Kinetics of oxidation of hydrocarbons by quinolinium dichromate

1991 ◽  
Vol 4 (4) ◽  
pp. 217-224 ◽  
Author(s):  
G. C. Sarma ◽  
M. K. Mahanti
Keyword(s):  
Kinetics Of Oxidation ◽  
Oxidation Of Hydrocarbons ◽  
Kinetics Of

The kinetics of oxidation of benzaldehyde. I

1953 ◽  
Vol 216 (1124) ◽  
pp. 10-29 ◽  
Keyword(s):  
Benzene Solution ◽  
Point Of View ◽  
Peroxide Formation ◽  
Kinetics Of Oxidation ◽  
Oxidation Of Hydrocarbons ◽  
Complicated Manner ◽  
Short Period ◽  
The Relationship ◽  
Kinetics Of ◽  
Dibenzoyl Peroxide

For the study of the mechanism of oxidation of hydrocarbons and other organic compounds it is desirable to find systems suitable for kinetic study in which the mechanism of peroxide formation is not complicated by autocatalysis. The oxidation of benzaldehyde in benzene solution in the absence of light has been examined from this point of view. It was found that in the absence of catalysts and inhibitors consistently reproducible rates of oxidation are to be obtained only with special precautions in the preparation and handling of the materials. For a short period after the beginning of the reaction, the amount of peroxide in the solution corresponds closely to the oxygen taken up. There is no sign of autocatalysis. The reaction, on the contrary, is self-inhibiting. The rate of oxidation is extremely sensitive to the presence of inhibitors, the effect of 10~e mole /?-naphthol/mole solution being easily detected. The reaction is catalyzed by dibenzoyl peroxide according to the relationship ρ = ρ u + k [ Bz 2 O 2 ]1/2 , P and pu being the initial rates in the presence and absence of dibenzoyl peroxide respectively and k a constant. Two conclusions are drawn from this result: (i) in the peroxide catalyzed reaction the chains are terminated by mutual interaction and (ii) the mechanism of the uncatalyzed dark reaction involves different chain carriers from those of the catalyzed reaction. In the presence of dibenzoyl peroxide both reactions take place simultaneously but independently. The oxidation is also catalyzed, though in a rather more complicated manner, by Pyrex glass.

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.

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.

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.

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