Determination of trace molybdenum in vegetable and food samples by spectrophotometry with p-carboxyphenylfluorone

A new highly sensitive and selective chromogenic reagent, p-carboxyphenylfluorone (p-CPF), was studied for spectrophotometric determination of trace molybdenum. In 0.36 mol L(-1)phosphoric acid medium, p-CPF reacts with molybdenum(VI) to form a 1:3 red complex, which has a sensitive absorption peak at 531 nm. Under optimal conditions, the reaction of molybdenum(VI) with p-CPF completed rapidly and absorbance remains almost constant for at least 24 h. Molybdenum(VI) obeyed Beer's law in the range 0-2.0 microg mL(-1); the apparent molar absorption coefficient, Sandell's sensitivity and the limit of detection were found to be 1.03 x 10(5) L mol(-1) cm(-1), 1.028 ng cm(-2)and 0.73 ng mL(-1) respectively; the effect of various foreign ions were examined in detail. It was found that most coexisting ions can be tolerated in considerable amounts, especially 800 mg of Mn(II), 200 mg of Mg(II), Fe(II), Co(III), Ni(II) and Cd(II), 50 mg of Ca(II) and Al(III), 25 mg of Cu(II) and Fe(III), 10 mg of Hg (II), La(III), Bi(III), Pb(II) and Zn(II) don't interfere with the determination of molybdenum(VI). The proposed method is very simple, sensitive and selective, it has been applied to determine molybdenum in vegetable and food samples with a very high precision and accuracy. Moreover, the synthesis of the reagent and the conditions of the colour reaction were also studied in detail.     

Kinetochromic spectrophotometry-II Determination of sulphate by catalysis of the zirconium-methylthymol blue reaction

A direct spectrophotometric method is proposed for the determination of sulphate, based on its ability to catalyse the slow reaction between Methylthymol Blue and zirconium in slightly aged solution. The procedure is operated in the same way as a normal spectrophotometric method but with stricter control of timing. The interference of 100-fold excesses of 40 other ions was studied. Of these, Ce(III), Sr, Fe(III), Th, Sn(II), U(V), Mn(II), Sb(III), Se(IV), Bi(III), Te(IV), SO(3)(2-), F(-), PO(4)(3-), AsO(4)(3-), S(2-), tartrate, oxalate and citrate interfered. Cationic interferences may be removed by cation-exchange. The interference of equimolar ratios of arsenate, fluoride and phosphate may be removed by preliminary treatment with magnesium oxide. Sulphate may be determined in the range 0.1-2.4 ppm by the recommended procedure with a net molar absorptivity of 2.0 x 10(4) at 586 nm. The colour development time is 60 min.     

Voltammetric determination of mercury(II) at a carbon paste electrode in aqueous solutions containing tetraphenylborate ion

The determination of mercury(II) ions can be achieved by monitoring the decrease in the oxidation peak of the tetraphenylborate ion in the presence of this metal ion at a carbon paste electrode. The reaction between mercury(II) and the tetraphenylborate ion results in the formation of diphenylmercury, thus providing the method with good selectivity over other metal ions. Using anodic stripping voltammetry in a neutral electrolyte, a linear dependence of the decrease of peak height was observed on increasing the mercury(II) concentration in the range 1 x 10(-6)-8 x 10(-9)M mercury(II). Zinc(II), cadmium(II), lead(II), nickel(II), cobalt(II), tin(II), potassium(I) and ammonium(I) ions did not interfere at a 1000-fold concentration excess. Iron(III) and chromium(III) did not interfere at a 250-fold and 50-fold concentration excess, respectively. Following masking procedures, copper(II), bismuth(III) and silver(I) did not interfere at a 100-fold concentration excess. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal.     

Spectrofluorimetric determination of microgram amounts of lead

The violet fluorescence at 480 mmu of lead in concentrated hydrochloric acid-potassium chloride solution (excitation maximum 270 mmu) provides a method for the spectrofluorimetric determination of 10-60mug of lead. The optimum conditions for the determination have been established, and the effect of 31 foreign ions examined at the 50-fold molar excess level. The interference from iron(III) and vanadium(V) is eliminated by addition of tin(II) chloride, and that of chromium(VI) by treatment with sodium sulphite.     

Determination of trace amounts of vanadium in air samples with 2-(8-quinolylazo)-5-N,N-diethylaminophenol by reversed-phase liquid chromatography

A reversed-phase liquid chromatographic method for the determination of trace amounts of vanadium is described. Metal ions are converted into 2-(8-quinolylazo)-5-N,N-diethylaminophenol chelates in an off-line system. The chelates are injected onto a Zorbax CN column and separated with an aqueous acetonitrile mobile phase containing no chromogenic reagent. Unter these conditions, only vanadium(V) is spectrophotometrically detected at 540 nm among the metal ions Al(III), Ba(II), Ca(II), Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Ga(III), Hg(II), Mg(II), Mn(II), Ni(II), Pb(II), V(V) and Zn(II). Amounts of 8.0–200 pg of vanadium(V) in 100-μl injections can be determined without interference from 10-fold molar excesses of many cations. At 0.001 a.u.f.s., the detection limit (twice the peak-to-peak noise) for vanadium(V) is 8.0 pg in 100 μl of injected solution and the relative standard deviation at 120 pg of vanadium(V) in a 100-μl injection is 3.5%. The proposed method is applied to the determination of vanadium in rain water and airborne particulates.     

Highly sensitive and selective spectrophotometric method for determination of trace gold in geological samples with 5-(2-hydroxy-5-nitrophenylazo)rhodanine

A excellent sensitive and selective method for spectrophotometric determination of trace gold has been developed, the method is based on the color reaction of gold(III) with new reagent 5-(2-hydroxy-5-nitrophenylazo)rhodanine (HNAR). Under optimal conditions, HNAR reacts with gold(III) to form a 1:5 orange complex, which has an maximum absorption peak at 480 nm. Maximum enhancement of the absorbance of the complex was obtained in the presence of the mixed surfactant of Triton X-100 and CTMAB; the reaction completed rapidly and the absorbance is stable for 5 h at least at 20 degrees C; 0-48 microg L(-1) Au(III) obeyed Beer's law. The apparent molar absorptivity of the complex, Sandell's sensitivity, the limit of quantification, the limit of detection and relative standard deviation were found to be 2.0x10(6) L mol(-1) cm(-1), 0.000,098,483 micro g cm(-2), 1.02 ng mL(-1), 0.35 ng mL(-1) and 1.09%, respectively. The effect of co-existing ions was studied seriously; most metal ions can be tolerated in considerable amounts. Its sensitivity and selectivity are remarkably superior to other reagents in the literature. The proposed method was used successfully to determine trace gold in geological samples. Moreover, the synthesis, characteristics and analytical reaction of HNAR with gold are also described in detail.     

Spectrophotometric study of the reactions of arsenazo III with alkaline-earth metals

Arsenazo III is used as a spectrophotometric reagent for alkaline-earth metals. The molar absorptivities of the calcium, strontium and barium complexes at 650 nm are 4.40 x 10(4), 4.00 x 10(4) and 3.65 x 10(4) l.mole(-1).cm(-1) respectively. The interference of magnesium is eliminated at pH 5-6. The use of sodium sulphate as masking agent permits the determination of small amounts of calcium, strontium and magnesium in the presence of barium. The alkaline-earth ions can be determined in the presence of each other at pH 4.2 at the 2-10 mug level. Some organic solvents such as dioxan, acetone and ethanol increase the sensitivity and selectivity in acidic medium. The stability constants have been measured and the structure of the complexes is discussed.     

Catalytic effect of some inorganic ligands on a ligand substitution reaction involving mercury(II) and its application as a differential kinetic method of analysis

To design a sensitive and selective kinetic method for determining a catalyst, the kinetics of the ligand substitution reaction between the mercury(II)-4-(2-pyridylazo)resorcinol complex and 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid together with the catalytic effect of some inorganic ligands on this reaction were studied. The rate constant for a catalyzed reaction path was found to be linearly correlated with the electron donor constant of the catalyst. From this correlation, the difference in reactivity between sulfite or thiosulfate and sulfate was established. Under the selected conditions, sulfite up to 1.5 x 10(-6) M and thiosulfate up to 7 x 10(-7) M could be determined with detection limits of 3 x 10(-8) and 2 x 10(-8) M in the presence of 10 000 and 25 000-fold molar amounts of sulfate, respectively. The tolerance level in the determination of 1 x 10(-6) M of sulfite and 4 x 10(-7) M of thiosulfate was studied for 15 inorganic anions and 44 metal ions.     

Amperometric titration of calcium,strontium and barium and their mixtures in presence of large amounts of alkali metal salts

Trace amounts of alkaline earth metals are titrated with triethylenetetraaminehexaacetic acid; lead(II) is added as indicator and the current is measured by square-wave polarography. At pH 13.3, calcium, strontium and barium give a common end-point corresponding to the total content of alkaline earth ions. Copper and cadmium interfere but small concentrations of Ni, Al, Mg, Zn, Mn(II) and Fe(III) are tolerated. The alkaline earth metals can be determined in the presence of 1000-fold amounts of lithium and 10⁵- fold amounts of sodium or potassium ions.     

1-(2,3,4-Trihydroxybenzylideneamino)-8-hydroxynaphthalene-3,6-disulfonic acid as reagent for spectrophotometric determination of boron in plants

A highly sensitive and selective method has been developed for spectrophotometric determination of boron in plants, the method based on the color reaction of new reagent 1-(2,3,4-trihydroxybenzylideneamino)-8-hydroxynaphthalene-3,6-disulfonic acid (THBA) with boron (III). In an ammonium acetate solution of pH 8.0, boron(III) reacts with THBA to form a 1:2 yellow complex which has a maximum absorption peak at 430 nm. The reaction can complete within 90 min and the absorbance of the complex remains maximum and almost constant at least for 24 h under a temperature range from 0 to 35 °C. The apparent molar absorptivity and Sandell's sensitivity are 2.95 × 10⁴ l mol⁻¹ cm⁻¹ and 0.00036 ng cm⁻², respectively. The limit of quantification, limit of detection and relative standard deviations were found to be 5.1, 1.5 ng ml⁻¹ and 1.12%, respectively. Under the optimum conditions, the absorbency of the complex (λ_max = 430 nm) increases linearly with concentration up to 0.8 μg ml⁻¹ of boron(III). The influences of foreign ions on the determination of boron were investigated in detail. Most of foreign ions can be tolerated in considerable amounts. Experiments have indicated that THBA as chromogenic reagent for spectrophotometric determination of boron has excellent analytical characteristics. Its sensitivity is more than 4.2-fold that of azomethine-H, and stability is advantage over other derivatives of azomehine-H remarkably. Moreover, the synthesis of THBA and its physicochemical properties of THBA were also investigated in detail. Proposed method has been applied to the determination of boron in plants with satisfactory results.     

Analytical application of second-harmonic a.c. polarography

Phase-selective second-harmonic a.c. polarography can be used to distinguish two different species having similar reduction potentials. Because each species has a different phase angle depending on the electrode kinetics, a certain phase angle can be chosen to detect only one component in the mixture. In 1 M potassium chloride solution, indium-(III) at the 4 × 10^-6 M level can be determined in the presence of 50-fold amounts of cadmium(II), and zinc(II) at the 2 × 10^-5 M level in the presence of 100-fold amounts of nickel(II).     

Determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea by stripping voltammetry

Conditions were studied for the stripping voltammetric determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea (PMT), the most efficient polymer complexant for the membrane preconcentration of heavy metal ions. It was shown that PMT significantly enhances the selectivity of determining Pb(II) and Cd(II) in solutions of Cu(II) by stripping voltammetry. Pb(II) and Cd(II) can be determined in the presence of up to 200- and 50-fold amounts of Cu(II), respectively. The limits of detection for Pb(II) and Cd(II) after a 40-s accumulation were 6.9 x 10^-8 and 6.8 x 10^-7 M, respectively.     

Investigation and Analytical Application of the β-Type Chelate of Lanthanoids With Chlorophosphonazo III

Abstract

The color-reaction of chlorophosphonazo III (CPA III) with lanthanide ions has been studied. It is found that under optimum conditions a light and heavy rare earth binuclear chelate with CPA III, of which the ratio of the metals to CPA III is 1:1:3, can be formed and used for determination of trace amounts of light rare earths in the presence of heavy rare earths. The molar absorptivity maximum of the chelate is 5x10⁵ 1 mol^?1 cm^?1.     

Polymer Supported Schiff Base Complexes of Iron(III), Cobalt(II) and Nickel(II) Ions and their Catalytic Activity in Oxidation of Phenol and Cyclohexene

The polymer supported transition metal complexes of N,N′‐bis (o‐hydroxy acetophenone) hydrazine (HPHZ) Schiff base were prepared by immobilization of N,N′‐bis(4‐amino‐o‐hydroxyacetophenone)hydrazine (AHPHZ) Schiff base on chloromethylated polystyrene beads of a constant degree of crosslinking and then loading iron(III), cobalt(II) and nickel(II) ions in methanol. The complexation of polymer anchored HPHZ Schiff base with iron(III), cobalt(II) and nickel(II) ions was 83.30%, 84.20% and 87.80%, respectively, whereas with unsupported HPHZ Schiff base, the complexation of these metal ions was 80.3%, 79.90% and 85.63%. The unsupported and polymer supported metal complexes were characterized for their structures using I.R, UV and elemental analysis. The iron(III) complexes of HPHZ Schiff base were octahedral in geometry, whereas cobalt(II) and nickel(II) complexes showed square planar structures as supported by UV and magnetic measurements. The thermogravimetric analysis (TGA) of HPHZ Schiff base and its metal complexes was used to analyze the variation in thermal stability of HPHZ Schiff base on complexation with metal ions. The HPHZ Schiff base showed a weight loss of 58% at 500°C, but its iron(III), cobalt(II) and nickel(II) ions complexes have shown a weight loss of 30%, 52% and 45% at same temperature. The catalytic activity of metal complexes was tested by studying the oxidation of phenol and epoxidation of cyclohexene in presence of hydrogen peroxide as an oxidant. The supported HPHZ Schiff base complexes of iron(III) ions showed 64.0% conversion for phenol and 81.3% conversion for cyclohexene at a molar ratio of 1∶1∶1 of substrate to catalyst and hydrogen peroxide, but unsupported complexes of iron(III) ions showed 55.5% conversion for phenol and 66.4% conversion for cyclohexene at 1∶1∶1 molar ratio of substrate to catalyst and hydrogen peroxide. The product selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was 90.5% and 96.5% with supported HPHZ Schiff base complexes of iron(III) ions, but was found to be low with cobalt(II) and nickel(II) ions complexes of Schiff base. The selectivity for catechol (CTL) and epoxy cyclohexane (ECH) was different with studied metal ions and varied with molar ratio of metal ions in the reaction mixture. The selectivity was constant on varying the molar ratio of hydrogen peroxide and substrate. The energy of activation for epoxidation of cyclohexene and phenol conversion in presence of polymer supported HPHZ Schiff base complexes of iron(III) ions was 8.9 kJ mol^?1 and 22.8 kJ mol^?1, respectively, but was high with Schiff base complexes of cobalt(II) and nickel(II) ions and with unsupported Schiff base complexes.     

Simultaneous spectrophotometric determination of thorium and rare earth metals with m-carboxychlorophosphonazo (CPAmK) and cetylpyridinium chloride

Th and rare earth elements (REE) react with m-carboxychlorophosphonazo (CPAmK) in the absence of cetylpyridinium chloride (CPC) to form colour complexes. The molar absorptivities for Th and Ce are 1.03 x 10(5) and 1.06 x 10(5) 1.mole(-1).cm(-1) respectively. In the presence of CPC, REE-complexes are not formed because of micellar masking, while Th gives a more sensitive reaction with CPAmK ( = 1.50 x 10(5)). Most of the foreign ions are tolerated in considerable amounts; 360-1000-fold amounts of rare earths do not interfere with the determination of Th. The optimum conditions of the complex-formation reactions and the compositions of Th-CPAmK complexes are described. A simple method is proposed for simultaneous determination of Th and rare earths without previous separation.     

Spectrophotometric determination of antimony with Bromopyrogallol Red

Bromopyrogallol Red may be used as a reagent for the spectrophotometric determination of antimony(III) in the range 10-100 microg. The colour system, in the presence of EDTA, cyanide ion or fluoride ion as masking agents, is unaffected by 200-fold molar excesses of 18 cations examined, and a further 5 cations can be tolerated at lower concentrations. The procedure is simple and rapid, and with a molar absorptivity coefficient in excess of 35,000, it compares favourably with the most sensitive of the techniques used at present.     

Determination of nickel in biological samples spectrophotometrically involving complexation reaction with some thiazolylazo compounds

Three new heterocyclic azo compounds, 5(2-benzothiazolylazo)2,2 biphenyldiol (I), 5-(2-benzothiazolylazo)-8-hydroxyquinolene (II) and 4-(2-benzothiazo-lylazo)3-hydroxy-2-naphthoic acid (III) were synthesized. The formation constant of the reagents in 30% (v/v) ethanol and reactions with various metal ions were studied. These reagents (I-III) reacts with nickel ion to form (2:1) colored complex with an absorption band at 604, 635 and 643 nm. The apparent stability constants and the optimum conditions for complete color development were investigated. Beer's law is obeyed over the concentration ranges of 0.05-3.50, 0.05-4.00 and 0.05-3.10 micrograms ml-1. For more accurate analyses, Ringbom optimum concentration ranges were found to be 0.20-3.25, 0.20-3.80 and 0.20-2.90 micrograms ml-1 using reagents I, II and III, respectively. The apparent molar absorptivity and Sandell sensitivity were also calculated. The interference of various foreign ions on the determination of nickel was investigated. The proposed method has been successfully applied to the determination of nickel substrates in various biological samples.     

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with polyacrylic acid

The trivalent metal ion (M(III)=Cm, Eu)/polyacrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L(-1)-50 g L(-1)) and metal ion concentrations (2x10(-9)-10(-3) M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFlFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(III)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant.     

A simple and rapid spectrophotometric determination of thallium(III) with trifluoperazine hydrochloride.

A simple, sensitive and rapid spectrophotometric method was developed for the determination of thallium(III) using trifluoperazine hydrochloride (TFPH). The method is based on the oxidation of TFPH by thallium(III) in a phosphoric acid medium to form a red-colored radical cation with an absorption maximum at 505 nm. Beer's law is valid over the concentration range of 0.5 - 6.5 microg ml(-1) of thallium(III). The molar absorptivity and Sandell's sensitivity of the color system are 2.14 x 10(4) l mol(-1) cm(-1) and 0.0095 microg cm(-2), respectively. The optimum reaction conditions and other analytical parameters were evaluated. The tolerance limit of the method towards various ions usually associated with thallium has been studied. The proposed method has been successfully applied to the analysis of thallium in alloys, minerals, standard reference material, water, and urine samples.     

Simultaneous spectrophotometric determination of thorium and rare earth metals with pyrimidine azo dyes and cetylpyridinium chloride

Thorium and rare earth elements (REE) react with 5-(2',4'-dimethylphenylazo)6-hydroxypyrimidine-2,4-dione (I) and 5-(4'-nitro-2',6'-dichlorophenylazo)6-hydroxypyrimidine-2,4-dione (II) in the absence of cetylpyridinium chloride (CPC) to form red complexes. The molar absorptivity and Sandell sensitivity were calculated in absence of CPC. In its presence, REE - complexes are not formed due to miceller masking, whereas Th(4+) has a sensitive reaction with the studied reagents I and II, with enhancement of the color intensity of the complex. Most of the foreign ions are tolerated in considerable amounts; 150-2400-fold amounts of rare earth do not interfere with the determination of thorium. The optimum experimental conditions of the complex formation reactions and the compositions of thorium complexes are described. A simple method is proposed for simultaneous determination of thorium and rare earth element without previous separation.