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).     

The oxidation of thallium(I) by alkaline ferricyanide

A simple method for the potentiometnc determination of thallium is described. Thus is based essentially on the precipitation of thallic hydroxide by alkaline ferricyanide and the back titration of excess K₃[FeCN)₆] by standard sodium arsemte according to Kolthoff's method Under thc specified experimental conditions. the reduction of trivalent thallium is not effected by As₂O₃ and the procedure offers therefore a unique advantage of simplicity and accuracy.     

Sequential oxidimetric determination of thallium(I) and (III)

The reaction between thallium(III) and oxalic acid in sulphuric acid medium has been investigated. Spectrophotometric results show that thallium(III) can be quantitatively reduced to thallium(I) with oxalic acid in aqueous medium when heated to near boiling point. Conditions for the estimation of the excess of oxalic acid with cerium(IV) sulphate in the presence of thallium(I) and for the estimation of a mixture of thallium(I) and thallium(III) have been investigated. The method is simpler than many other redox methods reported for the determination of thallium(III) and is free from many interferences encountered in these titrations. The reagents are cheap and quite stable.     

The oxidation of thallium(I) by selenious acid

A new and simple method for the quantitative determination of thallium based on the oxidation of TI(I) to TI(III) by selenious acid has been described. The precipitated selenium is weighed directly. Furthermore, the thallic hydroxide obtained by the addition of excess alkali to the filtrate is dissolved in HCl and determined iodometrically. The excess selenious acid in the filtrate is also estimated iodometrically or by gravimetric method after reduction to metallic selenium. Under the specified operative conditions the results are reproducible and accurate within the limits of experimental error.     

Kinetics of the oxidation of cyclohexene by thallium(III) acetate

The kinetics of the reaction by which thallium(III) acetate oxidizes cyclohexene in glacial acetic acid medium, has been studied by UV spectrophotometric observation at 30°C. The consumption of thallium(III) acetate follows a second-order rate law exhibiting first-order dependence on each of thallium(III) acetate and cyclohexene; however, the first-order dependence on cyclohexene disappears at high cyclohexene concentrations as pseudo-first-order conditions prevail above 0.2 M cyclohexene. A steady-state model of the following form is proposed: where Tl, Cy, and Com are units of Thallium(III) acetate, cyclohexene, and a reaction complex. The value of k₂ has been evaluated as 0.00027 and (k_?1 + k₂) as 0.0385k₁. For low thallium(III) acetate concentrations the reaction kinetics follow the rate law: where α = the excess concentration of cyclohexene over thallium(III) triacetate. For thallium(III) acetate concentrations above 0.02 M, double salt formation of thallium(III) acetate with product thallium(I) acetate removes thallium(III) acetate from the reaction and a modified rate law is observed. Runge–Kutta numerical solutions to the differential equations provide confirmation that the rate expressions are valid in predicting the observed concentrations of thallium(III) acetate.     

Kinetics and mechanism of oxidation of thallium(I) by 12-tungstocobaltate(III)in aqueous hydrochloric acid

The reaction between Tl^I and [Co^IIIW₁₂O₄₀]^5– proceeds in two one-electron steps, involving formation of unstable Tl^II in a slow first step followed by reaction with oxidant in a fast step. The reaction rate is unaffected by the [H⁺] as protonation equilibria are not involved with either reactant, whereas the accelerating effect of chloride ion is due to the formation of an active chloro-complex of the reductant, TlCl₃ ^2–. Increasing the ionic strength and decreasing 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 reactants. The activation parameters were also determined and the values support the proposed mechanism.     

Vanadium(V) oxidation of thallium(I) in hydrochloric acid

The reaction between V^V and Tl^I was studied in 4.0 mol dm^–3 HCl at an ionic strength of 4.1 mol dm^–3 at 25° C. The main active species under the reaction conditions were found to be VO _inf2 ^sup+ and TlCl _inf3 ^sup2– for the oxidant and reductant, respectively. A probable mechanism in terms of these species is given, and follows the rate law:

Kinetics and mechanism of oxidation of aliphatic ketoximes by thallium(III) acetate—part I

The oxidative cleavage of some aliphatic ketoximes by thallium(III) acetate was studied in the temperature range of 20–40°C. The reactions were followed by determination of the rates of disappearance of thallium(III) acetate for variations in [substrate], [Tl(III)], [H⁺], ionic strength, temperature, etc. The reactions were found to be totally second order–first order with respect to each reactant. The second-order rate constants and thermodynamic parameters were evaluated and discussed. The mechanism proposed involves one-electron oxidation to the iminoxy radical followed by an another one-electron oxidation to the hydroxynitroso compound which dimerizes and decomposes to give the carbonyl compounds and hyponitrous acid.     

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.     

Ruthenium (III)-Schiff base complex catalyzed oxidation of secondary alcohols by N-methylmorpholine-N-oxide or thallium (III) acetate

The Ru(III) Schiff base complex [Ru(L)Cl₂]Cl; L = bis(picolinaldehyde) o-phenylenediimine, catalyzes the oxidation of secondary alcohols by N-methylmorpholine-N-oxide(NMO) or thallium(III) acetate as oxidant. Kinetic studies showed the formation of Ru(V) species as the active intermediate. © 1996 John Wiley & Sons, Inc.     

Oxidation of thallium(I) by hexacyanoferrate(III) in aqueous acetic acid

The hexacyanoferrate(III)-thallium(I) reaction in aqueous acetic acid containing large concentrations of hydrochloric acid is considerably accelerated both by hydrogen and chloride ions as well as increasing acetic acid in the medium. The experimental results obey the rate law (1) where β₁ to β₆ are the cumulative stability constants of the species TlCl, TlCl, TlCl, HFe(CN), H₂Fe(CN) and H₃Fe(CN)₆ respectively and k_a and k_b are the rate constants associated with the mono- and di-protonated oxidant species. The main active species are H₂Fe(CN) and TlCl.     

(Chloromethyl)thallium(III) compounds

Aryl(chloromethyl)thallium chlorides, Ar(ClCH₂)TlCl (Ar=C₆H₅, p-CH₃C₆H₄) have been prepared by treatment of arylthallium dichlorides with diazomethane. The derived carboxylates, Ar(ClCH₂)TlX, react with HgX₂ to give the dicarboxylates, (ClCH₂)TlX₂ (X = OCOCH₃, OCOC₃H₇-i) and with tetramethyltin to give CH₃(ClCH₂)TlX compounds. R(ClCH₂)TIX compounds (R = CH₃, C₆H₅, p-CH₃C₆H₄) undergo disproportionation in methanol to R₂TlX and (ClCH₂)₂TlX compounds.     

Titrimetric determination of microgram amounts of thallium(I) by thiocyanate amplification after precipitation as thallium hexathiocyanatochromate(III)

Summary Thallium (5–200g) is precipitated as Tl₃Cr(SCN)₆. The precipitate is collected, then treated with 10% sodium carbonate solution, and the thiocyanate dissolved is oxidized to sulphate by iodine at pH 8.2. After acidification, the excess of iodine is extracted into chloroform, and the iodide in the aqueous solution is determined by the Leipert amplification procedure. The method provides 76 iodine atoms for each original thallium(I) ion. Copper(II), mercury(II), bismuth, lead and silver interfere seriously, the first three causing negative errors and the other two positive errors.

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Maanalytische Bestimmung von Mikrogrammengen Thallium(I) durch Vervielfachung mit Thiocyanat nach Fällung als Thalliumhexathiocyanatochromat(III)

Zusammenfassung Thallium (5–200g) wird als Tl₃Cr(SCN)₆ gefällt. Der gesammelte Niederschlag wird mit 10% iger Sodalösung behandelt und das gelöste Thiocyanat mit Jod bei pH 8,2 zu Sulfat oxydiert. Nach Ansäuern wird der Jodüberschuß mit Chloroform extrahiert und das Jodid in der wäßrigen Lösung nach Leipert titriert. Dabei entsprechen 76 Jodatome einem ursprünglichen Thallium(I)ion. Cu(II), Hg(II), Bi, Pb und Ag stören stark und verursachen negative bzw. im Falle Pb und Ag positive Fehler.

     

Trimethylsilylmethyl derivatives of thallium(III)

Some trimethylsilylmethyl derivatives of thallium(III) have higher stability and unusual coordination behavior in comparison with simple alkylthallim(III) analogs for steric reasons.     

Influence of thallium(I) and thallium(III) on parameters of oscillating chemical reaction in a bromate-cerium(III,IV)-malonic acid-sulfuric acid system

The influence of thallium(I) and thallium(III) on the parameters of the Belousov-Zhabotinskii oscillating chemical reaction in the bromate-cerium(III, IV)-malonic acid-sulfuric acid system was studied. As a result of the addition of thallium(I) and thallium(III), the oscillation parameters change in the same way, which cannot be explained by the complexation of these ions with the bromide only. It was found that during the oscillating reaction, thallium(I) can be oxidized by bromine-containing compounds and thallium(III) reduced by the transformation products of malonic and bromomalonic acids. A scheme of action of a thallium(III)/thallium(I) two-electron redox pair in the oscillating chemical reaction studied has been proposed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 23, No. 1, pp. 106–111, January–February, 1987.     

Thallium(II) in the chemically induced thallium(I)-Thallium(III) exchange

The rate of the electron exchange between thallium(I) and thallium(III) induced by iron(II) has been measured at various concentrations of Tl(I), Tl(III), and Fe(II).²⁰⁴Tl tracer, initially in the Tl(I) state, was used. Exchange induced by the separation method was less than 0.01%. The mechanism earlier discussed is $$\begin{gathered} Tl^{III} + Fe^{II} \rightleftharpoons Tl^{II} + Fe^{III} \left( {k_1 ,k_{ - 1} } \right) \hfill \\ Tl^{II} + Fe^{II} \rightharpoonup Tl^I + Fe^{III} \left( {k_2 } \right) \hfill \\ *Tl^I + Tl^{II} \rightleftharpoons *Tl^{II} + Tl^I \left( {k_I } \right) \hfill \\ *Tl^{II} + Tl^{III} \rightleftharpoons *Tl^{III} + Tl^{II} \left( {k_{III} } \right), \hfill \\ \end{gathered} $$ which provides an exchange path in addition to the two-electron reaction^*Tl^I+Tl^III?^*Tl^III+Tl^I (k_ex). The rate law deduced from this mechanism agrees with experiment over a limited range of conditions but fails to account for the observed effect at low concentrations of Tl(I). The additional rate can be represented by inclusion of a term in which the rate of the induced exchange is independent of the concentration of Tl(I). When treated according to the resulting complete rate law the data are consistent with earlier photochemical studies. The present results in combination with other data give k₂=3·10⁶ M^?1·sec^?1 in 1M perchloric acid at 25°C. This is in satisfactory agreement with a recent pulse radiolysis measurement as well as with independent flash photolysis studies.     

A [205T1]-thallium NMR study of thallium(I) and thallium(III) fluorometalates in acetonitrile

The concentration-dependent behavior observed for ²⁰⁵T1 n.m.r. resonances from thallium(I) fluorometalates, PF₆^-, WF₇^-, MoF₆^- and UF₆^-, in acetonitrile indicates that some degree of ion-pairing is present in these solutions. The paramagnetic anion, UF₆^-, has a pronounced effect on ²⁰⁵T1 resonance in the T1⁺ salt, but its effect on T1³⁺ is very small. It is suggested that T1³⁺ is effectively solvated by MeCN and that direct ion-pairing is unimportant. The ²⁰⁵T1 shielding of T1³⁺ is decreased by the presence of T1⁺ in solution, possibly as a result of the increase in asymmetry of the T1³⁺ environment.