Kinetics of oxidation of bivalent iron by chlorate

1979 ◽  
Vol 44 (9) ◽  
pp. 2760-2768 ◽  
Author(s):  
Karel Mádlo
Keyword(s):  
Rate Equation ◽  
Heterogeneous Systems ◽  
Time Interval ◽  
Kinetics Of Oxidation ◽  
Homogeneous Systems ◽  
Spontaneous Change ◽  
Hydrolysis Products ◽  
Constant Ph ◽  
Bivalent Iron ◽  
Kinetics Of

Kinetics of Fe(II) oxidation by chlorate was studied in homogeneous systems (pH 1, HCLO4 and in heterogeneous systems involving precipitate of Fe(III) hydrolysis products (pH 1 to 5.5). The stoichiometry ( 6 Fe2+ : 1 ClO-3 : 6H+) as well as the rate equation (-d[Fe2+]/dt = kexp/.[Fe2+][ClO-3]) is the same in the two cases. Also the differences in the experimental activation energies and entropies for the two pH regions are insignificant. The [OH-]/[Fe3+] ratio passes a maximum during the spontaneous change of pH (pH0 5), whereas if the pH is maintained constant (pH 5) the ratio increases monotonically throughout the whole time interval followed. The balance of the Fe2+ and Fe3+ showed that part of the Fe2+ ( 10-3 mol l-1) was present during the reaction in the precipitate of the Fe(III) hydrolysis products, while part of the Fe3+ (5 . 10-3 mol l-1) existed outside this precipitate; the latter dropped by approximately two orders of magnitude only several tens of hours after the finishing of the Fe(II) oxidation.

scholarly journals Kinetics and Mechanism of Catalyzed Oxidation of L-Cysteine by Salen Schiff Base Complexes of Co(III), Fe (III) and Cr(III)

2021 ◽  
Vol 13 (2) ◽  
pp. 25
Author(s):  
Hamzeh M. Abdel-Halim ◽  
Hutaf M. Baker ◽  
Akef I. Alhmaideen ◽  
Adnan S. Abu-Surrah
Keyword(s):  
Schiff Base ◽  
Metal Ion ◽  
Reduction Potential ◽  
Order Conditions ◽  
Schiff Base Complexes ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Constant Ph ◽  
Kinetics Of ◽  
Catalyzed Oxidation

Kinetics of oxidation of L-cysteine by new series of substituted ONNO-donor salen-type Schiff base complexes of general formula [MIII(L)Cl] (M = Co, Fe, Cr; L = Schiff base ligand) have been studied in aqueous solutions. Measurements were run at constant temperature (25º C), constant ionic strength (0.20 M), and constant pH (7.0) under pseudo-first order conditions, in which the concentration of cysteine is around two orders of magnitude greater than that of metal complex. The observed rate constant was determined by following the change in absorbance of reaction mixture at a predetermined wavelength with time. Results show that the rate of oxidation depends on the type of metal center, with Co(III) complexes were found to have the highest rates due to higher reduction potential of Co(III). The oxidation rate was also found to depend on steric factor and the electron withdrawing / releasing ability of the ligand bound to the metal ion.

Cinétique d'oxydation des oximes du benzaldéhyde et de l'acétophénone par l'ion thallique

1980 ◽  
Vol 58 (13) ◽  
pp. 1305-1310 ◽  
Author(s):  
Robert Lortie ◽  
Miklos Zador
Keyword(s):  
Reaction Mechanism ◽  
Aqueous Medium ◽  
Rate Equation ◽  
Chloride Ions ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

The kinetics of oxidation of benzaldehyde and acetophenone oximes by Tl(III) in aqueous medium has been studied. The reaction occurs in two consecutive steps: formation of a nitroso intermediate and its decomposition. The oxime forms a complex with Tl(III) leading to the rate equation: −d[oxime]/dt = K1/k2[oxime][Tl(III)]/(1 + K1[Tl(III)]). The formation of the final carbonyl product is inhibited by Tl(III), a resuit of the formation of a complex resistant to decomposition. Coordination of Tl(III) by chloride ions affects the rate of the above two steps. The reaction mechanism is discussed. [Journal translation]

Spectrocoulometry – a new spectro-electrochemical technique

1987 ◽  
Vol 52 (6) ◽  
pp. 1386-1396 ◽  
Author(s):  
Ján Mocák ◽  
Michal Németh ◽  
Mieczyslaw Lapkowski ◽  
Jerzy W. Strojek
Keyword(s):  
Optical Probe ◽  
Optical Signal ◽  
Open Circuit ◽  
Electrochemical Technique ◽  
Kinetics Of Oxidation ◽  
Hydrolytic Reaction ◽  
Experimental Errors ◽  
Mechanism And Kinetics ◽  
Kinetics Of

A spectrocoulometric macrocell with a direct-view optical probe was designed and constructed, where the optical signal is transferred by light-conducting glass or quartz fibres permitting to work at wavelengths above 410 or 300 nm. The method of measurement on the proposed equipment is described; it was tested in the study of the mechanism and kinetics of oxidation of Fe(bipy)32+ ions (bipy = 2,2'-bipyridyl) with the use of potentiostatic coulometric electrolysis with open-circuit relaxation at a suitable time. The primary product of electrolysis, Fe(bipy)33+, undergoes a follow-up hydrolytic reaction with the formation of a binuclear complex. The rate constant of the reaction of the first order involves the contributions, kBi, from all bases present in solution; the corresponding values for H2O, OH-, bipy, and CH3COO- ions at a ionic strength 0·5 mol dm-3 and 25 °C were determined as kOH = (5·0 ± 0·6) . 105 mol-1 dm3 s-1, kbipy = (1·3 ± 0·2) . 10-1 mol-1 dm3 s-1, kAc = (5·8 ± 1·0) . 10-2 mol-1 dm3 s-1, and kH2O is not significant with respect to experimental errors.

Effects of salts on the kinetics of oxidation of alkenes by thallic salts in aqueous solutions

1981 ◽  
Vol 46 (3) ◽  
pp. 693-700 ◽  
Author(s):  
Milan Strašák ◽  
Jaroslav Majer
Keyword(s):  
Aqueous Solutions ◽  
Phase Transfer ◽  
Heterogeneous Reaction ◽  
Qualitative Model ◽  
Kinetic Effect ◽  
Tetraalkylammonium Salts ◽  
Reaction Conditions ◽  
Kinetics Of Oxidation ◽  
Kinetics Of ◽  
Heterogeneous Reaction Conditions

The kinetics of oxidation of alkenes by thallic sulphate in aqueous solutions, involving the two reaction steps-the hydroxythallation and the dethallation - was studied, and the effect of salts on the kinetics was examined; this made it possible to specify more precisely the reaction mechanism and to suggest a qualitative model of the reaction coordinate. It was found that in homogeneous as well as in heterogeneous reaction conditions, the reaction can be accelerated appreciably by adding tetraalkylammonium salts. These salts not only operate as catalysts of the phase transfer, but also exert a significant kinetic effect, which can be explained with a simplification in terms of a stabilization of the transition state of the reaction.

Kinetics of oxidation of ammonia on cobalt catalyst I model of the reactor with catalytically active wall

1982 ◽  
Vol 47 (8) ◽  
pp. 2087-2096 ◽  
Author(s):  
Bohumil Bernauer ◽  
Antonín Šimeček ◽  
Jan Vosolsobě
Keyword(s):  
Parabolic Equations ◽  
Cobalt Catalyst ◽  
Nonlinear Parabolic Equations ◽  
Catalytic Reactions ◽  
Temperature Profiles ◽  
Dimensional Model ◽  
Kinetics Of Oxidation ◽  
Nonlinear Parabolic ◽  
Catalytically Active ◽  
Kinetics Of

A two dimensional model of a tabular reactor with the catalytically active wall has been proposed in which several exothermic catalytic reactions take place. The derived dimensionless equations enable evaluation of concentration and temperature profiles on the surface of the active component. The resulting nonlinear parabolic equations have been solved by the method of orthogonal collocations.

Kinetics of catalytic reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst

1983 ◽  
Vol 48 (11) ◽  
pp. 3202-3208 ◽  
Author(s):  
Zdeněk Musil ◽  
Vladimír Pour
Keyword(s):  
Carbon Monoxide ◽  
Nitrogen Oxide ◽  
Rate Equation ◽  
Catalytic Reduction ◽  
Zero Order ◽  
Spectroscopic Measurements ◽  
First Order ◽  
Ir Spectroscopic ◽  
Kinetics Of ◽  
Al2o3 Catalyst

The kinetics of the reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst (8.36 mass % CuO) were determined at temperatures between 413 and 473 K. The reaction was found to be first order in NO and zero order in CO. The observed kinetics are consistent with a rate equation derived from a mechanism proposed on the basis of IR spectroscopic measurements.

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

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