Kinetics of oxidation of 2,4-pentanedione with Ce(IV) ions in relation to Belousov-Zhabotinskii reaction

1981 ◽  
Vol 46 (8) ◽  
pp. 1734-1739 ◽  
Author(s):  
Ľudovít Treindl ◽  
Peter Kaplán
Keyword(s):  
Induction Period ◽  
Sulphuric Acid ◽  
Reaction Step ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Inner Sphere ◽  
Belousov Zhabotinskii Reaction ◽  
Kinetics Of

Oxidation of 2,4-pentanedione with Ce(IV) ions in a solution of sulphuric acid is an inner-sphere reaction which proceeds via an intermediary complex. The reaction is of the first order with respect to both reactants, it is catalysed with H3O+ ions, and its rate diminishes with increasing concentrations of HSO4- and Ce(III) ions. According to the proposed mechanism, the rate-determining reaction step is an intramolecular redox step of the intermediary complex. The modified Belousov-Zhabotinskii reaction with 2,4-pentanedione as substrate is interesting in that oscillations with an increasing amplitude are formed after an induction period even in the absence of stirring.

Kinetics of oxidation of α-ketoglutaric acid with Ce(IV) ions in relation to Belousov-Zhabotinskii reaction

1982 ◽  
Vol 47 (11) ◽  
pp. 2831-2837 ◽  
Author(s):  
Ľudovít Treindl ◽  
Vasil Dorovský
Keyword(s):  
Redox Reaction ◽  
Platinum Electrode ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Redox Catalyst ◽  
Oscillation Reaction ◽  
Belousov Zhabotinskii Reaction ◽  
Kinetics Of

Oxidation of α-ketoglutaric acid with Ce(IV) ions in a solution of sulphuric acid is a reaction of the first order with respect to both Ce(IV) ions and substrate, is acid catalysed, and its rate is proportional to the reciprocal square of the equilibrium HSO4- concentration. From the temperature dependence of the rate constant in 1.5M-H2SO4, the activation parameters were determined as ΔH##f = 57 kJ/mol and ΔS##f = -45 J mol-1 K-1. The redox reaction proper consists apparently of two steps: in the first one, the enol form of α-ketoglutaric acid reacts with Ce(IV) ions with the formation of the corresponding radical; in the second one, the latter is oxidized further with Ce(IV) to give malonic and succinic acids. Conditions are indicated under which α-ketoglutaric acid serves as substrate for the Belousov-Zhabotinskii oscillation reaction in the presence of Ce(IV)-Ce(III) redox catalyst. Oscillations of Ce(IV) and Br2 concentrations, shifted in phase, can be recorded polarographically with a rotating platinum electrode.

Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions

1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan
Keyword(s):  
Ionic Strength ◽  
Fractional Order ◽  
Activation Parameters ◽  
Order Reaction ◽  
First Order Reaction ◽  
Intermediate Complex ◽  
Constant Ionic Strength ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

Kinetics of oxidation of hexane-1,6 diol by cerium(IV) in sulphuric acid

1982 ◽  
Vol 263 (1) ◽  
Author(s):  
K. Behari ◽  
N. N. Pandey ◽  
R. K. Khanna ◽  
R. S. Shukla
Keyword(s):  
Sulphuric Acid ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

Oxidation of 1- and 2-acetylnaphthalenes by iodate - a kinetic study

1990 ◽  
Vol 55 (6) ◽  
pp. 1535-1540 ◽  
Author(s):  
Prerepa Manikyamba
Keyword(s):  
Solvent Effect ◽  
Enol Form ◽  
Aqueous Methanol ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Carbonium Ion ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting ◽  
Kinetics Of

Kinetics of oxidation of 1- and 2-acetylnaphthalenes by iodate in the presence of sulphuric acid in aqueous methanol has been studied. The reaction is first order with respect to both [iodate] and [acetylnaphthalene]. Solvent effect indicates a cation-dipole type of interaction in the rate limiting step. A mechanism is proposed with a slow attack of IO2+ on enol form of acetylnaphthalene forming an intermediate carbonium ion, which ultimately gives corresponding ω-hydroxyacetylnaphthalene. The higher reactivity of 2-acetyl isomer is attributed to the greater stability of the corresponding carbonium ion than that of 1-acetyl isomer.

scholarly journals Kinetics and Mechanism of Oxidation of Diethanolamine and Triethanolamine by Potassium Ferrate

2011 ◽  
Vol 8 (2) ◽  
pp. 903-909 ◽  
Author(s):  
Shan Jinhuan ◽  
Zhang Jiying
Keyword(s):  
Activation Parameters ◽  
Rate Equations ◽  
Potassium Ferrate ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Dependence ◽  
Rate Determining Step ◽  
Thermodynamic Activation Parameters ◽  
Plausible Mechanism ◽  
Kinetics Of

The kinetics of oxidation of diethanolamine and triethanolamine by potassium ferrate(VI)in alkaline liquids at a constant ionic strength has been studied spectrophotometrically in the temperature range of 278.2K-293.2K. The reaction shows first order dependence on potassium ferrate(VI), first order dependence on each reductant, The observed rate constant (kobs) decreases with the increase in [OH-], the reaction is negative fraction order with respect to [OH-]. A plausible mechanism is proposed and the rate equations derived from the mechanism can explain all the experimental results. The rate constants of the rate-determining step and the thermodynamic activation parameters are calculated.

scholarly journals Kinetics of Oxidation of Glutathione by Micelle Trapped Tris(benzhydroxamato)iron(III)

2007 ◽  
Vol 4 (2) ◽  
pp. 279-283 ◽  
Author(s):  
B. L. Hiran ◽  
S. S. Dulawat ◽  
Renu Rathore ◽  
Neeru Rathore
Keyword(s):  
Aqueous Phase ◽  
Sodium Dodecyl Sulphate ◽  
Sodium Dodecyl ◽  
Stern Layer ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

Kinetics of the oxidation of glutathione (GSH) by micelle Sodium dodecyl sulphate (SDS) trapped tris(benzhydroxamato)iron(III) (TBH) at pH 3.3 and at 298 K has been described. The reaction is first order in TBS and GSH. Increase in pH decreased the rate. Order in H+is one The reaction between TBH and GSH on micellar surface (Stern layer) differs from that occurring in bulk aqueous phase in absence of micelle (SDS). Reactive FeL3species on micellar surface is FeL2+.

Sign in / Sign up

Export Citation Format

Share Document