Osmium(VIII) Catalyzed Oxidation of Acetone and Ethylmethyl Ketone by Chloramine-T

The Osmium (VIII) catalyzed oxidation of acetone and ethylmethyl ketone by chloramine-T, in highly alkaline solutions showed first order dependence to chloramine-T and osmium (VIII). The order of the reactions with respect to alkali and ketone were found to be fractional, being ~-0.82 and 0.3 respectively. No effects of ionic strength were evident. The mechanism has been proposed on the basis of the formation of a complex between N-chlorotoluene-p-sulfonamide and osmium (VIII) in the slow step, which in turn oxidizes the enol anion of the reducing substrate in the fast step.During the study of the mechanism of oxidations by chloramine-T, the kinetics of the oxidation of α-hydroxy acids 1 in presence of osmium (VIII) as catalyst, glycerol2 in neutral and alkaline media, p-cresol3 in an acidic medium, hexacyanoferrate (II)4 in a feebly acidic medium (pH 6-7) and aliphatic aldehydes 5 in alkaline media have been investigated.Despite the high redox potential6 of the chloramine-T/toluene sulfonamide system (1.138 V at pH 12), the oxidation of acetone does not take place in absence of catalyst and that of ethylmethyl ketone proceeds only in highly alkaline solutions7 (NaOH>0.01 M). In the present note the kinetics of the osmium (VIII) catalyzed oxidation of acetone and ethylmethyl ketone have been recorded.

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Kinetics of Photochemical Oxidation of Glucose by Chloramine-T in Acidic Medium: A Mechanistic Approach

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.816-817.7 ◽

2013 ◽

Vol 816-817 ◽

pp. 7-12

Author(s):

Meena Wadhwani ◽

Shubha Jain

Keyword(s):

Acidic Medium ◽

Reaction Rate ◽

Accurate Method ◽

Photochemical Oxidation ◽

First Order ◽

Mechanistic Approach ◽

Excess Concentration ◽

Chloramine T ◽

Kinetics Of ◽

Oxidation Of Glucose

A simple, convenient and accurate method for the kinetic study of photochemical oxidation of glucose by chloramine-T in acidic medium is described. The kinetic investigation shows the first order dependence of reaction rate on chloramine-T. With excess concentration of other reactants the reaction rate follows fractional order kinetics with respect to substrate. The reaction is catalyzed by H+ ions as well. A small salt effect and increase in reaction rate with increasing the intensity of light source is also observed. Addition of p-toluene sulphonamide retards the reaction rate. A suitable mechanism in agreement with observed kinetics has been proposed

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Entropy-Controlled Cu(II)-Catalyzed Oxidation of N-Acetyl-L-Cysteine by Methylene Blue in Acidic Medium

Zeitschrift für Physikalische Chemie ◽

10.1515/zpch-2016-0853 ◽

2017 ◽

Vol 231 (6) ◽

Author(s):

Ranjana Sharma ◽

Mahender Pal ◽

K.K. Mishra

Keyword(s):

Methylene Blue ◽

Acidic Medium ◽

Hydrogen Ions ◽

First Order ◽

First Order Kinetics ◽

Rate Of Reaction ◽

Entropy Of Activation ◽

Size And Morphology ◽

Kinetics Of ◽

Catalyzed Oxidation

AbstractKinetics of the oxidation of N-acetyl-L-cysteine (NAC) by methylene blue (MB) catalyzed by Cu(II) have been investigated in presence of HCl. The reaction follows a first order kinetics in MB while the concentration order in NAC is zero. Hydrogen ions retard the rate of reaction. The reaction involves the participation of nanoparticles as revealed by SEM, XRD and FTIR techniques and a gel-like Cu-NAC network acts like the effective catalyst. The reaction conforms to Eley-Rideal mechanism at lower [NAC] while at higher [NAC], the kinetics are explained by extended Eley-Rideal mechanism. The reaction is regulated by the size and morphology of the nanoparticles and is controlled by the entropy of activation.

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Kinetics and reactivities of ruthenium(III)- and osmium(VIII)-catalyzed oxidation of ornidazole with chloramine-T in acid and alkaline media: A mechanistic approach

Journal of Molecular Catalysis A Chemical ◽

10.1016/j.molcata.2009.05.015 ◽

2009 ◽

Vol 310 (1-2) ◽

pp. 24-33 ◽

Cited By ~ 43

Author(s):

Puttaswamy ◽

Anu Sukhdev ◽

J.P. Shubha

Keyword(s):

Alkaline Media ◽

Mechanistic Approach ◽

Chloramine T ◽

Catalyzed Oxidation

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Kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of diethylene glycol by chloramine-T in acidic medium

Journal of the Serbian Chemical Society ◽

10.2298/jsc0307535b ◽

2003 ◽

Vol 68 (7) ◽

pp. 535-542 ◽

Cited By ~ 5

Author(s):

V.W. Bhagwat ◽

J. Tiwari ◽

A. Choube ◽

B. Pare

Keyword(s):

Diethylene Glycol ◽

Acidic Medium ◽

Cetyltrimethylammonium Bromide ◽

Reaction Rate ◽

Chloride Ions ◽

Kinetics And Mechanism ◽

Product Analysis ◽

Rate Determining Step ◽

Chloramine T ◽

Catalyzed Oxidation

The kinetics and mechanism of the C16TABcatalyzed oxidation of diethylene glycol (2,2?-oxydiethanol) by chloramine-T in acidic medium has been studied. The reaction has a first-order dependence on chloramine-T. With excess concentrations of other reactants, the reaction rate follows fractional order kinetics with respect to [diethylene glycol]. The micellar effect due to cetyltrimethylammonium bromide, a cationic surfactant, has been studied. The reaction is catalyzed by chloride ions as well. The small salt effect and increase in the reaction rate with increasing dielectric constant suggest the involvement of neutral molecules in the rate determining step. Addition of p-toluenesulfonamide retards the reaction rate. On the basis of product analysis, a pertinent mechanism is proposed.

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Kinetics and mechanism of the copper(II)-catalyzed oxidation of lactic acid with chloramine T (CAT) in alkaline solutions

Inorganic Chemistry ◽

10.1021/ic00151a026 ◽

1983 ◽

Vol 22 (9) ◽

pp. 1393-1395 ◽

Cited By ~ 12

Author(s):

Shailendra Jha ◽

P. D. Sharma ◽

Y. K. Gupta

Keyword(s):

Lactic Acid ◽

Kinetics And Mechanism ◽

Alkaline Solutions ◽

Chloramine T ◽

Catalyzed Oxidation

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Kinetics and Mechanism of the Oxidation of Naphthol Green B by Peroxydisulphate Ion in Aqueous Acidic Medium

International Journal of Inorganic Chemistry ◽

10.1155/2014/768575 ◽

2014 ◽

Vol 2014 ◽

pp. 1-4

Author(s):

B. Myek ◽

S. O. Idris ◽

J. F. Iyun

Keyword(s):

Acidic Medium ◽

Reaction Medium ◽

Intermediate Complex ◽

Kinetic Investigation ◽

Hydrogen Ions ◽

First Order ◽

Order Dependence ◽

Naphthol Green B ◽

Kinetics Of ◽

Aqueous Acidic Medium

The kinetics of the oxidation of naphthol green B (NGB3−) by peroxydisulphate ion has been carried out in aqueous acidic medium at λmax of 700 nm, T=23±1°C, and I=0.50 mol dm−3 (NaCl). The reaction shows a first-order dependence on oxidant and reductant concentration, respectively. The stoichiometry of the NGB—S2O82- reaction is 1 : 2. Change in hydrogen ions concentration of the reaction medium has no effect on the rate of the reaction. Added cations and anions decreased the rate of the reaction. The results of spectroscopic and kinetic investigation indicate that no intermediate complex is probably formed in the course of this reaction.

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Iridium(III) Catalyzed Oxidation of Leucine by Chloramine-T in Acidic Medium: A Kinetic and Mechanistic Study

Proceedings of the National Academy of Sciences India Section A Physical Sciences ◽

10.1007/s40010-017-0355-8 ◽

2017 ◽

Vol 87 (2) ◽

pp. 163-170

Author(s):

Abhishek Verma ◽

Jyoti Pandey ◽

Sheila Srivastava

Keyword(s):

Acidic Medium ◽

Mechanistic Study ◽

Chloramine T ◽

Catalyzed Oxidation

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Substrate Inhibition in Ruthenium(III) Catalyzed Oxidation of Propane-1,3-diol by Periodate in Acidic Medium: A Kinetic Study

Asian Journal of Chemistry ◽

10.14233/ajchem.2020.22646 ◽

2020 ◽

Vol 32 (7) ◽

pp. 1569-1575

Author(s):

K.V.S. Koteswara Rao ◽

R. Venkata Nadh ◽

K. Venkata Ratnam

Keyword(s):

Acid Medium ◽

Perchloric Acid ◽

Acidic Medium ◽

Reaction Rate ◽

Substrate Inhibition ◽

Potassium Periodate ◽

First Order ◽

Plausible Mechanism ◽

Aqueous Perchloric Acid ◽

Catalyzed Oxidation

Ruthenium(III) catalyzed oxidation of propane-1,3-diol by potassium periodate was studied in aqueous perchloric acid medium. Orders of reaction with respect to concentrations of oxidant, substrate, acid and catalyst were determined. First order in oxidant and catalyst concentrations, and inverse fractional order in acid medium were observed. In addition, substrate inhibition (i.e. a decrease in reaction rate with an increase in substrate concentration) was observed. Effect of addition of salt and solvent was studied. Based on the studies of temperature variation, Arrhenius parameters were calculated. Plausible mechanism was also proposed based on observed kinetics.

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

E-Journal of Chemistry ◽

10.1155/2011/572603 ◽

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.

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