scholarly journals Kinetic Evidence of a Common Mechanism in the Oxidation by Chromium(vi) Complexes: Oxidation of Benzyl Alcohol

2000 ◽  
Vol 2000 (3) ◽  
pp. 114-115 ◽  
Author(s):  
Chockalingam Karunakaran ◽  
Sadasivam Suresh
Keyword(s):  
Acetic Acid ◽  
Benzyl Alcohol ◽  
Perchloric Acid ◽  
Mineral Acid ◽  
Common Mechanism ◽  
Aqueous Acetic Acid ◽  
First Order ◽  
Chromium Vi ◽  
Oxidation Of Benzyl Alcohol

The oxidation of benzyl alcohol by dichromate and seven chromium(VI) complexes in aqueous acetic acid in the presence of perchloric acid is first order each in the oxidants, the alcohol and the mineral acid. The oxidation conforms to the isokinetic and Exner relationships and follows a common mechanism.

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.

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

REPLACEMENT REACTIONS IN THE QUINIC ACID SERIES

1963 ◽  
Vol 41 (10) ◽  
pp. 2417-2423 ◽  
Author(s):  
P. A. J. Gorin
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Acetic Acid ◽  
Magnetic Resonance ◽  
Quinic Acid ◽  
Mineral Acid ◽  
Aqueous Acetic Acid ◽  
Nuclear Magnetic

The action on D-quinic acid of hot 95% acetic acid containing mineral acid gave, after complete acetylation, 1,4,5-tri-O-acetyl-epi-quinide consisting of approximately equal portions of the (−)- and (±)-isomers, and tetra-O-acetyl-scyllo-quinic acid. The stereochemistry of the products and their derived free polyols were determined by nuclear magnetic resonance (n.m.r.) spectroscopy and synthesis.Elimination of the tosyloxy group in 5-tosyl-epi-quinicol was shown to take place readily in aqueous acetic acid with participation of the primary carbinol group to give an anhydro quinicol derivative and epi-quinicol.

The Acidity Function of Perchloric Acid in Aqueous Acetic Acid

1954 ◽  
Vol 76 (14) ◽  
pp. 3853-3854 ◽  
Author(s):  
Frederick J. Ludwig ◽  
Kenneth H. Adams
Keyword(s):  
Acetic Acid ◽  
Perchloric Acid ◽  
Aqueous Acetic Acid ◽  
Acidity Function

scholarly journals OXIDATION OF BENZALDEHYDE BY QUINOXALINIUM DICHROMATE

2016 ◽  
Vol 12 (9) ◽  
pp. 4396-4403 ◽  
Author(s):  
K Anbarasu ◽  
N. GEETHA
Keyword(s):  
Acetic Acid ◽  
Perchloric Acid ◽  
Reaction Rate ◽  
Sodium Perchlorate ◽  
Activation Parameters ◽  
Probable Mechanism ◽  
Water Medium ◽  
First Order ◽  
Rate Of Reaction ◽  
Acetic Acid Water

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.

scholarly journals Mechanism of the Oxidation of Methyl n-Propyl Ketone by Manganese (III) Sulphate

1971 ◽  
Vol 26 (4) ◽  
pp. 318-319 ◽  
Author(s):  
K. K. Banerji ◽  
P. Nath ◽  
G. V. Bakore
Keyword(s):  
Acetic Acid ◽  
Activation Parameters ◽  
Solvent Composition ◽  
Aqueous Acetic Acid ◽  
Keto Form ◽  
First Order ◽  
Propyl Ketone

The oxidation of methyl n-propyl ketone by Mn (III) sulphate in aqueous acetic acid is first order with respect to the ketone and Mn (III). The rate independent of acidity and solvent composition. Added Mn (II) does not alter the rate. The activation parameters for the oxidation and enolisation reactions were evaluated. The oxidation is faster than the enolisation under similar conditions. A mechanism involving an attack on the keto-form by Mn (III) sulphate complex is proposed.

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