scholarly journals Kinetics and mechanism of the oxidation of a cobaloxime by sodium hypochlorite in aqueous solution: Is it an outer-sphere mechanism?

2017 ◽  
Vol 454 ◽  
pp. 254-265
Author(s):  
Michael J. Celestine ◽  
Lorne S. Joseph ◽  
Alvin A. Holder
Keyword(s):  
Aqueous Solution ◽  
Sodium Hypochlorite ◽  
Outer Sphere ◽  
Kinetics And Mechanism ◽  
Sphere Mechanism

Kinetics and mechanism of redox reactions of U(III) ions with monochloroacetic and dichloroacetic acids

1979 ◽  
Vol 44 (2) ◽  
pp. 401-405 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Alcohol Concentration ◽  
Kinetics And Mechanism ◽  
Solvent Structure ◽  
Influence Of Ph ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reactions of U3+ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U3+ with CHCl2COO- ions and oxidation of U3+ with CHCl2.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.

Prometryne Oxidation by Sodium Hypochlorite in Aqueous Solution: Kinetics and Mechanism

1995 ◽  
Vol 29 (12) ◽  
pp. 2987-2991 ◽  
Author(s):  
G. Mascolo ◽  
A. Lopez ◽  
R. Foldenyi ◽  
R. Passino ◽  
G. Tiravanti
Keyword(s):  
Aqueous Solution ◽  
Sodium Hypochlorite ◽  
Kinetics And Mechanism ◽  
Solution Kinetics

scholarly journals Kinetics and mechanism of the reduction of n-(2-hydroxyethyl)ethylenediaminetriacetatoiron(III) complex by thioglycol in bicarbonate buffer medium

2018 ◽  
Vol 6 (1) ◽  
pp. 102 ◽  
Author(s):  
I U. Nkole ◽  
C R. Osunkwo ◽  
A D. Onu ◽  
O D. Onu
Keyword(s):  
Salt Effect ◽  
Reaction Medium ◽  
Outer Sphere ◽  
Reaction Rates ◽  
Kinetics And Mechanism ◽  
Bicarbonate Buffer ◽  
First Order ◽  
Buffer Medium ◽  
Activated Complex ◽  
Sphere Mechanism

The kinetics and mechanism of reduction of N-(2-hydroxyethyl) ethylenediaminetriacetatoiron (III) complex (hereafter [Fe(III)HEDTAOH2]) by thioglycol (hereafter RSH) has been studied spectrophotometrically in a bicarbonate buffer medium. The study was carried out under pseudo-first order conditions of an excess of thioglycol concentration at 28 ± 1℃, I = 0.44 mol dm-3 (KNO3) and λmax = 490 nm. The reaction is first order in [Fe(III)HEDTAOH2] and half order in [RSH] and a stoichiometric mole ratio of [Fe(III)HEDTAOH2]: RSH is 2:1. Reaction rates increased with increase in ionic strength (I) and dielectric constant (D) of the reaction medium of the reaction. The reaction displayed positive primary salt effect, which suggests the composition of activated complex are likely charged reactants ions. Test for possibility of an intermediate complex formation shows negative as Michaelis-Menten plot was linear with very negligible intercept. Based on the findings, outer-sphere mechanism is proposed for the reaction. The experimental rate law obtained is; - = k2 [Fe(III)HEDTAOH2][RSH]½   

Kinetics and mechanism of the oxidation of the sulphite ion by the Mn(III)–cydta complex ion

1995 ◽  
Vol 73 (9) ◽  
pp. 1531-1537 ◽  
Author(s):  
Uttra Chandrawat ◽  
Aditya Prakash ◽  
Raj N. Mehrotra
Keyword(s):  
Outer Sphere ◽  
Kinetics And Mechanism ◽  
The Other ◽  
Rapid Scan ◽  
Complex Ion ◽  
Sphere Mechanism

The reinvestigated oxidation of S(IV), HSO3−/SO32−ions, by [Mn(cydta)(OH)]− confirmed that S(IV) is oxidized in two parallel paths; the order with respect to [S(IV)] is one in one of the paths and two in the other. The nature of the dependence of the rate on [H+] is also confirmed. However, the rapid scan of the reaction mixture and measurement of the initial absorbance of the reaction mixture at different wavelengths at the beginning of the reaction suggest an outer-sphere mechanism. The rate parameters are of the same order as obtained in known reactions of an outer-sphere mechanism and this mechanism is further supported by the Marcus cross relation. Keywords: kinetics, outer-sphere mechanism, [Mn(cydta)]−, SO32−.

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 oxidation of V(II) ions with trichloroacetic acid

1980 ◽  
Vol 45 (12) ◽  
pp. 3287-3292 ◽  
Author(s):  
Ľubica Adamčíková
Keyword(s):  
Exchange Rate ◽  
Redox Reaction ◽  
Trichloroacetic Acid ◽  
Outer Sphere ◽  
Kinetics And Mechanism ◽  
Kinetic Measurements ◽  
Exchange Rate Constant ◽  
Marcus Equation ◽  
Mechanism Of Oxidation ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reaction of V(II) ions with trichloroacetic acid were studied in the medium of 0.04-2.0M-HClO. The results of kinetic measurements were compared with the analogous oxidation of U(III) ions with trichloroacetic acid, and the exchange rate constant for the reaction U3+ + *U4+ → U4+ + *U3+ was calculated. The influence of binary mixtures on the kinetic parameters of the reaction and the application of the Marcus' equation show that the oxidation of V2+ions with trichloroacetic acid proceeds by an outer-sphere mechanism.

scholarly journals Kinetics and mechanism of oxidation of mandelic acid with Bi(V) in phosphoric acid medium

2020 ◽  
Vol 16 (5) ◽  
pp. 50-57
Author(s):  
MUKESH KUMAR JHA ◽  
◽  
AVINASH KUMAR ◽  
Keyword(s):  
Electron Transfer ◽  
Phosphoric Acid ◽  
Acid Medium ◽  
Mandelic Acid ◽  
Reaction Rate ◽  
Outer Sphere ◽  
Kinetics And Mechanism ◽  
Opposite Charge ◽  
Mechanism Of Oxidation ◽  
Sphere Mechanism

The kinetics and mechanism of oxidation of Mandelic acid with Bi(V) has been investigated in phosphoric acid medium. The order with respect to substrate and oxidant each is one. The reaction rate is independent of [H+] ion as well as [Bi(III)]. The reaction rate decreases with increasing ionic strength indicating reactive species of opposite charge. The simple rate law explained all the experimental observations. The mode of electron transfer from the substrate to Bi(V) has been indicated is a bridged outer sphere mechanism.

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.

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