Kinetic studies in the chemistry of rubber and related materials. II. The kinetics of oxidation of unconjugated olefins

1946 ◽  
Vol 42 ◽  
pp. 236 ◽  
Author(s):  
J. L. Bolland ◽  
Geoffrey Gee
Keyword(s):  
Kinetic Studies ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

scholarly journals Kinetics and Mechanism of Oxidation oft-Butylbenzylamine by Diperiodatoargentate(III) in Aqueous Alkali

2012 ◽  
Vol 9 (1) ◽  
pp. 203-210 ◽  
Author(s):  
Mahantesh A. Angadi ◽  
Suresh M. Tuwar
Keyword(s):  
Kinetic Studies ◽  
Active Species ◽  
Alkali Concentration ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Middle Range ◽  
Wide Range ◽  
Rate Of Reaction ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

t-Butylbenzylamine (t-BA) is used as a free base in the synthesis of salbutamol drug. Its mechanism of oxidation was proposed from kinetic studies. The kinetics of oxidation oft-butylbenzylamine by diperiodatoargentate(III) (DPA) was studied spectrophotometrically by monitoring decrease in absorbance of DPA. The reaction was found to be first order each in [DPA] and [t-BA]. The effect of alkali concentration in a wide range on rate of reaction was studied. The rate of reaction was found to be increased with increase in [OH–] in the lower range of [OH–], decreasing effect in the middle range and at higher range again increasing effect on rate of reaction was observed. The added periodate retarded the rate of reaction. The polymerization test revealed that oxidation was occurred with the intervention free radical. A suitable mechanism was proposed for a middle range of [OH–]. The active species of silver(III) periodate for all the three different stages of [OH–] are assayed. Rate law was derived and verified. The oxidative product oft-BA was characterized by LC-ESI-MS spectra.

Kinetic Studies in the Chemistry of Rubber and Related Materials. II. The Kinetics of Oxidation of Unconjugated Olefins

1947 ◽  
Vol 20 (3) ◽  
pp. 609-617 ◽  
Author(s):  
J. L. Holland ◽  
Geoffrey Gee
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Studies ◽  
Chain Termination ◽  
Low Oxygen ◽  
Chain Reaction ◽  
Kinetics Of Oxidation ◽  
Chain Initiation ◽  
A Chain ◽  
Kinetics Of ◽  
Direct Attack

Abstract A brief review is given of kinetic work on the oxidation of representative mono, 1,4 and 1,5 olefins. The essential process in each case is identified as a chain reaction in which hydrocarbon radicals are formed, absorb oxygen, and then react with another molecule of olefin to give a hydroperoxide and a new free radical. Three methods of chain initiation are considered: (1) direct attack of oxygen on the olefin, (2) thermal decomposition of the hydroperoxide, (3) thermal decomposition of added benzoyl peroxide. Chain termination results from interaction of two free radicals; except at low oxygen pressures, these are both peroxidic.

scholarly journals Kinetic Studies on the Oxidation of Someparaandmeta-Substituted Cinnamic Acids by Pyridinium Bromochromate in the Presence of Oxalic Acid (A Co-oxidation Study)

2009 ◽  
Vol 6 (3) ◽  
pp. 920-927 ◽  
Author(s):  
G. Vanangamudi ◽  
S. Srinivasan
Keyword(s):  
Oxalic Acid ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Cinnamic Acids ◽  
Kinetics Of Oxidation ◽  
Oxidation Study ◽  
Low Dielectric ◽  
Rate Of Reaction ◽  
Acetic Acid Water ◽  
Kinetics Of

The kinetics of oxidation of cinnamic acids by pyridinium bromochromate (PBC) in the presence of oxalic acid has been studied in acetic acid-water (60:40%) medium. The reaction shows unit order dependence each with respect to oxidant as well as oxalic acid [OX], the order with respect to [H+] and [CA] are fractional. The reaction is acid catalyzed and a low dielectric constant favours the reaction. Increase the ionic strength has no effect on the reaction rate. In the case of substituted cinnamic acids the order with respect to substrate vary depending upon the nature of the substituent present in the ring. In general, the electron withdrawing substituents retard the rate while the electron releasing substituents enhance the rate of reaction. From the kinetic data obtained the activation parameters have been computed and a suitable mechanism has been proposed.

scholarly journals Wet Oxidation of Dairy Sewage: The Kinetic Study of Decomposition of the Milk Components

2013 ◽  
Vol 20 (3) ◽  
pp. 531-541
Author(s):  
Klara Piotrowska ◽  
Mirosław Imbierowicz ◽  
Andrzej Chacuk
Keyword(s):  
Oxidation Process ◽  
Kinetic Studies ◽  
Milk Composition ◽  
Wet Oxidation ◽  
Kinetics Of Oxidation ◽  
Tank Reactor ◽  
Kinetics Of Decomposition ◽  
Milk Components ◽  
Composition Analyzer ◽  
Kinetics Of

Abstract The article presents the results of kinetic studies of the wet oxidation process of dairy sewage. The dairy sewage, obtained straight from the production line, was subjected to oxidation at pH close to the natural value of 7. Experiments were carried out in a stirred batch tank reactor at the oxygen partial pressure equal to 1 MPa and at temperature ranging from 473 to 593 K. The effectiveness of organic compounds decomposition was estimated based on the measurement of TOC. The kinetics of decomposition of milk components, ie lactose, protein and fat, as well as the kinetics of oxidation of intermediate products was the aim of the study. Measurement of the concentration of protein, fat and lactose was done with a milk composition analyzer, calibrated in relation to the dairy sewage. The obtained results were used to develop a mathematical model of wet oxidation of dairy sewage, including the group of analyzed compounds.

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.

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.

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