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.     

Determination of thallium in the presence of large excess of lead by anodic stripping voltammetry

The paper is concerned with the determination of traces of thallium, as T1(I), in the presence of very large amounts of lead, by d.c. anodic stripping voltammetry, by adding both a complexing agent and anionic surfactant. The supporting complexing agent was 0.1M solution of EDTA (pH 4.4). The influence of the several surfactants on the signals of lead and thallium was investigated.In 0.1M EDTA at pH 4.4 at the absence of a surfactant, lead does not interfere at concentrations below 10^–4 M. When the electrolyte contains also an anionic surfactant, lead can be tolerated at concentrations up to 2 × 10^–3–6 × 10^–3 M (depending on the type of the surfactant), and the height of the thallium peak remains unaffected. This makes the determination of 10^–8 M T1(I) possible when the molar excess of lead is 2–6 × 10⁵ fold. The method has been tested by determining the thallium content of soil extracts.     

Application of polyethylene glycol for "electrochemical masking" in direct-current polarography

The use of polyethylene glycols (PEG) of molecular weight from 200 to 15,000 for electrochemical masking has been investigated. A pH-4.4 tartrate buffer was found to be the most suitable supporting electrolyte, and 0.1% the optimum PEG concentration. PEGs of m.w. below 600 had little effect on the waves examined, and are useless for electrochemical masking. Under the conditions chosen, the waves of Bi(III), Sb(III) and In(III) are completely suppressed; the Cd(II) and Pb(II) waves are shifted to more negative potentials, and the Tl(I) wave is scarcely affected by PEGs. The Cu(II) wave behaves differently from the others. A method is proposed for the determination of lead and/or thallium in the presence of up to 5000-fold w/w ratios of bismuth, antimony or indium. The determination of both lead and thallium is only possible when the amounts are not too different, as the waves are quite close. Copper(II) interferes.     

Anodic stripping voltammetry with mercury electrodes in extracts of cadmium,lead, thallium and indium diethyldithiocarbamate complexes and analysis of mixtures

The selectivity of the determination of traces of cadmium, lead, thallium and indium is improved by direct coupling of liquid/liquid extraction and anodic stripping voltammetry. Metals are extracted from aqueous solution to benzene or chloroform after the addition of sodium or zinc diethyldithiocarbamate. Stripping voltammetry of Cd, Tl and Pb at a hanging mercury drop electrode or mercury film electrode is done in benzene/methanol medium (1:1) with 0.1 M NaClO₄ as supporting electrolyte. For indium, the medium is chloroform/ethanol/water (1:4:1) with 0.005 M sodium acetate/0.06 M KBr/0.06 M HCl as supporting electrolyte. The complexes in acidic solution can be decomposed by mercury (II) ions, which provides useful shifts of deposition potentials. Calibration graphs are linear at concentrations of about 10^?7 M with a detection limit of 1×10^?8 M. The method is applied to determine a single metal in the presence of a large amount (1000-fold) of interfering metal.     

Anodic stripping voltammetric determination of thallium as [TlBr4]-rhodamine B complex

The anodic stripping voltammetric behaviour of the [TlBr₄]-rhodamine B complex is described and compared with that of thallium(I) and thallium(III) ions. The electrolyte composition, the best potential for the deposition of thallium from the complex in the selected electrolyte, the duration of the electrolysis, and the possibility of reduction of thallium in the [TlBr₄]-rhodamine B complex before the electrolysis with ascorbic acid were investigated. The results showed good reproducibility of the measurements of thallium as [TlBr₄]-rhodamine B complex and are similar to those obtained for thallium as Tl(I) and Tl(III) ions. As the [TlBr₄]-rhodamine B complex is strongly adsorbed on polyethylene, a previous preconcentration step on a column, packed with polyethylene powder, allowed the voltammetric determination of thallium as [TlBr₄]-rhodamine B complex in samples of KCl and NaCl as solid salts after the separation of the matrix. With this procedure it was possible to reach enrichment factors of 25 with recoveries from 96.7 to 107.9% for thallium concentrations from 5 to 40 μg L^–1 and RSD between 4.2 and 9.2%. The procedure was used to determine thallium traces in KCl and in sea salt. The results of these determinations were compared with the results obtained by graphite furnace atomic absorption spectrometry.     

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.     

Anodic stripping voltammetric determination of thallium as [TlBr4]-rhodamine B complex

The anodic stripping voltammetric behaviour of the [TlBr₄]-rhodamine B complex is described and compared with that of thallium(I) and thallium(III) ions. The electrolyte composition, the best potential for the deposition of thallium from the complex in the selected electrolyte, the duration of the electrolysis, and the possibility of reduction of thallium in the [TlBr₄]-rhodamine B complex before the electrolysis with ascorbic acid were investigated. The results showed good reproducibility of the measurements of thallium as [TlBr₄]-rhodamine B complex and are similar to those obtained for thallium as Tl(I) and Tl(III) ions. As the [TlBr₄]-rhodamine B complex is strongly adsorbed on polyethylene, a previous preconcentration step on a column, packed with polyethylene powder, allowed the voltammetric determination of thallium as [TlBr₄]-rhodamine B complex in samples of KCl and NaCl as solid salts after the separation of the matrix. With this procedure it was possible to reach enrichment factors of 25 with recoveries from 96.7 to 107.9% for thallium concentrations from 5 to 40 μg L^–1 and RSD between 4.2 and 9.2%. The procedure was used to determine thallium traces in KCl and in sea salt. The results of these determinations were compared with the results obtained by graphite furnace atomic absorption spectrometry. Received: 5 February 1998 / Revised: 19 May 1998 / Accepted: 29 May 1998     

Thallium(I) Tropolonates: Synthesis,Structure, Spectral Characteristics,and Antimicrobial Activity Compared to Lead(II) and Bismuth(III) Analogues

Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR (¹H, ¹³C, ¹⁹F and ²⁰⁵Tl), UV–vis, and luminescence spectra characteristics were described for series of thallium(I) compounds: thallium(I) triflate (Tl(OTf)), 1:1 co-crystals of thallium(I) triflate and tropolone (Htrop), Tl(OTf)·Htrop, as well as simple thallium(I) chelates: Tl(trop) (1), Tl(5-metrop) (2), Tl(hino) (3), with Htrop, 5-methyltropolone (5-meHtrop), 4-isopropyltropolone (hinokitiol, Hhino), respectively, and additionally more complex {Tl@[Tl(hino)]₆}(OTf) (4) compound. Comparison of their antimicrobial activity with selected lead(II) and bismuth(III) analogs and free ligands showed that only bismuth(III) complexes demonstrated significant antimicrobial activity, from two- to fivefold larger than the free ligands.     

Second harmonic a.c. anodic stripping voltammetry of metals at trace level: simultaneous determination of lead and thallium, and bismuth and antimony

Pairs of elements with very small differences in their half-wave potentials were determined at trace levels by second harmonic a.c. anodic stripping voltammetry. The simultaneous determination of lead and thallium as well as that of bismuth and antimony in 1M hydrochloric acid as supporting electrolyte was found to be possible in the range of concentration ratios: 7:1 > or = C(Pb):C(Tl) > or = 1:36 and 45:1 > or = C(Sb):C(Bi) > or = 1:35, with <5 % relative error due to mutual interference. The limit of detection was approximately 10(-8)M for all four elements, and the precision and error were 2-3%. The simultaneous determination of these metals in mixtures with concentration ratios outside the quoted ranges is still feasible by the standard-addition technique.     

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.     

Determination of copper in the presence of a large excess of bismuth by differential-pulse anodic-stripping voltammetry without preliminary separation

Conditions have been found which make possible the determination of copper in the presence of a large excess of bismuth by differential-pulse and anodic-stripping voltammetry without preliminary separation. The electrochemical activity of the bismuth, which usually interferes in the determination of copper, is inhibited by using tetrabutylammonium chloride (TBAC) as surfactant. In 0.2M EDTA and 0.01M ascorbic acid at pH 4.5 as supporting electrolyte without the surfactant present, trace levels of copper (1.5 x 10(-8)M) can be determined accurately if the molar ratio of bismuth to copper is not higher than 3, but if the electrolyte also contains TBAC at 0.01M concentration, bismuth can be tolerated in concentrations up to 10(-4)M, and the height of the copper peak is unaffected.     

Solubility, complex formation, and redox reactions in the Tl2O3-HCN/CN(-)-H2O system. Crystal structures of the cyano compounds Tl(CN)3.H2O, Na[Tl(CN)4].3H2O, K[Tl(CN)4], and Tl(I)[Tl(III)(CN)4] and of Tl(I)2C2O4

Thallium(III) oxide can be dissolved in water in the presence of strongly complexing cyanide ions. Tl(III) is leached from its oxide both by aqueous solutions of hydrogen cyanide and by alkali-metal cyanides. The dominating cyano complex of thallium(III) obtained by dissolution of Tl2O3 in HCN is [Tl(CN)3(aq)] as shown by 205Tl NMR. The Tl(CN)3 species has been selectively extracted into diethyl ether from aqueous solution with the ratio CN-/Tl(III) = 3. When aqueous solutions of the MCN (M = Na+, K+) salts are used to dissolve thallium(III) oxide, the equilibrium in liquid phase is fully shifted to the [Tl(CN)4]- complex. The Tl(CN)3 and Tl(CN)4- species have for the first time been synthesized in the solid state as Tl(CN)3.H2O (1), M[Tl(CN)4] (M = Tl (2) and K (3)), and Na[Tl(CN)4].3H2O (4) salts, and their structures have been determined by single-crystal X-ray diffraction. In the crystal structure of 1, the thallium(III) ion has a trigonal bipyramidal coordination with three cyanide ions in the equatorial plane, while an oxygen atom of the water molecule and a nitrogen atom from a cyanide ligand, attached to a neighboring thallium complex, form a linear O-Tl-N fragment. In the three compounds of the tetracyano-thallium(III) complex, 2-4, the [Tl(CN)4]- unit has a distorted tetrahedral geometry. Along with the acidic leaching (enhanced by Tl(III)-CN- complex formation), an effective reductive dissolution of the thallium(III) oxide can also take place in the Tl2O3-HCN-H2O system yielding thallium(I), while hydrogen cyanide is oxidized to cyanogen. The latter is hydrolyzed in aqueous solution giving rise to a number of products including (CONH2)2, NCO-, and NH4+ detected by 14N NMR. The crystalline compounds, Tl(I)[Tl(III)(CN)4], Tl(I)2C2O4, and (CONH2)2, have been obtained as products of the redox reactions in the system.     

A mercury-free electrochemical sensor for the determination of thallium(I) based on the rotating-disc bismuth film electrode

A bismuth film electrode was tested and proposed as an environmentally friendly sensor for the determination of trace levels of Tl(I) in non-deoxygenated solutions. Determination of thallium was made by anodic stripping voltammetry at a rotating-disc bismuth film electrode plated in situ, using acetate buffer as the supporting electrolyte. The stripping step was carried out by a square wave potential-time excitation signal. A univariate optimisation study was performed with several experimental parameters as variables. Under the selected optimised conditions, a linear calibration plot was obtained in the submicromolar concentration range, allowing the electrochemical determination of thallium in trace amounts; the calculated detection limit was 10.8 nM and the relative standard deviation for 15 measurements of 0.1 μM Tl(I) was ±0.2%, for a 120 s accumulation time. Interference of other metals on the response of Tl(I) was investigated. Application to real environmental samples was tested. The bismuth film electrode appears to be a promising tool for electroanalytical purposes, ensuring the use of clean methodology.     

Triton X-100存在下镉试剂分光光度法测定痕量铊(III)

本文首次提出了在Triton X-100存在下, 以镉试剂作显色剂于水相直接分光光度法测定了痕量铊, 结果表明: 该体系具有很高的灵敏度, 是目前分光光度法测定铊的最灵敏方法之一.     

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.     

Electrochemical masking of large amounts of copper in dpasv and the determination of thallium in the presence of a large excess of copper

The influence of the following surfactants on the peak of copper in 0.2M EDTA at pH 4.5 was investigated: polyoxyethylated alkylphenols having an average of 3 and 9.5 ethylene oxide units; polyoxyethylene alcohols having 4 and 7 ethylene oxide units; poly(ethylene glycols) having M.W. 4000, 9000 and 20000; hexadecyltributylphosphonium bromide (HDTBPB), tetraphenylphosphonium bromide (TPPB),N,N,N,N,N',N',N-examethylhexamethylenediammonium bromide (HMB), benzyl(di-isobutylphenoxyethoxy) dimethylammonium chloride (Hyamine 1622), hexadecyltrimethylammonium bromide (HDTMAB), hexadecyldimethylbenzylammonium chloride (HDDMBAC) and tetrabutylammonium chloride (TBAC). HDDMBAC, as well as all the substances examined which contained an ethylene oxide chain, completely suppressed the copper peak. HDTBPB and TPPB partially suppressed the peak, whereas HDTMAB, HMB and Hyamine 1622 enhanced it. TBAC was without effect. In 0.2M EDTA at pH 4.5 containing TBAC at 0.01M concentration and 10 ppm of Rokafenol N-3, Cu(II), Pb(II) and Bi(III) can be tolerated at concentrations of up to 0.05M, the height of the thallium peak being unaffected. The precision of the determination (3–10%) and the recovery are satisfactory. A 10³-fold ratio of Fe(III) to Tl(I) does not interfere with the determination.     

Resolution of strongly overlapped responses in square-wave voltammetry by using the Kalman filter

Various approaches have been proposed for resolving overlapped voltammograms. Such methods have become incresingly important since the advent of small computers and commercial electrochemical instrumentation capable of rapid-scan techniques. The combination of high-resolution, rapid-scan square-wave voltammetry and a linear, recursive estimator known as the Kalman filter is described. Results of the application of this combination to mixtures of thallium(I) and lead(II) in 0.9 M nitric acid are shown. Practical considerations for filter usage such as the choice of models, variances, and initial guesses are discussed, as are limits to the filter. With the Kalman filter, it was possible to quantify thallium in solutions containing as much as a 30-fold excess amount of lead, and it was possible to quantify lead in solutions containing a 60-fold excess amount of thallium. The filter is thus a useful tool for use with empirical models in multicomponent quantitation.     

Speciation Analysis of Thallium by Reversed‐phase Liquid Chromatography ‐ Inductively Coupled Plasma Mass Spectrometry

An inductively coupled plasma mass spectrometer (ICP‐MS) was used as a liquid chromatographic detector for the speciation analysis of thallium in environmental samples. In this study, ionic thallium species, namely Tl(I) and Tl(III) were well separated by reversed‐phase high performance liquid chromatography (RP‐HPLC) with a C8‐HPLC column as the stationary phase and 1 mmol L^?1 tetrabutylammonium phosphate (TBAP), 2 mmol L^?1 diethylenetriamine pentaacetic acid (DTPA) in 1% v/v methanol solution (pH 6) as the mobile phase. Effluent from the HPLC column was delivered to the nebulizer of the ICP‐MS for the determination of thallium. The separation was complete in less than 3 min. Detection limit was 0.002 μg L^?1 for both Tl(I) and Tl(III) compounds based on peak height. The relative standard deviation of the peak areas for five injections of a mixture containing 1 μg Tl L^?1 was better than 3.4%. The concentrations of Tl compounds were determined in standard reference materials, including NIST SRM 1643e Trace Elements in Water and NRCC NASS‐5 Open Ocean Seawater and water samples collected in Kaohsiung area, Taiwan. The HPLC‐ICP‐MS results of the reference samples agreed with the reference values. This method has also been applied to determine Tl(I) and Tl(III) compounds in custard apple (Annona squamosa) leaves collected from Chai‐shan Mountain, Kaohsiung and Taitung City, Taiwan. The thallium species were quantitatively leached from the leaves with a 5 mmol L^?1 DTPA in 100 mmol L^?1 ammonium acetate solution in an ultrasonic bath during a period of 30 min. The HPLC‐ICP‐MS result that was obtained after the analysis of leaves sample showed a satisfactory agreement with the total thallium concentration obtained by ICP‐MS analysis of completely dissolved sample.     

Determination of thallium(I) in solutions containing cations interfering in potentiometric ion-pair formation-based titrations

The possibility of the use of simple potentiometric coated-wire sensors in the analysis of mixtures of ions, the determination of which is based on the ion-pairing principle, was studied. Attention was especially paid on the determination of thallium(I) in the presence of alkali metal ions, mercury(II), copper(II) and silver(I). It was found that thallium(I) can selectively be titrated with sodium tetraphenylborate in diluted solutions. Interferences of ions of the alkali metals are practically negligible if their concentrations are lower than 10(-3) mol dm(-3). Interference of Cu(II) is minimized using EDTA as a masking agent, Hg(II) and Ag(I) ions are sufficiently screened by additions of sodium cyanide. In mixtures containing higher concentrations of alkali metals, thallium(I) can be oxidized to thallium(III) and selectively titrated as TlCl(-)(4) with a cationic titrant.     

Indirect determination of thallium by differential-pulse polarography

The method is based on the separation of Tl(I) as Tl(2)HPMo(12)O(40), stripping of the molybdate, and measurement of the peak current in differential-pulse polarography of the molybdenum. The calibration graph is linear over the range 2-12 ppm of thallium. The relative standard deviation is 1.2% (7 replicates each containing 500 microg of thallium). The current due to reduction of the molybdenum is three times that for reduction of the equivalent amount of Tl(I) in the thallous phosphomolybdate precipitate, making the indirect approach more sensitive than direct polarographic determination of the Tl(I).