14627-67-9Relevant academic research and scientific papers
Polar trifluoromethylation reactions: syntheses of trifluoromethyl gallium, indium, and thallium compounds. The mechanism of polar trifluoromethyl group transfer
Naumann, Dieter,Strauss, Werner,Tyrra, Wieland
, p. 1 - 15 (1991)
The reactions of Cd(CF3)2 complexes with GaCl3, InCl3, and TlX3 (X: Cl, OCOCH3, OCOCF3) in aprotic basic solvents have given the compounds Ga(CF3)3dmf, Ga(CF3)2Cldmf, 2, In(CF3)32CH3CN, In(CF3)2Cldmf, and Tl(CF3)32dmf, which have been characterized by NMR spectroscopy, mass spectrometry, vibrational spectroscopy, and elemental analysis.All trifluoromethylmetal halides formed as intermediates were detected by 19F NMR spectroscopy.The dependence of the chemical shifts and the coupling constants 2J(203/205Tl-19F) on the number ofCF3-groups bound to the central atom provides unambiguous evidence for the formular of trifluoromethyl gallates and thallates and the existence of the --anion has been confirmed by 71 Ga NMR spectroscopy.A mechanism for successful polar trifluoromethyl group transfer is discussed on the basis of Pearson's HSAB concept and the results of conductivity measurements.
The kinetics of the silver(II)-thallium(I) reaction in nitric acid
Dundon, Robert W.,Gryder, John W.
, p. 986 - 989 (1966)
Kinetic data for the Ag(II)-Tl(I) reaction in 6.18 F HNO3 at 26.2° are interpreted in terms of the mechanism (Chemical Equation Presented) Values for combinations of rate constants found from a least-square treatment of the data are k1 = 0.403, k2/(k1k3) = 2.03 × 10-2, and k2k4/(k1k3k5) = 1.41 × 10-6 where time is in seconds, concentrations are in moles/liter, and rate is expressed as disappearance of Ag(II). These values are consistent with equilibrium and rate constants for related reactions. Unlike other reactions with Ag(II), the oxidation of Tl(I) is independent of HNO3 concentration over the range 4.66 to 8.82 F.
The Oxidation Reaction of Tl(I) to Tl(III) by the Peroxodisulfate Ion. I. Kinetics and Mechanism in an Aqueous Solution
Kimura, Masaru,Akazome, Tsuneko,Takenaka, Kayo,Kobayashi, Akiko
, p. 1271 - 1277 (1980)
The oxidation reaction of the thallium(I) ion to the thallium(III) ion by the peroxodisulfate ion has been studied in an aqueous acidic solution.The reaction constituted a chain reaction initiated by the thermal decomposition or the peroxodisulfate ion, the reaction involving no direct reactions between the thallium(I) and peroxodisulfate ions.At thallium(I) ion concentrations larger than 0.004 mol dm-3, the reaction mechanism was assumed to be: .The rate of the reaction was described as -d2->/dt = (k1 + k2+>)2-> + k4(k1/k5)1/22->3/2.The rate constants at an ionic strength of 0.16 mol dm-3 were determined to be k1 = 1.99 * 1019 exp -1/RT>s-1, k2 = 2.75 * 1012 exp-1/RT>dm3 mol-1 s-1, and k4(k1/k5)1/2 = 2.81 * 1013 exp-1/RT>dm3/2 mol-1/2 s-1 in 0.01 mol dm-3 perchloric acid, the k4 value being increased with a decrease in the hydrogen-ion concentration.The ionic strength (μ) dependence was described as log k4(k1/k5)1/2 = -4.17 - 1.05 μ1/2 in 0.01 mol dm-3 perchloric acid at 40 deg C.The reaction rate was completely retarded by the addition of 1percent acrlyronitrile, 5 * 10-6 mol dm-3 cerium(III) sulfate, 1 * 10-3 mol dm-3 cerium(IV) sulfate, or 0.1 mol dm-3 sodium acetate, and it was also remarkably retarded by the addition of 1 * 10-3 mol dm-3 tetranitromethane.The copper(II) ion and molecular oxygen did not appreciably affect the reaction rate, but the iron(III) ion accelarated it greatly.
Oxidative conversion of benzoic and o-chlorobenzoic acid hydrazides to their corresponding acids by thallium(III): A mechanistic study
Tardale,Phadkule,Patil,Gokavi
, p. 79 - 82 (2007/10/03)
The reactions between thallium(III) and benzoic acid and o-chlorobenzoic acid hydrazides have been studied in a mixture of perchloric and hydrochloric acid medium. The reaction involves formation of complex between the reactants, which decompose in the subsequent step to give products. The reaction proceeds by direct two electron transfer without intervention of free radicals. Increase in [H+] and [Cl-] decreases the rate of the reaction. The increase in the ionic strength does not affect the rate of the reaction while decrease in the relative permitivity increases the same. The effect of temperature on the reaction has been studied between 25 to 45°C and the activation parameters were determined for the slow step of the reaction.
Kinetics and mechanism of pyridinium chlorochromate oxidation of thallium(I)
Gokavi
, p. 307 - 310 (2007/10/03)
The oxidation of TI(I) by pyridinium chlorochromate has been studied in 2.0 mol dm-3 hydrochloric acid. The reaction exhibits total second order kinetics, first order in each reactant and it is catalysed by hydrogen and chloride ions. The active species have been found to be protonated pyridinium chlorochromate of the oxidant and TICl2 of the reductant respectively. Added products, TI(III), and Mn(II) have no significant effect on the reaction. The protonation constant of the pyridinium chlorochromate has also been evaluated as 8.0 × 10-2 dm3 mol-1 from the [H+] dependence of the reaction. A plausible mechanism is proposed based on the experimental observations.
Oxidation of thalium(I) by permanganate in aqueous perchloric acid
Chimatadar, S A,Hiremath, S C,Raju, J R
, p. 190 - 192 (2007/10/02)
Permanganate oxidation of thallium(I) in aqueous perchloric acid has 2:3 stoichiometry (oxidant: reductant) and manganese(IV) and thallium(III) are the products.A clean second order kinetics is followed by the reaction with fractional dependence on .The results are explained by a mechanism involving HMnO4 as the active oxidant species.
Equilibrium dynamics in the thallium(III)-bromide system in acidic aqueous solution. A205Tl NMR study
Bányai, István,Glaser, Julius
, p. 4703 - 4710 (2007/10/02)
Kinetics of ligand exchange in the thallium(III)-bromide system in aqueous 3 M perchloric acid solution was studied by measuring 205Tl NMR line widths at 25 °C. Three types of parallel second-order reaction paths were found to be dominant. For the reactions TlBrm3-m + *TlBrn3-n ? *TlBrm3-m + TlBrn3-n the rate constants are k01 = 2.8 × 104 (1.25 × 104 at 10 °C), k12 = 7.5 × 104, k23 = 8.2 × 106, and k34 = 2.3 × 107 M-1 s-1. For the reactions Tl3+ + TlBr2+ ? TIBr2+ + TlBr2+ TlBr2+ + TlBr3, ? TlBr2+ + TlBr2+ k02 = 7.1 × 105, k11 = 6.1 × 103, and k13 = 2.4 × 107 M-1 s-1 (k22 = 2.3 × 105 M-1 s-1, calculated by use of equilibrium constants), and for the complex formation (anation) reactions TlBrn3-n + Br- ? TlBrn+12-n k'01 10, k'12 = 5.8 × 109, k'23 = 5.6 × 1010, k'34 = 1.5 × 109, and k'45 ～ 6 × 106 M-1 s-1. The first and the second types of exchange dominate at low bromide to thallium ratios, (Brtot/Tltot) = R ≤ 2, whereas the third one becomes dominant at higher R values. The activation parameters for the reaction represented by k01 are ΔH* = 38 kj mol-1 and ΔS* = -32 J mol-1 K-1. A mechanism for this reaction is suggested to be a dissociatively activated interchange process. The present results are discussed and compared to the corresponding data for the thallium(III) chloride system. One important result of the present study is the estimation of the rate of water exchange for the hydrated thallium(III) ion, k ～ 3 × 108 s-1, which has not been possible to obtain by any other experimental method. Specific interaction theory calculation has been performed for the TlBrn3-n complexes in order to check the validity of the used equilibrium constants; values of the appropriate specific interaction coefficients are given.
Chromium(VI) Oxidation of Thallium(I) in Aqueous Acetic Acid and Effect of Added Vanadium(V) on the Reaction
Gokavi, G. S.,Raju, J. R.
, p. 494 - 497 (2007/10/02)
Chromium(VI) oxidation of thallium(I) in 60percent acetic acid containing 1.25 mol dm-3 hydrochloric acid is a second order reaction, understood to be between CrO3Cl(-) and TlCl.Increase in and accelerates the reaction.Added V(V) accelerates the reaction till slightly exceeds because of a 1:1 interaction between V(V) and Tl(I).At higher , the rate constant is lowered due to a specific cation effect.No interaction between added V(V) and Tl(I) is encountered in the case of the reaction in 40percent aqueous acetic acid; however, in 80 and 90percent aqueous acetic acid, 2:3 and 1:2 interactions between V(V) and Tl(I) are observed.
