Micelle mediated extraction of titanium and its ultra-trace determination in silicate rocks

A highly sensitive method for extractive spectrophotometric determination of titanium in silicate rocks is described. Titanium in the range 0-10 microg as TiO2 is extracted into benzene or toluene by the formation of a ternary complex of the metal with thiocyanate (SCN-) and cetyltrimethylammonium bromide (CTA) in the ratio 1:2:2. A deep yellowish-orange ternary complex thus formed is suitable for the determination of titanium at wavelength 421 nm. The optimum colour intensity of this ternary complex was attained when the complex was extracted from an aqueous solution having concentrations of thiocyanate and HCl, in the range, 1.5-2.5 and 1-5 mol L(-1), respectively. The molar absorptivity and Sandell's sensitivity of the extracted species were found to be 1.1-1.0x10(5) L mol(-1) cm(-1) and 0.47 ng cm(-2) (referred to titanium), respectively, at lambda(max) of 421 nm. Except Fe3+, Nb5+ and V5+, no interference was encountered in the estimation of titanium. While up to 10 mg L(-1) Nb and V did not interfere in the determination of titanium, the interference of Fe(3+) was eliminated by reducing it to Fe2+ using SnCl2 solution. The method is highly sensitive and selective. The results obtained for titanium estimation in a host of silicate rock samples have been found to be highly reproducible, accurate and favourably comparable with certified values of reference materials and those obtained from standard methods.     

Rapid, selective, direct and derivative spectrophotometric determination of titanium with 2,4-dihydroxybenzaldehyde isonicotinoyl hydrazone

A simple and sensitive spectrophotometric method is developed for the determination of titanium in aqueous medium. The metal ion forms a reddish brown coloured complex with 2,4-dihydroxybenzaldehyde isonicotinoyl hydrazone (2,4-DHBINH) in the pH range 1-7. The complex shows two absorption maxima, one at 430 nm and the other at 500 nm. The reagent shows appreciable absorbance of 430 nm and negligible absorbance at 500 nm at pH 1.5. Beer's law is obeyed in the range 0.09 to 2.15 mug ml(-1) of titanium(IV). The molar absorptivity and the Sandell's sensitivity of the method are 1.35 x 10(4) 1 mol(-1) cm(-1) and 0.0049 mug cm(-2), respectively. A method for the determination of titanium by first-order derivative spectrophotometry is also proposed. The methods have been employed successfully for the determination of titanium in several alloy and steel samples.     

Reversed phase HPLC determination of titanium(IV) and iron(III) with sodium 1,2-dihydroxybenzene-3,5-disulfonic acid

A highly sensitive method has been developed for the determination of titanium(IV) and iron(III) by ion-pair reversed phase liquid chromatography using sodium 1,2-dihydroxybenzene-3,5-disulfonic acid (Tiron) as a precolumn chelating reagent. The metal - Tiron chelates were separated on a C₁₈ (ODS) column; the mobile phase was a 2:8 (v/v) mixture of acetonitrile and acetate buffer (0.04 mol/L, pH 6.2) containing 2.0 × 10^?3 mol/L Tiron, 0.04 mol/L tetrabutylammonium bromide, and 0.1 mol/L potassium nitrate. The detection limits for titanium(IV) and iron(III) are 0.5 and 2.0 μg/L, respectively. The method has been applied to the simultaneous determination of titanium(IV) and iron(III) in river water samples and has furnished highly precise results.     

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.     

Study of the titanium-phenylfluorone complex formed in the presence of Triton X-305 and emulsifier OP

A highly sensitive method for the spectrophotometric determination of titanium with phenylfluorone (PF) in the presence of Triton X-305 and emulsifier OP has been developed. In acid medium (pH 1.4-2.2) Ti(IV) forms red-violet complexes with PF, Triton X-305 and OP. The complex exhibits maximum absorption at 540 nm. The molar absorptivity is 1.63 x 10(5) 1.mole(-1).cm(-1). The Ti:PF ratio in the complex is 1:2. Beer's law is obeyed in the titanium concentration range 0-0.2 microg/ml in the final solution. Fluoride and EDTA interfere. The method has been used for the rapid direct determination of microamounts of Ti(IV) in soils and cereals with satisfactory results.     

Simultaneous determination of titanium and molybdenum in steel samples using derivative spectrophotometry in neutral micellar medium

A simple, selective and sensitive spectrophotometric method has been developed for the individual and simultaneous determination of Ti(IV) and Mo(VI) using resacetophenone p-hydroxybenzoylhydrazone (RAPHBH) in presence of Triton X-100, without any prior separation. Beer's law is obeyed between 0.13-1.2 microg mL-1 and 0.18-1.90 microg mL-1 concentration of Ti(IV) and Mo(VI) at 455 nm and 405 nm, respectively. The molar absorptivity and Sandell's sensitivity of the coloured complexes at pH 3.0 are 3.1x10(4) L mol-1 cm-1, 4.2x10(4) L mol-1 cm-1, and 1.6 ng cm-2, 2.3 ng cm-2 for Ti(IV) and Mo(VI), respectively. The stoichiometry of the complexes were found to be 1:2 and 1:1 (metal:ligand) for Ti(IV) and Mo(VI), respectively. These metal ions interfere with the determination of each other in zero-order spectrophotometry. The first derivative spectra of these complexes permitted a simultaneous determination of Ti(IV) and Mo(VI) at zero crossing wavelengths of 500.0 nm and 455.0 nm, respectively. The effect of foreign ions in the determination of Ti(IV) and Mo(VI) were investigated. The proposed method has been successfully applied for the determination of titanium and molybdenum in standard alloy steel, mineral and soil samples.     

Selective extraction and photometric determination of trace vanadium with cinnamohydroxamic acid in MIBK and its application to steel and rock ore analysis

A sensitive and selective photometric method for the trace determination of vanadium with cinnamohydroxamic acid extracted from 1.8 M HCl in methyl isobutyl ketone is described. The wine-red chelate formed under an optimum acidity of 1.3-2.6 M HCl absorbs with a maximum at 525 nm. Beer's law is obeyed in the range 0-8 ppm of vanadium(V) and the optimum range of determination of vanadium is found to be 1-8 ppm. The molar absorptivity and Sandell's sensitivity are 6.0 x 10(3) l mol(-1) cm(-1) and 0.0086 mug cm(-2) of vanadium(V) at 525 nm. The photometric determination of trace amounts of vanadium in materials such as alloys, minerals and rock ores is also reported. The solvent extraction methods are simple, rapid and highly selective with fluoride used as a masking agent for Fe and Ti. The standard deviations are minimal and the mean error is only 0.015%.     

Spectrophotometric determination of thorium in standard samples and monazite sands based on the floated complex of thorium with N-hydroxy-N,N′-diphenylbenzamidine and thorin

A selective and sensitive spectrophotometric method for the determination of Th(IV) has been based on the reaction with thorin and subsequent extraction of the red-orange coloured complex with N-hydroxy-N,N'-diphenylbenzamidine (HDPBA) in benzene as floated complex at pH 2.2. The complex in ethanol exhibits a maximum absorbance at 495 nm, with a molar absorptivity of 6.0x10(4) l mol(-1) cm(-1), with a Sandell's sensitivity of 3.9x10(-3) microg cm(-2). The method follows Beer's law up to 3.0 microg Th(IV) ml(-1). None of the common cations and anions tested interfere. The detection limit of the method is 0.04 microg Th(IV) ml(-1), the RSD (n=10) is 1.4%. The method has been successfully employed for the determination of thorium in various standard and monazite samples.     

2-Hydroxy-1-naphthaldoxime as an analytical reagent for titanium(IV)

2-Hydroxy-1-naphthaldoxime is proposed as a new selective and sensitive reagent for titanium. The oxime complex can be dried to constant weight at 105-110 degrees and the conversion factor is 0.1793. The method is sensitive and gives reproducible results. Quantitative separation of titanium(IV) from iron(III) and other metals by this method gives good results. The method has been applied to the gravimetric determination of titanium(IV) in ilmenite and the results are in good agreement with those obtained by the cupferron method. The dried complex has definite composition [TiO(OH)(C(11)H(8)O(2)N)](2) and is a non-electrolyte. The dimeric structure proposed for the complex is based on evidence from elemental analysis, molecular weight determination, magnetic susceptibility and infrared spectral data.     

Spectrophotometric determination of lead in biological samples with dibromo-p-methyl-methylsulfonazo

A new highly sensitive and selective chromogenic reagent, dibromo-p-methyl-methylsulfonazo (DBM-MSA), was studied for determination of lead. In 0.24 mol l(-1) phosphoric acid medium, which greatly increases the selectivity, lead reacts with DBM-MSA to form a 1:2 blue complex which has a sensitive absorption peak at 642 nm. Under the optimal conditions, Beer's law was obeyed over the range 0-0.6 mug ml(-1) Pb(II). The molar absorptivity and Sandell's sensitivity are 1.02x10(5) l mol(-1) cm(-1) and 0.00203 mug cm(-2), respectively. The limit of quantification, limit of detection and relative standard deviations were found to be 7.30 and 2.21 ng ml(-1) and 1.1%, respectively. It is found that, except for Ca(II) and Ba(II), all foreign ions studied do not interfere with the determination. The interference caused by Ca(II) and Ba(II) can be easily eliminated by prior extraction with potassium iodide-methylisobutylketone. The method has been applied to the determination of lead in some biological samples with satisfactory results.     

A highly sensitive spectrophotometric determination of platinum(IV) using leuco xylene cyanol FF

A new, simple, highly sensitive and rapid spectrophotometric method has been described for the determination of platinum(IV). The method is based on the oxidation of leuco xylene cyanol FF (LXCFF) to its blue form of xylene cyanol FF by platinum(IV) in sulfuric acid medium (pH 1.0-2.5), the formed dye shows an absorption maximum at 620 nm in acetate buffer medium (pH 3.0-4.5). The method obeys Beer's law over a concentration range of 0.3 to 2.6 micro g mL(-1) platinum, having molar absorptivity and Sandell's sensitivity of 5.1x10(4) L mol(-)(1) cm(-1) and 0.0038 micro g cm(-2), respectively. The optimum reaction conditions and other analytical parameters have been evaluated. The developed method has been successfully applied to the determination of platinum in pharmaceutical preparations, soil, natural water, plant material, platinum-containing catalyst, and synthetic alloy samples.     

A chromogenic calixarene hydroxamic acid for the sequential separation of Ti(IV) and Zr(IV)

A new chromogenic calixarene with hydroxamic acid as chelating agent was synthesized by partial reduction of nitrocalixarene which was subsequently coupled with coumarin chloride. The reagent showed selective and quantitative extraction of Ti(IV) into chloroform at 6 M HCl and that of Zr(IV) at 0.5 M HCl. A facile liquid-liquid extraction method for the separation and spectrophotometric determination of Ti(IV) and Zr(IV) has been proposed. The validity of the method was checked by separating several synthetic mixtures. The method was successfully applied to the analysis of piezoelectric lead-zirconium-titanate (PZT) samples. The method shows remarkable simplicity and selectivity. The method can also be used for the determination of Ti(IV) and Zr(IV) in various environmental samples. The article is published in the original.     

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.     

New Spectrophotometric Method for the Determination of Titanium in Soil and Standard Geochemical Samples

Abstract

In the present communication a simple and rapid spectrophotometric method for the determination of titanium is described. The method is based on the reaction of Ti(IV) with a newly synthesized reagent, 6-(4-nitrophenylazo)-3,4,5-trihydroxy benzoic acid (NATHB), in ethanol medium at pH 3.2 to 4.2. The complex exhibits an absorption maximum at 495 nm and Beer's law is valid over the range of 0.04 – 1.00 μg.ml^?1 Ti. The molar absorptivity is 3.48 × 10⁴ dm³.mole^?1. cm^?1. Most of the foreign metal ions and anions do not produce any colorations with NATHB at selected conditions. Based on these results, a simple and direct spectrophotometric method with high selectivity and sensitivity was proposed. The method has been successfully applied for the determination of titanium in 5 soil and 3 standard geochemical samples.     

Extractive spectrophotometric determination of tungsten(VI) using 3-hydroxy-2-(2'-thienyl)-4-oxo-4H-1-benzopyran

A simple, rapid, highly sensitive and selective spectrophotometric method for the determination of tungsten(VI) in trace amounts is developed using 3-hydroxy-2-(2'-thienyl)-4-oxo-4H-1-benzopyran (HTB) as a reagent for the complexation of metal ion and extracting the 1:2 (metal:ligand) complex into dichloromethane from 0.2 M HCl solution. It obeys Beer's law in the range 0-2.8 microg Wml(-1) with molar absorptivity and Sandell's sensitivity at 415 nm as 6.45 x 10(4) L mol(-1) cm(-1) and 0.0029 microg W(VI) cm(-2), respectively. The method is free from the interference of a large number (39) of elements and handles satisfactorily the analysis of various samples of varying complexity.     

Rapid and sensitive spectrophotometric determination of cerium(IV) with 2,4-dihydroxy benzophenone benzoic hydrazone

A simple and sensitive spectrophotometric method for the determination of cerium(IV) in an aqueous medium is reported. The metal ion formed a 1:1 orange-red coloured complex with 2,4-dihydroxy benzophenone benzoic hydrazone (DHBPBH) at pH 10.0 showing an absorption maximum at 400 nm. The molar absorptivity and Sandell's sensitivity of the method are found to be 2.0 x 10(4)1/mol/cm and 0.007 mug/cm(2), respectively. Beer's law is obeyed in the range 0.7-7.0 mug/ml. Titanium, vanadium and molybdenum do not interfere. The extent of interferences by other ions is presented. The method is applied for the determination of cerium in simulated rock samples.     

Solvent extraction and spectrophotometric determination of titanium(IV) with 3-phenyl-3-methyl-2-mercaptopropenoic acid

The distribution equilibria of 3-phenyl-3-methyl-2-mercaptopropenoic acid (PhMMP) and the titanium(IV)-PhMMP complex have been studied. An extraction-photometric method for the determination of microamounts of titanium has been developed. We have investigated the influence of pH, the reagent, and the presence of electrolytes and masking agents in the aqueous phase on the equilibrium. From the slope analysis of the distribution curves the composition of the extracted species has been found to be Ti(OH)₂(HR)₂. The complex is extracted quantitatively. Beer's Law is followed over the range 0.09–3.74 μg ml^?1 of titanium(IV), the molar absorptivity is 1.65 × 10⁴ liters mol^?1 cm^?1, and the Sandell sensitivity is 2.8 ng cm^?2 at 439 nm. This method has been applied to the determination of titanium in a bauxite.     

Extractive-spectrophotometric determination of molybdenum with 4-unsubstituted-5-pyrazolones

A fairly sensitive and selective method for rapid determination of tracer amounts of molybdenum(V) as mixed-ligand complexes with thiocyanate and 4-unsubstituted-5-pyrazolones is described. The red complexes are extractable into chloroform from 1-5M hydrochloric or perchloric acid or 1-3M sulphuric arid media. The molar absorptivities are in the range 1.72-2.15 x 10(4)l.mole(-1).cm(-1) at 455 nm (lambda(max)). The method has been applied to the estimation of molybdenum in various synthetic and alloy-steel samples. In presence of excess of the reagent, Cu(II), Co(II), Mn(II), Fe(II), Fe(III), Al(III), Cr(III), Cr(VI), Ti(III), Ti(IV), Zr(IV), Hf(IV), V(III), V(IV), V(V), Nb(V), Ta(V), W(VI) and U(VI) do not interfere.     

Capillary electrophoresis and circular dichroism study of trichosanthin and its mutants

A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminoaniline (QADEAA) was synthesized. A highly sensitive, selective and rapid method for the determination of silver based on the rapid reaction of silver (I) with QADEAA has been developed. In the presence of sodium citrate-sodium hydroxide buffer solution (pH 6.5) and sodium dodecyl sulfonate (SDS) medium, QADEAA reacts with silver to form a violet complex of molar ratio 1:2 (silver to QADEAA). The molar absorptivity of the complex is 1.39x10(5) l mol(-1) cm(-1) at 580 nm. Beer's law is obeyed in the range of 0.01-0.6 mug ml(-1). The relative standard deviation for 11 replicate samples of 0.2 mug ml(-1) is 1.67%. This method can be applied to the determination of silver in water with satisfactory results.     

Spectrophotometric determination of silver with 2-(2-quinolylazo)-5-diethylaminophenol as chromogenic reagent

A new chromogenic reagent, 2-(2-quinolylazo)-5-diethylaminophenol (QADEAP) was synthesized. A highly sensitive, selective and rapid method for the determination of silver based on the rapid reaction of silver(I) with QADEAP has been developed. In the presence of citric acid-sodium hydroxide buffer solution (pH=5.0) and sodium dodecyl sulfonate (SDS) medium, QADEAP reacts with silver to form a violet complex of a molar ratio 1:2 (silver to QADEAP). The molar absorptivity of the complex is 1.33x10(5) L mol(-1) cm(-1)at 590 nm. Beer' s law is obeyed in the range of 0.01-0.6 micro g mL(-1). The relative standard deviations for eleven replicate samples of 0.2 microg mL(-1) is 1.38%. This method was applied to the determination of silver in water with satisfactory results.