followed by extraction in chloroform and HPLC determination on a Hypersil ODS (3 μm) column. The complex was eluted with the ternary mixture methanol-acetonitrile-water (40:30:30, v/v/v), with UV detection at 260 nm. Oxovanadium(IV), iron(III), copper(II), cobalt(II), nickel(II) and palladium(II) were completely separated and did not interfere in the determination of uranium. The linear calibration range and detection limits have been obtained. The method has been applied to the determination of uranium together with copper, iron and nickel in mineral ore samples.     

High performance liquid chromatographic separation and UV determination of cobalt, copper iron and platinum in pharmaceutical preparations using bis(isovalerylacetone)ethylenediimine as complexing reagent

The reagent bis(isovalerylacetone)ethylenediimine(H₂IVA₂en) has been examined for HPLC separation and UV determination of cobalt, copper, iron and platinum using off-line precolumn derivatization and extraction in chloroform. The complexes of cobalt(II), cobalt(III), iron(II), iron(III) and the reagent have been subsequently separated on a Microsorb C-18 column. The complexes were eluted isocratically using ternary mixtures of methanol/water/acetonitrile. Detection was achieved by UV monitoring. Detection limits for Co(II), Co(III), Fe(II) and Fe(III) were 2.5–5.0 ng/injection, based on 0.5–1.0 g/ml with 5 l/injection. The concentration of cobalt(II) and cobalt(III) in aqueous solution have been determined. The presence of oxovanadium(IV), platinum(II), and nickel(II) did not affect the determinations. The HPLC method developed has been applied to the determination of cobalt, copper, iron and platinum in pharmaceutical preparations at the 30 g/g to 15 mg/g level and the obtained results were compared to those of atomic absorption spectrometry.     

Kinetics and mechanism of formation and dissociation of copper(II) and nickel(II) complexes of the Schiff base bis(acetylacetone)ethylenediimine in aqueous-organic solvent media

Summary In NH₄NO₃+NH₄OH buffered 10% (v/v) dioxan-water media (pH 7.0–8.5), thePseudo-first-order rate constant for the formation of the title complexes M(baen),i.e. ML, conforms to the equation 1/k_obs=1/k+1/(kK_o.s · T_L), where T_L stands for the total ligand concentration in the solution, K_o.s is the equilibrium constant for the formation of an intermediate outer sphere complex and k is the rate constant for the formation of the complex ML from the intermediate. Under the experimental conditions the free ligand (pK_a>14) exists virtually exclusively in the undissociated form (baenH₂ or LH₂) which is present mostly as a keto-amine in the internally hydrogen-bonded state. Although the observed formation-rate ratio k^Cu/k^Ni is of the order of 10⁵, as expected for systems having normal behaviour, the individual rate constants are very low (at 25°C, k^Cu=50 s^–1 and k^Ni=4.7×10^–4s^–1) due to the highly negative S values (–84.2±3.3 JK^–1M^–1 for CuL and –105.8±4.1 JK^–1M^–1 for NiL); the much slower rate of formation of the nickel(II) complex is due to higher H value (41.2±1.0 kJM^–1 for CuL and 78.2±1.2 kJM^–1 for NiL) and more negative S value compared to that of CuL. The K_o.s values are much higher than expected for simple outer-sphere association between [M(H₂O)₆] and LH₂ and may be due to hydrogen bonding interaction.In acid media ([H⁺], 0.01–0.04 M) these complexes M(baen) dissociate very rapidly into the [M(H₂O)₆]²⁺ species and baenH₂, followed by a much slower hydrolytic cleavage of the ligand into its components,viz. acetylacetone and ethylenediamine (protonated). For the dissociation of the complexes k_obs=k₁[H⁺]+k₂[H⁺]². The reactions have been studied in 10% (v/v) dioxan-water media and also ethanolwater media of varying ethanol content (10–25% v/v) and the results are in conformity with a solvent-assisted dissociativeinterchange mechanism involving the protonated complexes.     

Thiotropolone as a chromogenic reagent for the simultaneous determination of cobalt(II) and nickel(II)

Thiotropolone forms chloroform-soluble reddish-brown and violet complexes with cobalt(II) and nickel(II), in the pH range 7.0-8.5 and 6.0-9.0 respectively. Based on this, a sensitive and rapid method for the spectrophotometric determination of traces of cobalt and nickel in metals and alloys has been developed. The two metals can be determined accurately in the range 0.6-2.6 ppm of cobalt and 0.75-4.57 ppm of nickel, simultaneously.     

Selective determination of copper with pyridoin phenylhydrazone as chromogenic extraction reagent

Summary The synthesis, characteristics and analytical applications of pyridoin phenylhydrazone are described. It reacts with copper(I) to produce an orange 11 complex ( _max=450 nm,=2.1×10⁴l· mole^–1·cm^–1) in aqueous ethanolic solution; it behaves as a cuproin type reagent. The orange complex can be extracted into amyl alcohol ( _max=440 nm,=2.0×10⁴l·mole^–1·cm^–1), and used for the spectrophotometric determination of trace amounts of copper. Interferences have been investigated.

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Zusammenfassung Synthese, Eigenschaften und analytische Anwendung von Pyridoin-phenylhydrazon wurden beschrieben. Es reagiert mit Cu(I) unter Bildung eines orange gefärbten 11-Komplexes in wäßrig-alkoholischer Lösung ( _max=450 nm,=2,1×10⁴l·mol^–1·cm^–1); das Reagens verhält sich ähnlich wie Cuproin. Der erwähnte Komplex läßt sich mit Amylalkohol extra-hieren ( _max=440 nm,=2,0×10⁴l·mol^–1·cm^–1) und zur spektrophoto-metrischen Bestimmung von Kupferspuren benützen. Auftretende Störungen wurden angegeben.

     

Acenaphthenequinone monoxime(AQM) as a selective reagent for the spectrophotometric determination of platinum(IV) by solvent extraction

Acenaphthenequinone monoxime has been found to be a selective reagent for spectrophotometric determination of 1-16 ppm of platinum in the pH range 1.90-3.20. With excess of the reagent, a 1 : 2 (metal : ligand) complex is formed with an absorption maximum at 390 nm and molar absorptivity of 9.0 x 10(3) 1.mole(-1).cm(-1). The effect of foreign ions has been investigated and other platinum metals do not interfere if present in similar amounts to the platinum.     

Extraction and spectrophotometric determination of nickel with 2-hydroxyacetophenone oxime and simultaneous determination of copper and nickel

It is observed that 2-hydroxyacetophenone oxime can be used for the quantitative extraction of nickel in the pH range 6.6-7.8 into methyl isobutyl ketone. The organic layer shows maximum absorbance at 375 nm. Beer's law is obeyed over the range 1-6 ppm. The colour of the organic layer is stable for more than 48 hr. Interferences have been studied and methods are suggested for their elimination. Copper and nickel are both quantitatively extracted at pH 7 and can be determined simultaneously and accurately in the range 1-6 microg/ml for copper and 1-4 microg/ml for nickel.     

Separation and simultaneous determination of cobalt, nickel and copper with 2-(4-methyl-2-quinolylazo)-5-diethylaminophenol by reversed-phase high-performance liquid chromatography

Performance of six quinolylazo compounds was studied as a pre-column derivatizing reagent for the separation of metal ions in the reversed-phase high-performance liquid chromatography. 2-(4-Methyl-2-quinolylazo)-5-diethylaminophenol (QADP) was suited for the determination of Co, Ni and Cu in the presence of a large amount of Fe. The detection limits under the optimized conditions [stationary phase: L-column ODS; mobile phase: acetone-water (62:38, v/v) containing 0.01 M NH(4)SCN and 0.01 M 2-morpholinoethanesulfonic acid-NaOH (pH 6); injection volume: 10 mul] were 0.24 ng for Co, 0.22 for Ni and 0.53 for Cu. This method was successfully applied to the determination of these metal ions in a standard steel sample.     

Simultaneous determination of vanadium and molybdenum as N-benzoyl-N-phenylhydroxamate complexes by combining solvent extraction and liquid chromatography

A normal-phase high-performance liquid chromatographic method for the selective simultaneous determination of vanadium and molybdenum with N-benzoyl-N-phenylhydroxylamine (BPHA) is described. The V(V)-BPHA and Mo(Vl)-BPHA complexes were preconcentrated by solvent extraction into chloroform and injected on to a nitrile-bonded column for chromatography. The mobile phase was a 5.9· 10⁻⁴ M solution of BPHA in chloroform (stabilized with amylene). The detection limits for vanadium and molybdenum were 2.1 and 3.3 ng ml⁻¹, respectively, for an aqueous to organic phase-volume ratio of 20:1. The procedure, applied to the analysis of a synthetic water, showed satisfactory accuracy and precision.     

Determination of uranium, iron, copper, and nickel from ore samples by MEKC using N,N'-ethylene bis(salicylaldimine) as complexing reagent

An analytical procedure has been developed for the separation of dioxouranium(VI), iron(III), copper(II), nickel(II), cobalt(II), cobalt(III), palladium(II), and thorium(IV) by MEKC using N,N'-ethylene bis(salicylaldimine) (H(2)SA(2)en) as a complexing reagent with total runtime <4.5 min. SDS was used as micellar medium at pH 8 with sodium tetraborate buffer (0.1 M). An uncoated fused-silica capillary with an effective length of 50 cm x 75 microm id was used with an applied voltage of 30 kV with photodiode array detection at 231 nm. Linear calibrations were obtained within 0.111-1000 microg/mL of each element with LODs within 37-325 ng/mL. The developed method was tested for analysis of uranium ore samples indicating its presence within 103-1789 microg/g with RSD within 0.79-1.87%. Likewise copper, nickel, and iron in their combined matrix were also simultaneously determined with RSD 0.4-1.6% (n = 6).     

Simultaneous solvent extraction and high-performance liquid chromatographic determination of uranium, iron, nickel and copper in mineral ore samples and phosphate rock residues using N,N′-ethylenebis(salicylaldimine) as complexing reagent

The reagent N,N-ethylenebis(salicylaldimine) (H₂SA₂en) has been examined for precolumn derivatization, followed by solvent extraction in chloroform and HPLC determination of uranium, iron, nickel and copper on a Hypersil ODS 3 μm column. Complexes were eluted isocratically using a ternary mixture of methanol-acetonitrile-water and UV detection was at 260 nm. The detection limit was 12 ng/injection for each of the elements. The method has been applied for the determination of metals in mineral ore samples and phosphate rock residues. The results obtained are compared using atomic absorption.     

Spectrophotometric determination of saccharin in different materials by a solvent extraction method using Nile Blue as reagent

In a slightly acidic medium (sodium acetate-acetic acid buffer, pH 4) saccharin and Nile Blue form an ion-association compound which is extractable into methyl isobutyl ketone and allows the spectrophotometric determination of saccharin. At 630 nm Beer's law is obeyed over the saccharin concentration range 0.1-3.5 microg/ml in the aqueous phase and the apparent molar absorptivity is 5.8 x 10(4) l.mole(-1).cm(-1). The method shows good selectivity and can be applied to the determination of saccharin in artificial sweeteners, soft drinks and toothpastes.     

Sequential extraction and determination of copper and nickel with 2,4-dihydroxyacetophenone thiosemicarbazone

2,4-Dihydroxyacetophenone thiosemicarbazone (DAPT) forms a 1:1 complex with copper(II) which can be extracted into n-butanol or ethyl acetate from acetic acid-sodium acetate (pH 5.0) buffer, and a 1:1 nickel(II) complex which can be extracted into n-butanol from ammonium chloride-ammonia (pH 7.5) buffer. The difference between the pH(1 2 ) values for extraction of the two complexes is 3.4 and this has been exploited for their sequential extraction and determination. The molar absorptivities for the copper and nickel complexes are 1.5 x 10(4)l.mole(-1).cm(-1) at 390 nm and 8.2 x 10(3)l.mole(-1).cm(-1) at 385 nm respectively. The procedure has been applied to the analysis of cupronickel.