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.     

Use of binary metal deposits on a cylindrical carbon-fiber microelectrode in the voltammetric determination of metal ions

The effect of binary metal deposits on a cylindrical carbon-fiber microelectrode on the determination of metals by direct and stripping voltammetry was studied. The electrolytic deposition of a binary system of copper and thallium, cadmium, lead, or mercury on the electrode in an alkaline solution resulted in the disappearance of the electroreduction peak of dissolved oxygen in the potential range from -0.8 to -1.4 V and in a decrease in the background current. Under the conditions of limited diffusion, the peak currents of Ni(II), Co(II), and Zn(II) in differential pulse voltammograms were 3–7 times higher than those calculated for a reversible electrode process under the conditions of semi-infinite diffusion. Because of this, the determination limit for metal ions in direct voltammetry was lowered to 1 X 10^-6 M. With a binary copper-thallium system, the peak current of zinc(II) reduction can be be detected in the presence of 5000-fold molar amounts of copper(II). The deposition of binary copper-lead and copper-thallium systems under the conditions of limited diffusion reduced the effect of negative interaction between the components of these systems and made possible the determination of lead(II) and thallium(I) by stripping voltammetry using additional peaks.     

Square-wave anodic stripping voltammetric determination of thallium(I) at a Nafion/mercury film modified electrode

A Nafion/mercury film electrode (NMFE) was used for the determination of trace thallium(I) in aqueous solutions. Thallium(I) was preconcentrated onto the NMFE from the sample solution containing 0.01 M ethylenediaminetetraacetate (EDTA), and determined by square-wave anodic stripping voltammetry (SWASV). Various factors influencing the determination of thallium(I) were thoroughly investigated. This modified electrode exhibits good resistance to interferences from surface-active compounds. The presence of EDTA effectively eliminated the interferences from metal ions, such as lead(II) and cadmium(II), which are generally considered as the major interferents in the determination of thallium at a mercury electrode. With 2-min preconcentration, linear calibration graphs were obtained over the range 0.05-100 ppb of thallium(I). An even lower detection limit, 0.01 ppb, were achieved with 5-min accumulation. The electrode is easy to prepare and can be readily renewed after each stripping experiment. Applicability of this procedure to various water samples is illustrated.     

A new resin containing benzimidazolylazo group and its use in the separation of heavy metals

A new resin incorporating benzimidazolylazo group into a matrix of polystyrene divinylbenzene has been prepared. The exchange capacity of the resin for the ions mercury(II), silver(I) and palladium(II) as a function of pH has been determined. The resin exhibits no affinity for alkali or alkaline earth metals. It is highly selective for Hg(II), Ag(I) and Pd(II). In column operation, it has been observed that Hg(II), Ag(I) and Pd(II) in trace quantities can be selectively separated from geological, medicinal and environmental samples.     

Extraction separation of thallium (III) from thallium (I) with n-octylaniline

A novel method is developed for the extraction separation of thallium(III) from salicylate medium with n-octylaniline dissolved in toluene as an extractant. The optimum conditions have been determined by making a critical study of weak acid concentration, extractant concentration, period of equilibration and effect of solvent on the equilibria. The thallium (III) from the pregnant organic phase is stripped with acetate buffer solution (pH 4.7) and determined complexometrically with EDTA. The method affords the sequential separation of thallium(III) from thallium(I) and also commonly associated metal ions such as Al(III), Ga(III), In(III), Fe(III), Bi(III), Sb(III) and Pb(II). It is used for analysis of synthetic mixtures of associated metal ions and alloys. The method is highly selective, simple and reproducible. The reaction takes place at room temperature and requires 15-20 min for extraction and determination of thallium(III).     

Determination of thallium in bismuth by differential pulse anodic-stripping voltammetry without preliminary separation

The determination of trace levels of thallium in bismuth and bismuth salts by differential pulse anodic-stripping voltammetry has been made possible by using a surfactant as an electrochemical masking agent, in addition to a complexing agent. In 0.2M EDTA at pH 4.5 as supporting electrolyte in the absence of surfactant, bismuth at concentrations below 10(-4)M does not interfere. When the electrolyte also contains tetrabutylammonium ions at 0.01 M concentration, bismuth can be tolerated at concentrations up 0.05M, and the height of the thallium peak is unaffected. It is thus possible to determine 1 nM Tl(I) in the presence of 0.05M Bi(III), i.e., Tl at the 1 x 10(-6)% level in bismuth. The precision of the determination and the recovery are satisfactory. Neither an 800-fold ratio of Cu(II) nor a 10(7)-fold ratio of Pb(II) to Tl(I) interferes in the determination. Other cations such as Zn(2+), Cd(2+), In(3+), Hg(2+), Fe(3+), Sb(3+) and Sn(4+) in 10(4)-fold molar ratio to Tl(I) have no effect on the determination. Thallium has been determined in bismuth metal and in bismuth nitrate of various degrees of purity.     

Complexometric determination of some toxic mixtures of ions using bromo-cresol orange with visual endpoint indication

A rapid and simple general complexometric method was presented for the determination of lead, cadmium and thallium or mercury or arsenic(V) in laboratory synthesized mixtures similar to those of some ores, minerals and alloys of such metals. The precision and accuracy attainable in successive titrations of Pb(2+), Cd(2+) and Tl(3+) or Hg(2+) or AsO(3-)(4) (As(5+)) with 0.05 and/or 0.01 mol 1(-1) solutions of disodium ethylenediaminetetraacetate (Na(2)EDTA) and standard Pb(NO(3))(2) of the same concentration using Bromo-Cresol Orange (BCO) as a new metallochromic indicator with visual endpoint indication were studied. For the analysis of a three component mixtures of the aforementioned ions, Tl(3+) was at first directly titrated with Na(2)EDTA at pH 0.5-1 (HNO(3)) using BCO as indicator. At the thallium endpoint an excess of Na(2)EDTA was added and the pH was adjusted at pH approximately 4.8 using hexamine-HNO(3) buffer (solution A). The excess EDTA was back-titrated with standard solution of Pb(NO(3))(2). 1,10-Phenanthroline (1,10-phen) was added to release the EDTA combined with Cd(2+), while thiosemicarbazide (TSC) was used to liberate the EDTA from the mercury-EDTA chelate. To determine AsO(3-)(4) ion in such type of mixtures the pH of (solution A) was raised to a value of 10 using ammonia buffer. Excess standard Mg(2+) solution was added and the formed precipitate of MgNH(4)AsO(4) was separated, dissolved and its magnesium content equivalent to AsO(3-)(4) was determined complexometrically using Eriochrome Black-T (EBT) indicator. The interference caused by different anions, cations and organic acids was investigated. A comparison of the indicators BCO and Xylenol Orange (XO) for successive titration of the studied metal ions was carried out. The proposed successive titration method was applied successfully to some real samples of ores, minerals and alloys of the studied metal ions and the results were satisfactory and agreed with those obtained by AAS.     

The use of phenylfluorone in the presence of cetylpyridinium chloride and Triton X-100 for the spectrophotometric determination of copper(II) in blood serum

A simple and sensitive spectrophotometric method for determination of copper(II) is based on the formation of a blue coloured complex of Cu(II) with 9-phenyl-2,3,7-trihydroxy-6-fluorone (PF) in the presence of cetylpyridinium chloride (CP) and Triton X-100, has been developed. Optimum concentrations of PF, CP, Triton X-100 and pH ensuring maximum absorbance were defined. The complex Cu(II)-PF-CP-Triton X-100 shows maximum absorbance at 595 nm with a molar absorptivity value of 9.67x10(4) l mol(-1) cm(-1). The detection limit of the method is 0.028 mug ml(-1). Beer's law is obeyed for copper concentrations in the range 0.04-0.4 mug ml(-1). The studies of the effect of foreign ions on determination of copper, show that the selectivity of the method is poor. The cations of alkali metals and anions Br(-), Cl(-), I(-), F(-), NO(2)(-), NO(3)(-), CH(3)COO(-), SO(4)(2-), S(2)O(3)(2-), PO(4)(3-), citrates (examined in 1000-fold molar excess over copper) do not affect the determination. All cations forming complexes with PF have an interfering effect. The statistical evaluation of the method was carried out for six determinations using 10 mug of Cu and the following results were obtained: the standard deviation, SD=0.042, the confidence interval mu(95)=10.1+/-0.1 mug Cu. The method has been applied for determination of copper in blood serum.     

Analytical applications of a liquid anion-exchanger for the separation of uranium(IV) in malonate solution

Uranium was quantitatively extracted with 4% Amberlite LA-1 in xylene at pH 2.5-4.0 from 0.001 M malonic acid. It was stripped from the organic phase with 0.01 M sodium hydroxide and determined spectrophotometrically at 530 nm as its complex with 4-(2-pyridylazo) resorcinol. Of various liquid anion-exchangers tested, Amberlite LA-1 was found to be best. Uranium was separated from alkali and alkaline earth metal ions, thallium(I), iron(II), silver, arsenic(III) and tin(IV) by selective extraction, and from zinc, cadmium, nickel, copper(II), cobalt(II), chromium(III), aluminium, iron(III), lead, bismuth, antimony(III) and yttrium by selective stripping. The separation from scandium, zirconium, thorium and vanadium(V) was done by exploiting differences in the stability of chloro-complexes.     

Detection of metal ions using ion-channel sensor based on self-assembled monolayer of thioctic acid

Gold electrodes were chemically modified with thioctic acid monolayer designed to mimic biological ion-channel membranes. The technique was then used in the determination of alkali, alkaline earth, thallium(I), and lanthanum metal cations as analytes. Cyclic voltammograms (CV) of [Fe(CN)6]³⁻ an electroactive marker, were measured in the presence of the various types of analyte cations. In the absence of the analyte cation, electrostatic repulsion between the marker anions and the carboxylate groups of the receptor monolayer hindered the approach of the marker anion to the electrode surface and hence hindered its reduction. The modified electrodes responded well to the metal cations except the alkali metal cations. The sensors could detect the trivalent cation La³⁺ at concentrations as low as 10⁻⁸ M. The response of the sensor to the metal cations increase in the order alkali metal3+ can be discriminated in the ratio 1:100. This makes it possible to determine the trivalent ion in a sample matrix containing monovalent and divalent cations. Thallium(I) ion showed marked deviation in its response as compared to monovalent ions of the alkali metals. The ion-channel sensor based on self-assembled monolayer of thioctic acid therefore offers a potential alternative technique for the selective determination of metal ions.     

Complexometric determination of palladium(II) using thioacetamide as a selective masking agent

A simple, rapid and accurate complexometric method for the determination of palladium(II) is proposed, based on the selective masking property of thioacetamide towards palladium(II). In the presence of diverse metal ions, palladium(II) is complexed with excess of EDTA and the surplus EDTA is back titrated at pH 5-5.5 (acetic acid-sodium acetate buffer) with standard lead nitrate solution using xylenol orange as indicator. An excess of a 0.5% aqueous solution of thioacetamide is then added to displace EDTA from Pd(II)-EDTA complex. The released EDTA is titrated with the same standard lead nitrate solution as before. Reproducible and accurate results are obtained in the concentration range 0.5 mg - 17.80 mg of palladium with relative error of +/- 0.16% and coefficient of variation not exceeding 0.26%. The effect of diverse ions is studied. The method is used for the determination of palladium in its complexes, catalysts and synthetic alloy mixtures.     

Spectrophotometric extractive titrations-IV Determination of zinc in germanium dioxide and germanium chloride

A simple and selective determination of zinc in germanium chloride and germanium dioxide is described. The sample is dissolved in sodium potassium tartrate solution and zinc is titrated spectrophotometrically at 532 mug( with a dithizone solution in carbon tetrachloride without discarding the organic phase. Interfering ions such as Bi(III), Cu(II), Cd(II), Co(II), Ni(II), Pb(II), Sn(II), Fe(II), Fe(III), Mn(II) and T1(I) are masked with bis(2-hydroxyethyl)dithiocarbamate. The detection limit is 3-23 x 10(-5)% of zinc and this may be lowered by taking a larger sample and by performing the analysis in a closed system. A simplified technique, consisting of the simultaneous titration of the sample and blank, is described.     

Determination of trace amounts of thallium by adsorptive cathodic stripping voltammetry with xylenol orange.

Trace amounts of thallium(I) can be determined using adsorptive cathodic stripping voltammetry in the presence of Xylenol Orange (XO). The reduction current of the thallium(I)-XO complex ion was measured by square-wave cathodic stripping voltammetry. The peak potential was at -0.44 V vs. Ag/AgCl. The effect of various parameters (pH, ligand concentration, accumulation potential and collection time) on the response are discussed. The response was linearly related to the thallium concentration in the range 0.5-110 ng ml(-1) and 110-2000 ng ml(-1). The limit of detection was 0.2 ng ml(-1). The relative standard deviation for the determination of 80 ng ml(-1) thallium was 2.8%. Many common anions and cations did not interfere with the determination of thallium. The interference of lead was reduced by the addition of 0.003 M sodium carbonate. The voltammetric procedure was then successfully applied to the determination of thallium in various complex samples.     

Titration of cyanide and hexacyanoferrate(II) with silver nitrate-II Determination of sodium cyanide and sodium hexacyanoferrate(II) in a complexing agent

Cyanide and hexacyanoferrate(II) can be titrated with silver nitrate in the presence of a complexing agent masked with a suitable metal ion. A method for determination of sodium cyanide and sodium hexacyanoferrate(II) in the presence of sodium nitrilotriacetate masked with magnesium ions is given as an example.     

Potentiometric determination of silver(I), palladium(II) and gold(III) in mixtures by use of an iodide-selective electrode

Two procedures are proposed for the potentiometric determination of Ag(I), Pd(II) and Au(III) in binary mixtures, by titration with potassium iodide solution, and use of a commercial iodide electrode as sensor. In the first procedure, two aliquots of the mixture are titrated, at pH 2.0 ± 0.2 and 9.0 ± 0.2, adjusted with dilute sulphuric acid and ammonia solution. At pH 2.0, the titrant reacts with both metals, whereas at pH 9.0, Ag(I) is the only reactant. The second procedure utilizes titration of two aliquots of the mixture in the presence and absence of a selective masking agent. The methods have been applied to the determination of these metals in some jewellery alloys.     

6-phenyl-2,3-dihydro-assym-triazine-3-thione and 5,6-diphenyl-2,3- dihydro-asym-triazine-3-thione as gravimetric reagents for the determination of thallium and palladium

The analytical use of 6-phenyl-2,3-dihydro-asym-triazine-3-thione (PDTT) and 5,6-diphenyl-2,3-dihydro-asym-triazine-3-thione (DDTT) has been investigated. PDTT proved to be suitable for the determination of thallium(I) in the presence of cyanide whereas DDTT is more selective than PDTT in alkaline tartrate solution and is applied for the selective gravimetric determination of palladium. The method is more sensitive than the dimethylglyoxime method. The only metal ions interfering are Hg(II), Ag and Tl(I).     

Vanadium(III) as an analytical reagent: The titrimetric determination of iron, copper, thallium, molybdenum, uranium, vanadium, chromium and manganese

Vanadium(III) solutions can be used in direct titrations of iron(III), copper(II), thallium(III), molybdenum(VI), uranium(VI), vanadium(V), chromium(VI) and manganese(VII) in milligram amounts. The titrations are done at 70-80 degrees for iron(III), copper(II), thallium(III), molybdenum(VI) and at room temperature for vanadium(V), chromium(VI) and manganese(VII). Uranium(VI) is titrated at 70-80 degrees in presence of iron(II). The vanadium(III) solution is prepared by reduction of vanadium(V) to vanadium(IV) with sulphur dioxide, followed by addition of phosphoric acid and reduction with iodide, and is reasonably stable.     

Amperometry with two polarisable electrodes-XI Determination of bismuth by EDTA titration

Optimum conditions have been found for a highly selective determination of bismuth via EDTA titration with biamperometric indication of the end-point. The influence of the applied potential, pH and stirring on the accuracy and selectivity of the determination has been studied. In a medium of 0.4M nitric acid only high concentrations of iron(III) and copper(II) interfere with the determination of bismuth. Zirconium, thallium(III) and indium interfere even in small concentrations. The average error of the determination of 5-100 mg of bismuth (when titrated with 0.05M EDTA solution) is +/-0-1 % rel. and for the determination of 0.5-10 mg it is +/-0.3% rel. (0.005M EDTA). The method has been verified by the analysis of a Wood's metal of known composition.     

Quantitative separation of traces of lead,cadmium and many other elements from gram amounts of thallium by cation-exchange chromatography

Traces of lead and minor amounts up to 20 mg, can be separated from gram amounts of thallium by cation-exchange chromatography on a column containing only 2 g of AG50W-X4 resin. Thallium passes through the column in 0.1 M HCl in 40% acetone. The retained lead can be eluted with 3 M HCl or HNO₃. Other elements, including Cd, Zn, In, Ga, Cu(II), Fe(III). Mn(II), Co(II). Ni(II), U(VI) and Al, are retained quantitatively with lead. Only Hg(II), Au(III), the platinum metals, bismuth and elements forming oxyanions accompanying thallium. Results for the determination of trace elements in 99.999% pure thallium are presented.     

Semi-automatic catalytic titration of metal ion mixtures and its application to metallurgical samples

The semi-automatic catalytic titration of several metal ions and binary mixtures of iron(III) with copper(II), nickel or manganese(II) is described. The 4,4′-dihydroxybenzophenone thiosemicarbazone/hydrogen peroxide system was used in the presence of EDTA or EGTA as inhibitors with copper(II) as catalytic titrant. Two sample aliquots are necessary for the analysis of binary mixtures. In one, both metals are titrated in the presence of EDTA; in the other, only copper, nickel or manganese is titrated with EGTA or EDTA if a masking agent for iron(III) (triethanolamine or fluoride) is added. The iron/metal ratios tolerated range from 1:14 to 13:1 for the 0.2–3.0 μmol range, the relative standard deviation being 1–2%. The method was applied to metallurgical samples with good results.