scholarly journals Kinetics and mechanism of the oxidation of methionine by quinolinium chlorochromate

2005 ◽  
Vol 70 (2) ◽  
pp. 145-151 ◽  
Author(s):  
M. Pandeeswaran ◽  
John Bincy ◽  
D.S. Bhuvaneshwari ◽  
K.P. Elango

The oxidation of methionine by quinolinium chlorochromate (QCC) has been studied, in the presence of chloroacetic acid, and in water-acetic acid mixtures of varying mole fractions. The reaction is first order with respect to methionine, QCC and acid. The reaction rates were determined at three different temperatures (25, 35 and 45 ?C) and the activation parameters were computed. The reaction rate increased with increasing mole fraction of acetic acid in the mixture and specific solvent-solvent-solute interactions were found to predominate (81 %). A solvation model and a suitable mechanism for the reaction are postulated.

2006 ◽  
Vol 71 (1) ◽  
pp. 19-25 ◽  
Author(s):  
John Bincy ◽  
M. Pandeeswaran ◽  
D.S. Bhuvaneshwari ◽  
K.P. Elango

The oxidation of methionine by imidazolium fluorochromate (IFC) were studied, in the presence of chloroacetic acid, in water-acetic acid mixtures of varying molar compositions. The reaction is first order with respect to methionine, IFC and acid. The reaction rates were determined at different temperatures and the activation parameters were computed. The reaction rate increases with increasing mole fraction of acetic acid in the mixture and specific solvent-solvent-solute interactions were found to predominate (86 %). A solvation model and a probable mechanism for the reaction are postulated.


2008 ◽  
Vol 73 (7) ◽  
pp. 735-744 ◽  
Author(s):  
D.S. Bhuvaneshwari ◽  
K.P. Elango

The oxidation of methionine by quinolinium fluorochromate (QFC) was studied in the presence of chloroacetic acid, in water/organic solvent mixtures of varying excess molar free energy function. The reaction is first order with respect to both QFC and acid. The reaction rates were determined at different temperatures and the activation parameters computed. The rate data was correlated with different solvent parameters using linear multiple regression analysis. From the results, information on the solvent-reactants and the solvent-transition state interactions was obtained. .


2003 ◽  
Vol 58 (12) ◽  
pp. 1201-1205 ◽  
Author(s):  
Hesham A. A. Medien

Quinolinium dichromate (QDC) in sulfuric acid oxidizes benzaldehydes to the corresponding acids in a 50% (v/v) acetic acid-water medium. The reaction is first order each in [QDC], [substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. The rate decreases with an increase in the water content of the medium. The effects of substituents have been studied. A suitable mechanism is proposed.


2011 ◽  
Vol 8 (2) ◽  
pp. 643-648 ◽  
Author(s):  
S. Sheik Mansoor

The kinetics of oxidation of methionine (Met) by tripropylammonium fluorochromate (TriPAFC) has been studied in the presence of chloroacetic acid in aqueous acetic acid medium. The reaction is first order with respect to methionine, TriPAFC and acid. The reaction rate has been determined at different temperatures and activation parameters calculated. With an increase in the amount of acetic acid in its aqueous mixture, the rate increases. The reaction does not induce polymerization of acrylonitrile. A suitable mechanism has been proposed.


2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
S. Shree Devi ◽  
B. Muthukumaran ◽  
P. Krishnamoorthy

Kinetics and mechanism of oxidation of substituted 5-oxoacids by sodium perborate in aqueous acetic acid medium have been studied. The reaction exhibits first order both in [perborate] and [5-oxoacid] and second order in [H+]. Variation in ionic strength has no effect on the reaction rate, while the reaction rates are enhanced on lowering the dielectric constant of the reaction medium. Electron releasing substituents in the aromatic ring accelerate the reaction rate and electron withdrawing substituents retard the reaction. The order of reactivity among the studied 5-oxoacids is p-methoxy ≫ p-methyl > p-phenyl > –H > p-chloro > p-bromo > m-nitro. The oxidation is faster than H2O2 oxidation. The formation of H2BO3+ is the reactive species of perborate in the acid medium. Activation parameters have been evaluated using Arrhenius and Eyring’s plots. A mechanism consistent with the observed kinetic data has been proposed and discussed. Based on the mechanism a suitable rate law is derived.


Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan

The kinetics of Oxidation of Phenol and aniline by quinolinium Chlorochromate (QCC) in aqueous acetic acid medium leads to the formation of quinone and azobenzene respectively. The reactions are first order with respect to both Phenol and aniline. The reaction is first order with respect to quinolinium chlorochromate (QCC) and is catalyzed by hydrogen ion. The hydrogen-ion dependence has the form: kobs = a+b [H+]. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The reaction does not induced the polymerization of acrylonitrile. The retardation of the rate by the addition of Mn2+ ions confirms that a two electron transfer process is involved in the reaction. The reaction rates have been determined at different temperatures and the activation parameters have been calculated. From the above observations kinetic results a probable mechanism have been proposed.


2001 ◽  
Vol 56 (3) ◽  
pp. 281-286 ◽  
Author(s):  
Ceyhan Kayran ◽  
Eser Okan

Abstract The kinetics of the thermal substitution of norbornadiene (nbd) by 2,2'-bipyridine (2,2'-bipy) in (CO)4Mo(C7H9) was studied by quantitative FT-IR and UV-VIS spectroscopy. The reaction rate exhibits first-order dependence on the concentration of the starting complex, and the observed rate constant depends on the concentration of both leaving nbd and entering 2,2'-bipy ligand. The mechanism was found to be consistent with the previously proposed one, where the rate determining step is the cleavage of one of the two Mo-olefin bonds. The reaction was performed at four different temperatures (35 -50 °C) and the evaluation of the kinetic data gives the activation parameters which now support states.


2016 ◽  
Vol 12 (9) ◽  
pp. 4396-4403 ◽  
Author(s):  
K Anbarasu ◽  
N. GEETHA

The kinetics and mechanism of oxidation of benzaldehyde by quinoxalinium dichromate has been studied in the presence of perchloric acid in 70 % acetic acid - water medium. The reaction follows first order with respect to benzaldehyde, quinoxalinium dichromate and fractional order with respect to perchloric acid. There is no effect on the reaction rate with increase in ionic strength of the medium by adding sodium perchlorate. The rate of reaction increases with increase in the percentage of acetic acid. The reaction does not induce the polymerization with acrylonitrile. The rate of reaction decreases with increase in the concentration of manganoussulphate. The thermodynamic and activation parameters have been calculated and a probable mechanism has been proposed.


2011 ◽  
Vol 8 (4) ◽  
pp. 1728-1733 ◽  
Author(s):  
N. M. I. Alhaji ◽  
S. Sofiya Lawrence Mary

The kinetics of oxidation of isoleucine withN-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.


Author(s):  
L. Pushpalatha

The oxidation of malic acid by N-bromonicotinamide in the presence of micellar system is studied. First order kinetics with respect to NBN is observed. The kinetics results indicate that the first order kinetics in hydroxy acid at lower concentrations tends towards a zero order at its higher concentrations. Inverse fractional order in [H+] and [nicotinamide] are noted throughout its tenfold variation. Variation of [Hg (OAc)2] and ionic strength of the medium do not bring about any significant change in the rate of reaction. Rate of the reaction increases with a decrease in the percentage of acetic acid. Decrease in the rate constant was observed with the increase in [SDS]. The values of rate constants observed at four different temperatures were utilized to calculate the activation parameters. A suitable mechanism consistent with the experimental findings has been proposed.


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