6-Chloro-3-hydroxy-2-(5'-methylfuryl)-4H-chromene-4-one as an analytical reagent for micro determination of molybdenum(VI).

6-Chloro-3-hydroxy-2-(5'-methylfuryl)-4H-chromene-4-one (CHMFC) has been used as an analytical reagent for the spectrophotometric determination of molybdenum. Molybdenum(VI) in the presence of several cations, anions and complexing agents forms a yellow 1:2 complex with CHMFC. The complex is quantitatively extractable into 1,2-dichloroethane from 1 mol dm(-3) acetic acid medium and is stable for more than 6 h. The complex shows an absorption maximum at 438 nm with a molar absorptivity of 5.36 x 10(4) dm3 mol(-1) cm(-1) and Sandell's sensitivity equal to 0.0017 microg Mo cm(-2). The method obeys Beer's law up to 1.9 microg Mo ml(-1). The relative standard deviations are 0.2% for solutions and 0.5-1.5% for solid samples. The method is simple, selective, precise and rapid, and has been satisfactorily applied to the micro determination of molybdenum in various synthetic and standard samples.     

Improved spectrophotometric determination of uranium(VI) with 4-(2-pyridylazo)resorcinol in the presence of benzyldimethylstearyltrimethylammonium chloride

An improved spectrophotometric determination of uranium(VI) is proposed using 4-(2-pyridylazo)resorcinol(PAR) in the presence of benzyldimethylstearyltrimethylammonium chloride(BSTAC) as a cationic surfactant. The calibration graph is linear in the range of 0.3-60 microg/10 ml uranium(VI), measuring the absorbance at 550 nm. The reproducibility for 19.0 microg/10 ml uranium(VI) is 0.57%. The third-derivative method using the third-derivative distance (d(3)A/dlambda(3)) among lambda(1) 530 nm, lambda(3) 594 nm and lambda(2) 565 nm was also investigated.     

Complexation of uranium by 2-(2-thiazolylazo)-4-methoxyphenol and 2-(2-thiazolylazo)-5-methoxyphenol

A comparative study has been made of the complexation of uranium(VI) by 2-(2-thiazolyl)-4-methoxyphenol (TAMH) and 2-(2-thiazolylazo)-5-methoxyphenol(TAMR). The complexes are less stable and have lower molar absorptivities than the PAR and TAR complexes but are still useful for determination of uranium. The TAMH chelate can be extracted into isobutyl methyl ketone. Both complexes are 1:1 metal :ligand. For the TAMH complex log beta(1) = 8.8, = 1.4 x 10(4) at 610 mmu; for the TAMR complex log beta(1) = 8.1, = 2.0 x 10(4) at 530 mmu.     

A new sensitive method for the spectrophotometric determination of molybdenum using 3-hydroxy-2-(2'-thienyl)-4H-chromen-4-one

A spectrophotometric method has been developed for the determination of Molybdenum (VI) using 3-hydroxy-2-(2'-thienyl)-4H-chromen-4-one as a complexing agent. The complex formed was dissolved in water in the presence of Triton X-100 and exhibits an absorption maximum at 410 nm. A large number of metal ions like Co(II), Ni(II), Mn(II), Cr(III), Zn(II), Cu(II), Hg(II), Bi(III), Fe(II), Fe(III), Zr(IV), V(V) can be tolerated at an appreciable concentrations. Molar absorptivity and Sandell's sensitivity of the method is 2.80 x 10(5) l mol-1cm-1 and 3.42 x 10(-4) micrograms cm-2, respectively. Beer's law is obeyed in the concentration range of 0.01-0.4 ppm Mo(VI). Aliquots containing 0.2 ppm of Mo(VI) give a mean absorbance of 0.56 with a relative standard deviation of 1.3%.     

Spectrophotometric determination of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol in the presence of anionic surfactant

A highly sensitive method for spectrophotometric determination of uranium has been devised. The method is based on formation of a red-violet 1:2 (metal:ligand) complex from the reaction of uranium(VI) with 2-(3,5-dibromo-2-pyridylazo)-5-diethylaminophenol (3,5-diBr-PADAP) in the presence of an anionic surfactant, sodium lauryl sulphate. Its molar absorptivity is found to be 9.1 x 10(4)l.mole(-1).cm(-1). The absorbance is constant in the range pH 8.4-9.9 Beer's law is obeyed for 0-1.4 mug/ml concentrations of uranium. In the presence of DCTA the method is selective for uranium, and can be used for the determination of trace amounts of uranium in water samples.     

3-Hydroxy-2-(2-thienyl)-4H-chromen-4-one as a new reagent for the extraction and trace determination of molybdenum(VI)

A simple, sensitive and selective method for the extraction and trace determination of molybdenum(VI) has been developed; it is based on its reaction with 3-hydroxy-2-(2-thienyl)-4H-chromen-4-one (HTC) in sulphuric acid medium. The 1:2 Mo (VI)-HTC yellow complex is quantitatively extractable into chloroform (_max 420 nm) and is stable for more than 4 h. The procedure eliminates the interference of a large number of metal ions and complexing agents. Beer's law is obeyed in the range of 0–2.85 g Mo/mL with a molar absorptivity, Sandell's sensitivity and standard deviation of 5.28×10⁴ L mol^–1 cm^–1, 0.0018 g Mo/cm² and ±0.0054, respectively. The method has successfully been used for the spectrophotometric determination of molybdenum in steel samples.     

Colour reaction of gold with 5-(4-sodium sulphonatephenylazo)-8-aminoquinoline and its analytical application

The synthesis of 5-(4-sodium sulphonatephenylazo)-8-aminoquinoline (SPAQ) is described, and a simple, rapid, selective and sensitive new spectrophotometric method for determination of gold is developed. SPAQ reacts with gold(III), and in the presence of cetyl trimethyl ammonium bromide cationic surfactant and upon making the solution alkaline, forms a blue-green 1:3 (metal:ligand) with an absorption maximum at 605 nm. Beer's law is obeyed over the concentration range 0-2 microg/ml gold. The molar absorptivity and Sandell's sensitivity of the method are 1.48 x 10(5) 1.mole(-1).cm(-1) and 0.0013 microg/cm(2), respectively. The interference of various ions has been studied and the method has been used for the determination of microamounts of gold in ores and anode slimes.     

A highly selective spectrophotometric determination of niobium (V) using 3-hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1-benzopyran as a complexing agent

3-Hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1benzopyran (HPCPB) is used as an analytical reagent for the spectrophotometric determination of niobium in trace amounts with which it forms a yellow coloured complex (4:1) in perchloric acid medium. The complex is extractable into chloroform and shows absorption maximum at 407-418 nm with a molar absorptivity of 2.79 x 10(4) L mol(-1) cm(-1) and Sandell's sensitivity equal to 0.0033 microg Nb(V) cm(-2), respectively. Beer's law holds good in the range 0-1.2 microg Nb ml(-1), with a standard deviation of +/- 0.0015 absorbance units. The method is free from the interference of a large number of elements and handles satisfactorily the analysis of various samples of varying complexity.     

Spectrophotometric determination of thorium in food using 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid

A new highly sensitive and selective chromogenic reagent, 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid (1), was synthesized and applied to the spectrophotometric determination of trace thorium. In 5 mL of a 6 M perchloric acid medium, which greatly increases the selectivity, thorium reacts with 1 to form a 1: 2 green complex, having a sensitive absorption peak at 670 nm. Under optimal conditions, Beer’s law is obeyed over the range from 0 to 0.8 μg/mL Th(IV) and the apparent molar absorptivity is 2.09 × 10⁵ L/mol cm. It is found that, uranium(VI), Ti(IV), heavy rare earths, and most of other common metal ions do not interfere. The method has been tested on the determination of thorium in food samples with satisfactory results. The text was submitted by the authors in English.     

Simultaneous determination of gallium and indium with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in cationic micellar medium using derivative spectrophotometry.

A new derivative spectrophotometric method for rapid and selective trace analysis of Ga3+ and In3+ and for their simultaneous determination using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in a cationic micellar medium is reported. Molar absorptivity and Sandell's sensitivity of 1:1 Ga+ and In3+ complexes at their lambda(max) 553 nm and 558 nm are: 7.22 x 10(4) l mol(-1) cm(-1) and 5.85 x 10(4) l mol(-1) cm(-1), and 0.96 ng cm(-2) and 1.96 ng cm(-2), respectively. Linearity is observed in the concentration range 0.023-0.700 microg ml(-1) for gallium and 0.076-1.52 microg ml(-1) for indium; IUPAC detection limit is 0.012 and 0.035 ng ml(-1), respectively. These metal ions interfere with the determination of each other. However, 0.07-0.70 microg ml(-1) Ga3+ and 0.115-1.150 microg ml(-1) In3+ could be determined simultaneously when present together by the derivative method without any prior separation. The proposed procedures have been successfully applied for the individual and simultaneous determination of gallium and indium in synthetic binary mixtures, standard reference materials and environmental samples.     

A kinetic and thermodynamic study of the unexpected comproportionation reaction between cis-[Os(VIII)O4(OH)2](2-) and trans-[Os(VI)O2(OH)4](2-) to form a postulated [Os(VII)O3(OH)3](2-) complex anion

A kinetic study of [OsO(4)] reduction by aliphatic alcohols (MeOH and EtOH) was performed in a 2.0 M NaOH matrix at 298.1 K. The rate model that best fitted the UV-VIS data supports a one-step, two electron reduction of Os(VIII) (present as both the [Os(VIII)O(4)(OH)](-) and cis-[Os(VIII)O(4)(OH)(2)](2-) species in a ratio of 0.34:0.66) to form the trans-[Os(VI)O(2)(OH)(4)](2-) species. The formed trans-[Os(VI)O(2)(OH)(4)](2-) species subsequently reacts relatively rapidly with the cis-[Os(VIII)O(4)(OH)(2)](2-) complex anion to form a postulated [Os(VII)O(3)(OH)(3)](2-) species according to: cis-[Os(VIII)O(4)(OH)(2)](2-) + trans-[Os(VI)O(2)(OH)(4)](2-) (k+2) (k-2) 2[Os(VII)O(3)(OH)(3)](2-). The calculated forward, k(+2), and reverse, k(-2), reaction rate constants of this comproportionation reaction are 620.9 ± 14.6 M(-1) s(-1) and 65.7 ± 1.2 M(-1) s(-1) respectively. Interestingly, it was found that the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion does not oxidize MeOH or EtOH. Furthermore, the reduction of Os(VIII) with MeOH or EtOH is first order with respect to the aliphatic alcohol concentration. In order to corroborate the formation of the [Os(VII)O(3)(OH)(3)](2-) species predicted with the rate model simulations, several Os(VIII)/Os(VI) mole fraction and mole ratio titrations were conducted in a 2.0 M NaOH matrix at 298.1 K under equilibrium conditions. These titrations confirmed that the cis-[Os(VIII)O(4)(OH)(2)](2-) and trans-[Os(VI)O(2)(OH)(4)](2-) species react in a 1:1 ratio with a calculated equilibrium constant, K(COM), of 9.3 ± 0.4. The ratio of rate constants k(+2) and k(-2) agrees quantitatively with K(COM), satisfying the principle of detailed balance. In addition, for the first time, the molar extinction coefficient spectrum of the postulated [Os(VII)O(3)(OH)(3)](2-) complex anion is reported.     

Rapid speciation analysis of Cr(VI) and Cr(III) by reversed-phase high-performance liquid chromatography with UV detection

A simple and rapid method is developed for the simultaneous determination of Cr(VI) and Cr(III) based on the formation of their different complexes with ammonium pyrrolidine-dithiocarbamate (APDC). Separation is performed using reversed-phase high-performance liquid chromatography coupled with UV detection. The conditions for complex formation and speciation are determined, such as solution pH, amount of APDC, temperature, and type of mobile phase. In order to substantially reduce the analysis time, the separation is carried out without extraction of chromium-APDC complexes from the mother liquor. Under the optimum analysis conditions, the chromatograms obtained show good peak separation, and the absolute detection limits (3s) are 2.2 microg/L for Cr(VI) and 4.5 microg/L for Cr(III). The calibration curves are linear from 3 to 5000 microg/L for Cr(VI) and 5 to 3000 microg/L for Cr(III). The relative standard deviations of peak areas in five measurements using a sample solution of 200 microg/L are less than 2% for Cr(VI) and 4% for Cr(III), indicating good reproducibility for this analytical method. Furthermore, simultaneous determination of Cr(VI) and Cr(III) is successful with the application of the proposed procedure in the synthetic wastewaters containing common heavy metal ions: Fe(III), Pb(II), Cd(II), Cu(II), and Zn(II).     

Extractive photometric determination of gold(III) with 1-(2',4',6'-trichlorophenyl)-4,4,6-trimethyl-(1H,4H)-2-pyrimidinethiol in presence of tri-iso-octylamine

Tervalent gold was determined spectrophotometrically as its anionic 1:4 gold-thiol complex extracted into chloroform from aqueous acidic medium (1.5M sulphuric acid) in the presence of tri-iso-octylamine. The complex exhibits maximum absorption at 480 nm (molar absorptivity 4.60 x 10(3) l.mole(-1).cm(-1)) and Beer's law is obeyed in the concentration range 5-50 microg of gold(III) per ml. The relative standard deviation and relative error, calculated from ten determinations of solutions containing 15 microg of gold(III) per ml were 1.0% and 0.8%. The method is simple, selective and reproducible. It permits separation of gold(III) from associated elements and its determination in synthetic mixtures.     

Determination of molybdenum(VI) by differential pulse polarographic technique using 4-(2-hydroxy phenyl ethaminodiol), benzene-1,3-diol(4-2-HPEDB-1,3,D)

A novel analytical reagent 4-(2-hydroxy phenyl ethaminodiol), benzene-1,3-diol(4-2-HPEDB-1,3,D) was synthesized for the determination of molybdenum(VI). The present paper reveals the detailed study of electroanalytical behaviour for [Mo-(4-2-HPEDB-1,3,D)] complex under optimized conditions. The peak obtained for [Mo-(4-2-HPEDB-1,3,D)] prevent the interference of foreign ions which shows the sensitivity of the proposed method. The linearity was maintained at the concentration range of 0.5–200 μg/mL at pH 4.5 with correlation factor 0.9997. The present method was successfully applied for the analysis of molybdenum(VI) in biological fluids and plant material. The results obtained from the proposed method show good agreement with reference method.     

4-(N,N-diethylamino) benzaldehyde thiosemicarbazone in the spectrophotometric determination of palladium

4-(N,N-diethylamino)benzaldehyde thiosemicarbazone(DEABT) is proposed as a sensitive and selective analytical reagent for the spectrophotometric determination of palladium(II). The reagent reacts with palladium (II) in a potassium hydrogen phthalate-hydrochloric acid buffer of pH 3.0, to form a yellow complex. Beer's law is obeyed in the concentration range up to 3.60 microgmL(-1). The optimum concentration range for minimum photometric error as determined by Ringbom plot method is 0.36 - 3.24 microg mL(-1). The yellow Pd(II)-DEABT complex shows a maximum absorbance at 408 nm, with molar absorptivity of 3.33 x 10(4) dm3 mol(-1) cm(-1) and Sandell's sensitivity of the complex from Beer's data, for D = 0.001, is 0.0032 microg cm(-2). The composition of the Pd(II)-DEABT complex is found to be 1:2 (M:L). The interference of various cations and anions in the method were studied. The proposed method was successfully used for the determination of Pd(II) in alloys, catalysts, complexes and model mixtures with a fair degree of accuracy.     

Extraction mechanism of Cr(VI) on the aqueous two-phase system of tetrabutylammonium bromide and (NH(4))(2)SO(4) mixture

An aqueous two-phase system of tetrabutylammonium bromide (TBAB) and (NH(4))(2)SO(4) mixture has been developed for the extractive preconcentration and separation of certain compounds. TBAB concentration in upper phase is much higher than that of bottom solution. This new aqueous two-phase system is proposed for the highly selective extraction of Cr(VI) from large amounts of Cr(3+). The Cr(VI) is found to be extracted into the TBAB-rich upper phase due to ion pair formation such as HCrO(4)(-) . TBAB(+). The Cr(VI) was sufficiently extracted into the upper phase in the pH range from 1 to 5. The proposed method has been applied to the determination of trace of Cr(VI) in wastewater samples with a coefficient of variation less than 3.2%. The recovery obtained was not lower than 90%. The determination limit for the Cr(VI) was found to be 60 mug l(-1) in 10 ml of sample solution.     

A chelating resin containing 1-(2-thiazolylazo)-2-naphthol as the functional group; synthesis and sorption behavior for trace metal ions

A new polystyrene-divinylbenzene resin containing 1-(2-thiazolylazo)-2-naphthol (TAN) functional group was synthesized and its sorption behavior for 19 metal ions including Zr(IV), Hf(IV) and U(VI) was investigated by batch and column experiments. The chelating resin showed a high sorption affinity for Zr(IV) and Hf(IV) at pH 2. Some parameters affecting the sorption of the metal ions are detailed. The breakthrough and overall capacities were measured under optimized conditions. The overall capacities of Zr(IV) and Hf(IV) that were higher than those of the other metal ions were 0.92 and 0.87 mmol/g, respectively. The elution order of metal ions at pH 4 was evaluated as: Zr(IV)>Hf(IV)>Th(IV)>V(V)>Nb(V)>Cu(II)>U(VI)>Ta(V)>Mo(VI)>Cr(III)>Sn(IV)>W(VI). Quantitative recovery of most metal ions except Zr(IV) was achieved using 2 M HNO₃. Desorption and recovery of Zr(IV) was successfully performed with 2 M HClO₄ and 2 M HCl.     

Redox-induced terpyridyl substitution in the Os(VI)-hydrazido complex, trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+)

Reaction between the Os(VI)-hydrazido complex, trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+) (tpy = 2,2':6',2"-terpyridine and O(CH(2))(4)N(-) = morpholide), and a series of N- or O-bases gives as products the substituted Os(VI)-hydrazido complexes, trans-[Os(VI)(4'-RNtpy)(Cl)(2)(NN(CH(2))(4)O)](2+) or trans-[Os(VI)(4'-ROtpy)(Cl)(2)(NN(CH(2))(4)O)](2+) (RN(-) = anilide (PhNH(-)); S,S-diphenyl sulfilimide (Ph(2)S=N(-)); benzophenone imide (Ph(2)C=N(-)); piperidide ((CH(2))(5)N(-)); morpholide (O(CH(2))(4)N(-)); ethylamide (EtNH(-)); diethylamide (Et(2)N(-)); and tert-butylamide (t-BuNH(-)) and RO(-) = tert-butoxide (t-BuO(-)) and acetate (MeCO(2)(-)). The rate law for the formation of the morpholide-substituted complex is first order in trans-[Os(VI)(tpy)(Cl)(2)(NN(CH(2))(4)O)](2+) and second order in morpholine with k(morp)(25 degrees C, CH(3)CN) = (2.15 +/- 0.04) x 10(6) M(-)(2) s(-)(1). Possible mechanisms are proposed for substitution at the 4'-position of the tpy ligand by the added nucleophiles. The key features of the suggested mechanisms are the extraordinary electron withdrawing effect of Os(VI) on tpy and the ability of the metal to undergo intramolecular Os(VI) to Os(IV) electron transfer. These substituted Os(VI)-hydrazido complexes can be electrochemically reduced to the corresponding Os(V), Os(IV), and Os(III) forms. The Os-N bond length of 1.778(4) A and Os-N-N angle of 172.5(4) degrees in trans-[Os(VI)(4'-O(CH(2))(4)Ntpy)(Cl)(2)(NN(CH(2))(4)O)](2+) are consistent with sp-hybridization of the alpha-nitrogen of the hydrazido ligand and an Os-N triple bond. The extensive ring substitution chemistry implied for the Os(VI)-hydrazido complexes is discussed.     

Rapid spectrophotometric determination of chromium(III)

A spectrophotometric procedure is suggested for the determination of Cr(III). The reaction between Cr(III) and 2-(5-bromo-2-pyridylazo)-5-dimethylaminophenol is accelerated by sodium dodecyl sulphate(SDS), sodium benzoate causes a further increase in the absorbance of the chelate. The optimum pH range for the reaction is 5-5.8(benzoate buffer). The chelate exhibits maximum absorbance at 590 nm, obeys Beer's law over the concentration range 0.02-0.56 microg/ml of Cr(III), has molar absorptivity of 7.8 x 10(4) 1. mol(-1) cm(-1) and a Sandell sensitivity of 0.66 ng/cm. The metal to ligand ratio is 1:2 in the absence of SDS and 1:1 in its presence. A procedure for the determination of Cr(III) and Cr(VI), when present together, is described. The method has been applied to the analysis of Cr(III) in tap water.     

Rapid leaching of Cr(VI) in soil with Na3PO4 in the determination of hexavalent chromium by electrothermal atomic absorption spectrometry

A method has been developed that leaches Cr(VI) selectively from soil samples. Hexavalent chromium was leached completely from soil with 0.01molL(-1) Na(3)PO(4). This was achieved by boiling the soil-reagent solution mixture for a period of 5min. The leached Cr(VI) was then quantified by electrothermal atomic absorption spectrometry (ET-AAS) after filtration of the sample solutions through Hydrophilic Millipore PVDF 0.45microm filter. Statistical evaluations indicated that the new developed method is reliable since neither its comparison with the established method nor the comparison of the sum of the concentrations of chromium species to that of the total concentration of chromium show any difference at 95% level of confidence. The spiking of soil samples with Cr(III) standards before pretreatment show that Cr(III) was not oxidized to Cr(VI) during leaching as the Cr(VI) content never increased. The detection limit established was 0.07microg g(-1), which is an improvement to that of the US EPA method 3060A by a factor of more than 500. The maximum concentrations of Cr(VI) found in soil samples collected around the new chromium mine was 8.0microg g(-1) and falls within acceptable level of 15microg g(-1) in accordance with the Italian Guidelines.