scholarly journals Kinetics and Mechanistic Study of Cetyltrimethylammonium Bromide Catalyzed Oxidation of Tetraethylene Glycol byN-Chlorosaccharin in Acidic Medium

2008 ◽  
Vol 5 (3) ◽  
pp. 598-606
Author(s):  
Vandana Sharma ◽  
K. V. Sharma ◽  
V. W. Bhagwat
Keyword(s):  
Cetyltrimethylammonium Bromide ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Mechanistic Study ◽  
Tetraethylene Glycol ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
First Order ◽  
Dielectric Effect ◽  
Catalyzed Oxidation

The kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of tetraethylene glycol [2,2'-(oxibis(ethylenoxy)diethanol)] byN-chlorosaccharin in aqueous acetic acid medium in presence of perchloric acid have been investigated at 323K. The reaction is first order dependence on Nchlorosaccharin. The reaction rate follows first order kinetics with respect to [tetraethylene glycol] with excess concentration of other reactants. The miceller effect due to cetyltrimethylammonium bromide, a cationic surfactant has been studied. The change in ionic strength shows negligible salt effect. The dielectric effect is found to be positive. Addition of one of the products (saccharin) retards the reaction rate. Activation parameters are calculated from the Arrhenious plot. A possible mechanism consistent with the experimental results has been proposed.

scholarly journals Perborate Oxidation of Substituted 5-Oxoacids in Aqueous Acetic Acid Medium: A Kinetic and Mechanistic Study

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
S. Shree Devi ◽  
B. Muthukumaran ◽  
P. Krishnamoorthy
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Mechanistic Study ◽  
Aqueous Acetic Acid ◽  
Sodium Perborate ◽  
Acetic Acid Medium

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.

scholarly journals Reactivity of Phenol and Aniline towards Quinolinium Chloro Chromate: A Comparative Oxidation Kinetic Study

2015 ◽  
Vol 59 ◽  
pp. 81-92
Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan
Keyword(s):  
Oxidation Kinetic ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Reaction Rates ◽  
Hydrogen Ion ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
First Order ◽  
Different Temperatures ◽  
Kinetics Of

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.

scholarly journals Kinetics and mechanism of the oxidation of some cis-Alpha- Phenylcinnamic acids by Pyridinium Chlorochromate

2017 ◽  
Vol 12 (5) ◽  
pp. 4434-4441
Author(s):  
S. Nalini ◽  
R. Udhayakumar ◽  
K. Anbarasu ◽  
P. Manivannan ◽  
K. Raghu
Keyword(s):  
Reaction Rate ◽  
Activation Parameters ◽  
Sodium Chlorate ◽  
Dipole Interaction ◽  
Slow Step ◽  
Pyridinium Chlorochromate ◽  
Cinnamic Acids ◽  
Acetic Acid Medium ◽  
First Order ◽  
Rate Of Reaction

Oxidation of cis α-phenyl cinnamic acids by pyridinium chlorochromate (PCC) was studied in acetic acid–water mixturecontaining perchloric acid. The reaction rate is first order in [PCC] and fractional order in [H+] and has aldehyde as aproduct. The rate of reaction increases with increase in the percentage of acetic acid medium. The reactions exhibit kineticisotope effect. The activation parameters have been evaluated. The added Mn (II) decreases the rate of reaction. Theadded sodium chlorate has no effect on the reaction rate and indicates the absence of ion-ion (or) ion- dipole interaction inthe slow step. The deviation of Hammett plot is noted and a “V” shaped curve is obtained.

scholarly journals Kinetics of Oxidation of Cychlohexanol by N-Chloronicotinamide in Aqueous Acetic Acid Medium

2004 ◽  
Vol 3 (1) ◽  
pp. 1-6
Author(s):  
R. Sridharan ◽  
N. Mathiyalagan
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Activation Parameters ◽  
Acid Mixture ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Retarding Effect ◽  
Kinetics Of

Kinetics of oxidation o Cyclohexanol by N-Chloronicotinamide(NCN) in 50% V/V aqueous acetic acid mixture has been investigated in the presence of HCIO4 and NaCl. The observed rate of oxidation is first-order with respect to oxidation (NCN) and fractional-order with respect to cyclohexanol. A decrease in dielectric constant of the medium increases the rate. Addition of nicotinamide (NA), the reduction product of NCN, has a retarding effect an the rate of oxidation. Arrhenius and activation parameters are calculated. Kinetics of bromination1 and oxidation2,3 of saturated organic compounds by N-bromosuccinimide(NBS) have been received considerable attention. Kinetics and mechanism of oxidation of amino acids by NCN has been reported in aqueous acetic acid medium, we report herein the result of similar studies on the oxidation of cyclohexanol with NCN in aqueous acetic acid medium.

scholarly journals Kinetics of Oxidation of 3-Benzoylpropionic Acid byN-Chlorobenzamide in Aqueous Acetic Acid Medium

2011 ◽  
Vol 8 (2) ◽  
pp. 561-564 ◽  
Author(s):  
N. A. Mohamed Farook ◽  
G. A. Seyed Dameem
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Reaction Medium ◽  
Activation Parameters ◽  
Slow Step ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

The kinetics of oxidation of 3-benzoylpropionic acid(KA)byN-chlorobenzamide(NCB)in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order dependence each in[KA],[NCB]and [H+]. The main product of the oxidation is the corresponding carboxylic acid. The rate decreases with the addition of benzamide, one of the products of the reaction. Variation in ionic strength of the reaction medium has no significant effect on the rate of oxidation. But the rate of the reaction is enhanced by lowering the dielectric constant of the reaction medium. Hypochlorous acidium ion (H2O+Cl), has been postulated as the reactive oxidizing species. A mechanism consistent with observed results have been proposed and the related rate law deduced. The activation parameters have been computed with respect to slow step of the mechanism.

scholarly journals Kinetics of Oxidation of Benzoin by N. Bromosuccinimide

2005 ◽  
Vol 4 (1) ◽  
pp. 55-61
Author(s):  
R. Sridharan ◽  
N. Mathiyalagan
Keyword(s):  
Dielectric Constant ◽  
Acetic Acid ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Aqueous Acetic Acid ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Retarding Effect ◽  
Kinetics Of

Kinetics of Oxidation of Benzoin by N. Bromosuccinimide[NBS] 80% aqueous acetic acid has been investigated. The reaction follows first-order kinetics with respect to both[NBS] and [benzoin]. The effect of varying ionic strength and dielectric constant indicate the reaction is dipole-dipole type. Addition of succinimide(>NH), has a retarding effect on the rate of oxidation. The product of oxidation is benzil. By studying the effect of temparature on the reaction rate, the Arrhenius and the activation parameters have been calculated. A suitable mechanism has been proposed and a rate low explaining the experiment results is derived.

scholarly journals Kinetics and Mechanism of Oxidation of Benzyl Alcohol by Benzimidazolium Fluorochromate

2008 ◽  
Vol 5 (4) ◽  
pp. 754-760
Author(s):  
J. Dharmaraja ◽  
K. Krishnasamy ◽  
M. Shanmugam
Keyword(s):  
Benzyl Alcohol ◽  
Sodium Perchlorate ◽  
Activation Parameters ◽  
Aqueous Acetic Acid ◽  
Hydrogen Ions ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Oxidation Of Benzyl Alcohol ◽  
Kinetics Of

The kinetics of oxidation of benzyl alcohol (BzOH) by benzimidazolium fluorochromate (BIFC) has been studied in 50% aqueous acetic acid medium at 308 K. The reaction is first order with respect to [oxidant] and [benzyl alcohol]. The reaction is catalysed by hydrogen ions. The decrease in dielectric constant of the medium increases the rate of the reaction. Addition of sodium perchlorate increases the rate of the reaction appreciably. No polymerization with acrylonitrile. The reaction has been conducted at four different temperature and the activation parameters were calculated. From the observed kinetic results a suitable mechanism was proposed.

scholarly journals Oxidation of Methionine by Tripropylammonium Fluorochromate-A Kinetic and Mechanistic Study

2011 ◽  
Vol 8 (2) ◽  
pp. 643-648 ◽  
Author(s):  
S. Sheik Mansoor
Keyword(s):  
Acetic Acid ◽  
Activation Parameters ◽  
Chloroacetic Acid ◽  
Mechanistic Study ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Different Temperatures ◽  
Aqueous Mixture ◽  
Oxidation Of Methionine ◽  
Kinetics Of

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.

scholarly journals Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids

2014 ◽  
Vol 2014 ◽  
pp. 1-14 ◽  
Author(s):  
S. Shree Devi ◽  
P. Krishnamoorthy ◽  
B. Muthukumaran
Keyword(s):  
Hydrogen Peroxide ◽  
Kinetic Data ◽  
Reaction Rate ◽  
Acidic Solution ◽  
Activation Parameters ◽  
Reactive Species ◽  
Rate Law ◽  
First Order ◽  
Catalyzed Oxidation ◽  
Electron Withdrawing Substituents

Ruthenium(III) catalyzes perborate oxidation of substituted 5-oxoacids in acidic solution. The catalyzed oxidation is first order with respect to the oxidant and catalyst. The rate of ruthenium(III) catalyzed oxidation displays the Michaelis-Menten kinetics on the reductant and is independent of [H+] of the medium. Hydrogen peroxide is the reactive species of perborate and the kinetic results reveal formation of ruthenium(III) peroxo species-5-oxoacid complex. Electron-releasing substituents accelerate the reaction rate and electron-withdrawing substituents retard it. The order of reactivity among the studied 5-oxoacids is p-methoxy ≫  p-methyl > p-phenyl > −H > p-chloro > p-bromo > m-nitro. Activation parameters are evaluated using Arrhenius and Eyring’s plots. A mechanism consistent with the observed kinetic data is proposed and discussed. A suitable rate law is derived based on the mechanism.

scholarly journals Kinetics and mechanism of meso-tetraphenylporphyriniron(III) chloride (TPP) catalysed oxidation of indole by sodium perborate

2013 ◽  
Vol 15 (2) ◽  
pp. 107-111 ◽  
Author(s):  
D. Kungumathilagam ◽  
K. Karunakaran
Keyword(s):  
Acetic Acid ◽  
Catalytic Activity ◽  
Reaction System ◽  
Kinetic Scheme ◽  
Mechanistic Study ◽  
Radical Mechanism ◽  
Aqueous Acetic Acid ◽  
Sodium Perborate ◽  
Acetic Acid Medium ◽  
Catalysed Oxidation

Developing catalyst is very significant for biologically important reactions which yield products, used as drugs. Mechanistic study on meso-tetraphenylporphyriniron(III) chloride (TPP) catalysed oxidation of indole by sodium perborate in aqueous acetic acid medium have been carried out. The reaction follows a fractional order with respect to substrate and catalyst. The order with respect to oxidant was found to be one. Increase in the percentage of acetic acid and increase in the concentration of [H+] decreased the rate. The reaction fails to initiate polymerization, and a radical mechanism is ruled out. Activation and thermodynamic parameters have been computed. A suitable kinetic scheme based on these observations has been proposed. Significant catalytic activity is observed for the reaction system in the presence of TPP.

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