scholarly journals Oxidation of Some Aliphatic Alcohols by Pyridinium Chlorochromate -Kinetics and Mechanism

2009 ◽  
Vol 6 (1) ◽  
pp. 237-246 ◽  
Author(s):  
Sapana Jain ◽  
B. L. Hiran ◽  
C. V. Bhatt
Keyword(s):  
Dielectric Constant ◽  
Carbonyl Compounds ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Hydrogen Ion ◽  
Pyridinium Chlorochromate ◽  
Secondary Alcohols ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

Kinetics of oxidation of some aliphatic primary and secondary alcoholsviz.,ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl butanol by pyridinium chlorochromate (PCC) have been studied in water- perchloric acid medium. The reaction shows first order dependence with respect to pyridinium chlorochromate [PCC] and hydrogen ion [H+]. The rate of oxidation decreases with increase in dielectric constant of solvent suggests ion-dipole interaction. Activation parameters have been evaluated. Products are carbonyl compounds and free radical absence was proved. A tentative mechanism has been proposed.

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 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.

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.

scholarly journals Kinetics and Mechanism of Oxidation of Diethanolamine and Triethanolamine by Potassium Ferrate

2011 ◽  
Vol 8 (2) ◽  
pp. 903-909 ◽  
Author(s):  
Shan Jinhuan ◽  
Zhang Jiying
Keyword(s):  
Activation Parameters ◽  
Rate Equations ◽  
Potassium Ferrate ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Dependence ◽  
Rate Determining Step ◽  
Thermodynamic Activation Parameters ◽  
Plausible Mechanism ◽  
Kinetics Of

The kinetics of oxidation of diethanolamine and triethanolamine by potassium ferrate(VI)in alkaline liquids at a constant ionic strength has been studied spectrophotometrically in the temperature range of 278.2K-293.2K. The reaction shows first order dependence on potassium ferrate(VI), first order dependence on each reductant, The observed rate constant (kobs) decreases with the increase in [OH-], the reaction is negative fraction order with respect to [OH-]. A plausible mechanism is proposed and the rate equations derived from the mechanism can explain all the experimental results. The rate constants of the rate-determining step and the thermodynamic activation parameters are calculated.

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.

Kinetics of oxidation of α-ketoglutaric acid with Ce(IV) ions in relation to Belousov-Zhabotinskii reaction

1982 ◽  
Vol 47 (11) ◽  
pp. 2831-2837 ◽  
Author(s):  
Ľudovít Treindl ◽  
Vasil Dorovský
Keyword(s):  
Redox Reaction ◽  
Platinum Electrode ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Redox Catalyst ◽  
Oscillation Reaction ◽  
Belousov Zhabotinskii Reaction ◽  
Kinetics Of

Oxidation of α-ketoglutaric acid with Ce(IV) ions in a solution of sulphuric acid is a reaction of the first order with respect to both Ce(IV) ions and substrate, is acid catalysed, and its rate is proportional to the reciprocal square of the equilibrium HSO4- concentration. From the temperature dependence of the rate constant in 1.5M-H2SO4, the activation parameters were determined as ΔH##f = 57 kJ/mol and ΔS##f = -45 J mol-1 K-1. The redox reaction proper consists apparently of two steps: in the first one, the enol form of α-ketoglutaric acid reacts with Ce(IV) ions with the formation of the corresponding radical; in the second one, the latter is oxidized further with Ce(IV) to give malonic and succinic acids. Conditions are indicated under which α-ketoglutaric acid serves as substrate for the Belousov-Zhabotinskii oscillation reaction in the presence of Ce(IV)-Ce(III) redox catalyst. Oscillations of Ce(IV) and Br2 concentrations, shifted in phase, can be recorded polarographically with a rotating platinum electrode.

scholarly journals Kinetics and Mechanism of Oxidation of Glutamic Acid byN-Bromophthalimide in Aqueous Acidic Medium

2011 ◽  
Vol 8 (4) ◽  
pp. 1472-1477
Author(s):  
N. M. I. Alhaji ◽  
S. Sofiya Lawrence Mary
Keyword(s):  
Dielectric Constant ◽  
Ionic Strength ◽  
Glutamic Acid ◽  
Acidic Medium ◽  
Reaction Medium ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Mechanism Of Oxidation ◽  
Kinetics Of ◽  
Aqueous Acidic Medium

The kinetics of oxidation of glutamic acid (Glu) withN-bromophthalimide (NBP) was studied in perchloric acid medium at 30°C by potentiometric method. The reaction is first order each in NBP and glutamic acid and is negative fractional order in [H+]. Addition of KBr or the reaction product, phthalimide had no effect on the rate. Similarly variation of ionic strength of the medium did not affect the rate of the reaction. Also the rate increased with decrease in dielectric constant of the reaction medium. The thermodynamic parameters were computed from Arrhenius and Eyring plots. A suitable mechanism consistent with the kinetic results has been proposed.

Kinetics and mechanism of oxidation of lactic acid by KMnO4 in H2SO4 medium

1985 ◽  
Vol 63 (12) ◽  
pp. 3317-3321 ◽  
Author(s):  
M. M. Girgis ◽  
S. A. El-Shatoury ◽  
Z. H. Khalil
Keyword(s):  
Lactic Acid ◽  
Oxidation Rate ◽  
Arrhenius Equation ◽  
Activation Parameters ◽  
Initial Oxidation ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Acid Catalyzed ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

The initial oxidation stages of lactic acid by acid permanganate were investigated. The rate of the induction period was slow and then gradually increased. The kinetics of oxidation were second order, first order with respect to both lactic acid and Mn(VII). The reaction was acid catalyzed. Addition of Mn(II) ions largely increased the rate of the initial stages and decreased the rate of the following stages. The oxidation rate was decreased by the addition of F− or [Formula: see text] ions. The Arrhenius equation was valid for the reaction between 16.5 and 34 °C. Activation parameters were evaluated and a mechanism consistent with the results obtained was proposed.

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.

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