EQCM Study of the Couple Thallium(I)/Thallium Amalgam at a Thin Film Mercury Electrode

EQCM and voltammetric data show that thallium(I) ions, which are adsorbed in the region of the positive surface charge, most probably, in the form of the ionic pairs, are not reduced. In this potential region, thallium(I) ions are reduced directly from the solution. At more negative potentials, the previously adsorbed stable ionic pairs slowly undergo transition into the less stable form. From this form, thallium(I) ions can be reduced or desorbed into the solution. The process is best described by a model of one electron, i.e., full charge transfer.     

银微电极微分电位溶出分析法研究

本文首次报道了银微电极微分电位溶出分析法。用化学刻蚀法方便地制作了银微电极，用于ＤＰＳＡ具有背景值低，分辨率好、精密度及灵敏度高，在不搅拌，仅需一定酸度而酸度而无其它介质的条件下就能测试等优点，对人工试样及自来水样分析，结果令人满意。     

Theoretical and photoluminescence studies on the d10-s2 AuI-TlI interaction in extended unsupported chains

The reactions of solutions of TlPF(6) and OPPh(3) in tetrahydrofuran or acetone with NBu(4)[AuR(2)] (R=C(6)Cl(5), C(6)F(5)) gave the new complexes [Au(C(6)Cl(5))(2)](2)[Tl(OPPh(3))][Tl(OPPh(3))(L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh(3))(2)][Au(C(6)F(5))(2)] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(I) and thallium(I) centres. Moreover, the Tl(I) centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au(I)-Tl(I) interactions and are consistent with the presence of a high ionic contribution (80 %) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20 %) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl(I) centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl(I) geometrical environment.     

Complexometric determination of thallium(III) in pure solution,alloys, and complexes using semicarbazide hydrochloride as a releasing agent

A simple and accurate complexometric method is proposed for the determination of Tl(III) using semicarbazide hydrochloride as a releasing agent. In the presence of diverse metal ions, thallium is complexed first with a known excess of EDTA, and the surplus EDTA is then titrated with standard zinc sulfate at pH 5.0–6.0 (hexamine) using xylenol orange indicator. An excess of 5% aqueous neutral solution of semicarbazide hydrochloride is then added and the released EDTA is titrated against standard zinc sulfate solution. The method works well in the range 2–50 mg of Tl(III) with relative errors < 0.5%, standard deviations 0.05mg and coefficient of variation 0.4%. The method is applied for the determination of thallium content in complexes and alloy compositions     

NMR studies of interionic interactions in N-methylformamide

The NMR chemical shifts of alkali and thallium(I) salts with various monovalent anions have been measured in N-methylformamide solution. Lithium-7 chemical shifts are virtually concentration and counter-ion independent, presumably due to an absence of direct cation-anion interactions. The sodium-23, potassium-39 and cesium-133 chemical shifts of the salts studied depend on the anion and vary linearly with the concentration. The observed behavior can be accounted for by the formation of collisional ion pairs. On the other hand, the thallium-205 chemical shifts of thallium(I) nitrate and perchlorate were anion-dependent and varied non-linearly with the salt concentration. These results are indicative of contact ion pair formation; formation constants were calculated to be 2.6±0.4 M ^–1 for TlNO ₃ and 1.7±0.5 M ^–1 for TlClO ₄ . The cesium-133 NMR spectra of several mixed electrolyte systems also have been measured in N-methylformamide solution. The¹³³Cs chemical shifts also change linearly with the concentrations of the salts added to 0.10 M CsI/NMF solutions. The influence of the anions on the chemical shifts is the same as that observed for cesium salts alone.     

Kinetics and thermodynamics of the electrodeposition of palladium, thallium, and tellurium from different baths

Some kinetic and activation thermodynamic functions for the electrodeposition of palladium, thallium, and tellurium from the best selected baths, viz. niclosamide bath [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide] for Pd, alizarin red bath for Tl, and salicylaldehyde bath for Te, are determined. Reaction rate constant (k), half-lifetime (t _1/2), activation energy (E _a), and such activation thermodynamic parameters as entropy change (ΔS*), enthalpy change (ΔH*), and Gibbs free energy (ΔG*) are calculated by applying the rate theory of the first-order reaction and the Eyring theory of the reaction rate. The effect of temperature change in the range of 30–60°C on the above parameters is studied and thoroughly discussed. The effect of metal type on both the reaction rate and the activation energy is also investigated. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 3, pp. 264–271. The text was submitted by the authors in English.     

Determination of Thallium in Soil

Abstract

A new spectrophotometric method is described for the determination of thallium in soil by extraction of Tl(III) with a toluene solution of N,N′-diphenylbenzamidine after acidification with 0.2–4.0 M HCl, and reaction of the extract with Crystal violet in the presence of 0.01–0.8 M HCl. The value of molar absorptivity of Tl(III)-X-CV complex (where X = Cl or Br; CV = Crystal violet) in toluene is 7.00 × 10⁴ 1 mole^?1 cm^?1 at the absorption maximum of 610 nm. The detection limit of the method is 20 ng ml^?1. The present method is free from interference of almost metal ions commonly associated with Tl. The method has been applied for analysis of the metal to soils.     

Spectrophotometric Study of Complexation of Tri-Aza Dibenzosulfide and Dibenzosulfoxide Macrocyclic Compounds with Heavy Metal Ions

The complexation reactions between 7,10,13-triaza-1-thia-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione ( TTD ) and 7,10,13-triaza-1-sulfoxo-4,16-dioxa-20,24-dimethyl-2,3;17,18-dibenzo-cyclooctadecane-6,14-dione ( TSD ) macrocycles with Ag⁺, Cd²⁺, Cu²⁺, Pb²⁺, Sr²⁺, Tl⁺, and Zn²⁺ ions have been studied in ethanol and methanol solutions at 25°C. The complexes formed between macrocycles ( TTD ) and ( TSD ) with these metals cations had a stiochiometry of 1:1 and 1:2, respectively. The stability constants of the resulting complexes were determined and found to decrease in the order Cu²⁺ > Zn²⁺ > Ag⁺ > Tl⁺ > Cd²⁺ > Pb²⁺ > Sr²⁺ with macrocycle ( TTD ) and Tl⁺ > Zn²⁺ > Cd²⁺ > Pb²⁺ > Cu²⁺ > Ag⁺ > Sr²⁺ with macrocycle ( TSD ).     

地质样品中金,银,铊等元素的连续原子吸收光谱法测定

本文提出了一个一次称样连续测定金、银、铊的简便、快速的新方法。该法是以泡塑吸附金、铊，使银等定量地保留在溶液中。泡塑上的铊用ＥＤＴＡ解脱后，再用硫脲溶液继续解脱金，然后，采用原子吸收光谱法连续测定金、银、铊。方法用于黄铁矿、方铅等单矿矿物及岩石、土壤样品中ｘｎｇ／ｇ～ｘｘｘμｇ／ｇ金、银、铊的测定，获得满意结果。     

Ruthenium(III)-catalyzed oxidation of thallium(i) by 12-tungstocobaltate(III) in hydrochloric acid medium

The reaction between thallium(I) and [Co^IIIW₁₂O₄₀]^5- in the presence of ruthenium(III) as catalyst proceeds viainitial outer-sphere oxidation of the catalyst to ruthenium(VI). The ruthenium(IV) thus generated will oxidize thallium(I) to an unstable thallium(II) which by reacting with oxidant gives the final product, thallium(III). The formation of ruthenium(II) by direct two-electron reduction of the catalyst by thallium(I) is thermodynamically less favorable. The reaction rate is unaffected by the [ H⁺ ], whereas it is catalyzed by chloride ion . The formation of reactive chlorocomplex,TlCl, in a prior equilibrium is the reason for the chloride ion catalysis. Increasing the relative permittivity of the medium increases the rate of the reaction, which is attributed to the formation of an outer-sphere complex between the catalyst and oxidant. This revised version was published online in June 2006 with corrections to the Cover Date.