Kinetics of oxidation of hydrogen peroxide and ascorbic acid by a tribridged manganese(IV,IV) dimer in feebly acidic media

1999 ◽  
Vol 77 (4) ◽  
pp. 451-458 ◽  
Author(s):  
Anup Kumar Bhattacharya ◽  
Anath Bondhu Mondal ◽  
Anadi C Dash ◽  
G S Brahma ◽  
Rupendranath Banerjee
Keyword(s):  
Hydrogen Peroxide ◽  
Ascorbic Acid ◽  
Dehydroascorbic Acid ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetic Activity ◽  
First Order Kinetics ◽  
Oxidation Of Hydrogen ◽  
Kinetics Of ◽  
Complex Ion

In weakly acidic, aqueous buffer (MeCO2-+ bipy), the complex ion [Mn2IV(μ-O)2(μ-MeCO2)(bipy)2(H2O)2]3+, 1 (bipy = 2,2prime-bipyridine), coexists in rapid equilibrium with its hydrolytic derivatives, [Mn2IV(μ-O)2(bipy)2(H2O)4]4+, 2, and [Mn2IV(μ-O)2(μ-MeCO2)(bipy)(H2O)4]3+, 3. The solution quantitatively oxidizes hydrogen peroxide to oxygen and ascorbic acid to dehydroascorbic acid, itself being reduced to MnII. In the presence of excess reductant, the reactions follow simple first-order kinetics with no evidence for the accumulation of a significant amount of any intermediate manganese complex. The ascorbate anion shows overwhelming kinetic dominance over ascorbic acid, but no evidence is available for deprotonation of hydrogen peroxide. The preferred intimate mechanism for hydrogen peroxide is inner sphere but that for ascorbic acid is uncertain. For both reductants, increased extent of aquation leads to increased kinetic activity in the order: 1 < 2 < 3.Key words: kinetics, manganese, ascorbic acid, hydrogen peroxide, 2,2prime-bipyridine.

scholarly journals Kinetics of Oxidation of Cobalt(III) Complexes ofaAcids by Hydrogen Peroxide in the Presence of Surfactants

2008 ◽  
Vol 5 (1) ◽  
pp. 43-51 ◽  
Author(s):  
Mansur Ahmed ◽  
K. Subramani
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Bond Cleavage ◽  
Micellar Medium ◽  
Hydroxy Acids ◽  
Peroxide Oxidation ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

Hydrogen peroxide oxidation of pentaamminecobalt(III) complexes ofα-hydroxy acids at 35°C in micellar medium has been attempted. In this reaction the rate of oxidation shows first order kinetics each in [cobalt(III)] and [H2O2]. Hydrogen peroxide induced electron transfer in [(NH3)5CoIII-L]2+complexes ofα-hydroxy acids readily yields 100% of cobalt(II) with nearly 100% of C-C bond cleavage products suggesting that it behaves mainly as one equivalent oxidant in micellar medium. With unbound ligand also it behaves only as C-C cleavage agent rather than C-H cleavage agent. With increasing micellar concentration an increase in the rate is observed.

scholarly journals KINETICS OF OXIDATION WITH HYDROGEN PEROXIDE AND IRON(II) COMPLEX WITH A MACROCYCLIC BINUCLEATING LIGAND

1995 ◽  
Vol 3 (3) ◽  
pp. 55-62
Author(s):  
Lourdes T. Kist ◽  
Bruno Szpoganicz ◽  
Manuel G. Basallote ◽  
Maria J. F. Trujillo ◽  
Maria A. Mariez
Keyword(s):  
Hydrogen Peroxide ◽  
Macrocyclic Ligand ◽  
Kinetic Studies ◽  
Organic Substrates ◽  
Kinetics Of Oxidation ◽  
Oxidation Processes ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of ◽  
Catalyzed Oxidation

In the present study solutions of a complex of Fe(II) with a macrocyclic ligand were prepared and their oxidation kinetics with hydrogen peroxide examined. The kinetic studies of the oxidation processes lead to values of rate constant of two-step which occur via first-order kinetics. The results are expected to result in a better knowledge of the mechanism of H202 activation in catalyzed oxidation of organic substrates.

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.

Investigations into the kinetics and stoichiometry of bacterial oxidation of covellite (CuS) using a polarographic oxygen probe

1978 ◽  
Vol 24 (8) ◽  
pp. 998-1003 ◽  
Author(s):  
Pamela A. D. Rickard ◽  
Donald G. Vanselow
Keyword(s):  
Oxygen Uptake Rate ◽  
Zero Order ◽  
Bacterial Oxidation ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Cupric Ion ◽  
First Order Kinetics ◽  
Zero Order Kinetics ◽  
Cupric Sulphate ◽  
Kinetics Of

"Oxygraph" apparatus was used to measure quantitatively the kinetics of oxidation of synthetic covellite (CuS) in the presence and absence of Thiobacillus species. The expected stoichiometric relationship between oxygen consumed and cupric sulphate produced was verified by atomic absorption assays of cupric ion and sulphate ion. Thiobacillus cultures markedly increased the oxidation rate.The dependence of each oxygen-uptake rate on oxygen concentration was also measured. Sterile controls and some bacterial cultures showed first-order kinetics while other cultures showed zero-order kinetics.Addition of biological inhibitors to reacting slurries revealed that cultures showing first-order kinetics did not oxidize CuS itself but merely oxidized elemental sulphur formed by non-enzymic oxidation of CuS. Cultures showing zero-order kinetics oxidized CuS in a way that resulted in all oxygen reduction being enzymic. This mechanism possibly involves the cyclic oxidation and reduction of soluble iron.

Oxidation of the mercurous ion by peroxidase

1986 ◽  
Vol 64 (5) ◽  
pp. 969-972 ◽  
Author(s):  
Donald C. Wigfield ◽  
Season Tse
Keyword(s):  
Elemental Mercury ◽  
Order Rate Constant ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Rate ◽  
First Order Kinetics ◽  
Cold Vapour ◽  
Pseudo First Order ◽  
Kinetics Of ◽  
Mercurous Ion

The kinetics of oxidation of the mercurous ion by peroxidase have been measured by following the disappearance of mercurous ion using cold-vapour atomic absorption spectroscopy. Pseudo-first-order kinetics are observed with respect to mercurous ion, and the pseudo-first-order rate constants are linearly related to peroxidase concentration, showing first-order dependence on peroxidase. This behaviour is identical to oxidation of elemental mercury, and the second-order rate constant, 1.44 × 104 M−1 s−1 at 23 °C, is also, within experimental error, the same as that for elemental mercury oxidation. The data are interpreted in terms of peroxidase-induced disproportionation of the mercurous dimer, followed by two-electron oxidation of zero-valent mercury.

scholarly journals Kinetics of Oxidation of Hexakis (P-chloroaniline) Cobalt (II) Chloride by Potassium Iodate

2003 ◽  
Vol 2 (1) ◽  
pp. 34-38
Author(s):  
B. Edison ◽  
S. Peter
Keyword(s):  
Kinetic Parameters ◽  
Aqueous Medium ◽  
Neutral Salt ◽  
Complex Solution ◽  
Potassium Iodate ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

Vit B12 is an important complex of cobalt3 . The rate of oxidation of the Synthesized complex Hexakis(p-chloral aniline) cobalt((II) chloride follows first order kinetics with respect to the complex and oxidant potassium iodate1,2,4-8 in aqueous medium. Increasing in the concentration of complex solution increases the rate of the oxidation. The rate of the reaction is studied by changing the acid concentrations of the medium , by changing the temperature and by introducing the neutral salt (NaCl) in the Medium. From this study the kinetic parameters Ea, A,∆S#,∆G#,∆H# are found out. From the observed fats it is inferred that the reaction follows three steps.

scholarly journals Kinetics of the decomposition and the estimation of the stability of 10% aqueous and non-aqueous hydrogen peroxide solutions

2014 ◽  
Vol 27 (4) ◽  
pp. 213-216 ◽  
Author(s):  
Maria Zun ◽  
Dorota Dwornicka ◽  
Katarzyna Wojciechowska ◽  
Katarzyna Swiader ◽  
Regina Kasperek ◽  
...  
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Decomposition Rate ◽  
Aqueous Hydrogen Peroxide ◽  
Decomposition Rate Constant ◽  
First Order ◽  
First Order Kinetics ◽  
C 30 ◽  
The Stability ◽  
Kinetics Of

Abstract In this study, the stability of 10% hydrogen peroxide aqueous and non-aqueous solutions with the addition of 6% (w/w) of urea was evaluated. The solutions were stored at 20°C, 30°C and 40°C, and the decomposition of hydrogen peroxide proceeded according to first-order kinetics. With the addition of the urea in the solutions, the decomposition rate constant increased and the activation energy decreased. The temperature of storage also affected the decomposition of substance, however, 10% hydrogen peroxide solutions prepared in PEG-300, and stabilized with the addition of 6% (w/w) of urea had the best constancy.

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