Metal-ion oxidations in solution. Part XX. The mechanism of the reaction of thallium (III) with 2-mercaptosuccinic acid in perchlorate media

1977 ◽  
Vol 55 (20) ◽  
pp. 3575-3580 ◽  
Author(s):  
Zahid Amjad ◽  
John G. Chambers ◽  
Alexander McAuley
Keyword(s):  
Electron Transfer ◽  
Redox Reaction ◽  
Metal Ion ◽  
Reaction Scheme ◽  
Mercaptosuccinic Acid ◽  
Enthalpy Of Activation ◽  
Electron Transfer Pathways ◽  
Intramolecular Transfer ◽  
Mechanism Of The Reaction ◽  
Sphere Mechanism

The oxidation of 2-mercaptosuccinic (thiomalic) acid (HRSH) by thallium(III) proceeds via an inner sphere mechanism. Spectrophotometric and kinetic evidence are provided for the formation of a sulphur-bonded thallium(III) intermediate. The data are consistent with the reaction scheme[Formula: see text]in which the complex decomposes via a one-electron intramolecular transfer k2 = 3.8 × 10−4 s−1 at 25 °C, with K2 = 1650 M−1. The enthalpy of activation ΔH2≠ for the redox reaction (11.8 ± 1.2 kcal/mol) is considerably smaller than for other systems of this type and reflects the greater ease of reaction. Comparison is made of possible one- and two-electron transfer pathways.

Kinetics and mechanism of redox reaction of U(III) ions with trichloroacetic acid

1980 ◽  
Vol 45 (1) ◽  
pp. 26-31 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Electron Transfer ◽  
Redox Reaction ◽  
Trichloroacetic Acid ◽  
Outer Sphere ◽  
Elementary Step ◽  
Kinetics And Mechanism ◽  
Kinetic Measurements ◽  
Chloroacetic Acids ◽  
Acetic Acids ◽  
Sphere Mechanism

The kinetics and mechanism of redox reaction of U3+ ions with trichloroacetic acid in the medium of perchloric acid were studied. The form of the dependence of the rate constant on the concentration of H3O+ ions suggests that the U3+ion reacts in the first elementary step with the CCL3.COO- anion under formation of an intermediary radical which reacts rapidly in the second step.The results of kinetic measurements of all three chloro substituted acetic acids are compared. A detailed study of the influence of binary mixtures on kinetic parameters of the studied reaction (especially of water-tert-butanol mixtures) shows that the reduction of chloroacetic acids with U3+ ions proceeds by the outer sphere mechanism of the electron transfer.

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

scholarly journals Electron transfer pathways in photoexcited lanthanide(III) complexes of picolinate ligands

2021 ◽  
Author(s):  
Daniel Kovacs ◽  
Daniel Kocsi ◽  
Jordann A. L. Wells ◽  
Salauat R. Kiraev ◽  
Eszter Borbas
Keyword(s):  
Electron Transfer ◽  
Metal Binding ◽  
Binding Sites ◽  
Secondary Amide ◽  
Metal Binding Sites ◽  
Electron Transfer Pathways

A series of luminescent lanthanide(III) complexes consisting of 1,4,7-triazacyclononane frameworks and three secondary amide-linked carbostyril antennae were synthesised. The metal binding sites were augmented with two pyridylcarboxylate donors yielding octadentate...

Control of Electron Transfer Pathways in a Dye-Sensitized Solar Cell

2006 ◽  
Vol 97 (20) ◽  
Author(s):  
Ben Brüggemann ◽  
Juan Angel Organero ◽  
Torbjörn Pascher ◽  
Tõnu Pullerits ◽  
Arkady Yartsev
Keyword(s):  
Electron Transfer ◽  
Solar Cell ◽  
Dye Sensitized Solar Cell ◽  
Dye Sensitized ◽  
Electron Transfer Pathways

One and two electron transfer pathways in the photoreduction of flavin

1982 ◽  
Vol 54 (9) ◽  
pp. 1651-1665 ◽  
Author(s):  
R. Traber ◽  
H. E. A. Kramer ◽  
Peter Hemmerich
Keyword(s):  
Electron Transfer ◽  
Electron Transfer Pathways
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