scholarly journals Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

2012 ◽  
Vol 9 (2) ◽  
pp. 642-649 ◽  
Author(s):  
Y. I. Hassan ◽  
N. H. M. Saeed
Keyword(s):  
Diethyl Ether ◽  
Reaction Rate ◽  
Oxidation Products ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Dependence ◽  
Rate Limiting Step ◽  
Chloramine T ◽  
Rate Limiting ◽  
Kinetics Of

The kinetics of oxidation of diethyl ether (DE) with sodium N-chloro-p-toluenesulphonamide (CAT) in hydrochloric acid solution has been studied at (313°K).The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA) affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K) for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

Oxidation of 1- and 2-acetylnaphthalenes by iodate - a kinetic study

1990 ◽  
Vol 55 (6) ◽  
pp. 1535-1540 ◽  
Author(s):  
Prerepa Manikyamba
Keyword(s):  
Solvent Effect ◽  
Enol Form ◽  
Aqueous Methanol ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Carbonium Ion ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting ◽  
Kinetics Of

Kinetics of oxidation of 1- and 2-acetylnaphthalenes by iodate in the presence of sulphuric acid in aqueous methanol has been studied. The reaction is first order with respect to both [iodate] and [acetylnaphthalene]. Solvent effect indicates a cation-dipole type of interaction in the rate limiting step. A mechanism is proposed with a slow attack of IO2+ on enol form of acetylnaphthalene forming an intermediate carbonium ion, which ultimately gives corresponding ω-hydroxyacetylnaphthalene. The higher reactivity of 2-acetyl isomer is attributed to the greater stability of the corresponding carbonium ion than that of 1-acetyl isomer.

scholarly journals Kinetics of Oxidation of Metochlopramide withChloramine-T in HClO4 Medium

2009 ◽  
Vol 6 (2) ◽  
pp. 545-552 ◽  
Author(s):  
K. M. Meenakshi ◽  
K. Vasant Kumar Pai
Keyword(s):  
Thermodynamic Parameters ◽  
Fractional Order ◽  
Reaction Rate ◽  
Oxidation Products ◽  
Perchloric Acid Solution ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Different Temperatures ◽  
Negative Effect ◽  
Kinetics Of

The kinetics of oxidation of metochlopramide hydrochloride (MCP) with sodiumN-chlorop-toluenesulfonamide (CAT) in perchloric acid solution has been studied at 313K. The reaction rate shows a first order dependence on [CAT], fractional order on [MCP] and inverse fractional order on [H+]. There is a negative effect of dielectric constant of the solvent. The addition of the reduction product of CAT has no significant effect on the rate. The rate remained unchanged with the variation in the ionic strength of the medium. The reaction fails to induce the polymerization of acrylonitrile. Thermodynamic parameters have been computed by Arrhenius plot. The stoichiometry of the reaction was found to be 1:2 and oxidation products were identified. The Michaelis-Menten type of kinetics has been proposed. CH3C6H4SO2NHCl have been assumed to be the reactive oxidizing species. Thermodynamic parameters were computed by studying reactions at different temperatures. A mechanism consistent with observed kinetics is proposed.

scholarly journals A study of the oxidation of butan-1-ol and propan-2-ol by nicotinamide-adenine dinucleotide catalysed by yeast alcohol dehydrogenase.

1975 ◽  
Vol 147 (3) ◽  
pp. 541-547 ◽  
Author(s):  
C J Dickenson ◽  
F M Dickinson
Keyword(s):  
Alcohol Dehydrogenase ◽  
Ternary Complexes ◽  
Kinetics Of Oxidation ◽  
Yeast Alcohol Dehydrogenase ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Ph Range ◽  
Rate Limiting ◽  
Kinetics Of ◽  
Flow Experiments

1. The kinetics of oxidation of butan-1-ol and propan-2-ol by NAD+, catalysed by yeast alcohol dehydrogenase, were studied at 25 degrees C from pH 5.5 to 10, and at pH 7.05 from 14 degrees to 44 degrees C, 2. Under all conditions studied the results are consistent with a mechanism whereby some dissociation of coenzyme from the active enzyme-NAD+-alcohol ternary complexes occurs, and the mechanism is therefore not strictly compulsory order. 3. A primary 2H isotopic effect on the maximum rates of oxidation of [1-2H2]butan-1-ol and [2H7]propan-2-ol was found at 25 degrees C over the pH range 5.5-10. Further, in stopped-flow experiments at pH 7.05 and 25 degrees C, there was no transient formation of NADH in the oxidation of butan-1-ol and propan-2-ol. The principal rate-limiting step in the oxidation of dependence on pH of the maximum rates of oxidation of butan-1-ol and propan-2-ol is consisten with the possibility that histidine and cysteine residues may affect or control catalysis.

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.

Mechanism of Hg(II) Oxidation of D-Galactose in Alkaline Medium

1978 ◽  
Vol 33 (6) ◽  
pp. 657-659 ◽  
Author(s):  
M. P. Singh ◽  
A. K. Singh ◽  
Mandhir Kumar
Keyword(s):  
Alkaline Medium ◽  
Reaction Rate ◽  
Reducing Sugar ◽  
Zero Order ◽  
Ion Concentration ◽  
Kinetics Of Oxidation ◽  
Ion Concentrations ◽  
First Order ◽  
Kinetics Of ◽  
Direct Proportionality

Abstract The present paper deals with the kinetics of oxidation of D-galactose by Nessler's reagent in alkaline medium. The reaction is zero order with respect to Hg(II) and first order with respect to reducing sugar. The direct proportionality of the reaction rate at low hydroxide ion concentrations shows retarding trend at higher concentrations. The reaction rate is inversely proportional to iodide ion concentration. A mechanism has been proposed taking HgI3- as the reacting species

scholarly journals A study of the kinetics and mechanism of yeast alcohol dehydrogenase with a variety of substrates

1973 ◽  
Vol 131 (2) ◽  
pp. 261-270 ◽  
Author(s):  
F. M. Dickinson ◽  
G. P. Monger
Keyword(s):  
Alcohol Dehydrogenase ◽  
Ethanol Oxidation ◽  
Ternary Complexes ◽  
Kinetics Of Oxidation ◽  
Yeast Alcohol Dehydrogenase ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Binary Complexes ◽  
Rate Limiting ◽  
Kinetics Of

1. The kinetics of oxidation of ethanol, propan-1-ol, butan-1-ol and propan-2-ol by NAD+ and of reduction of acetaldehyde and butyraldehyde by NADH catalysed by yeast alcohol dehydrogenase were studied. 2. Results for the aldehyde–NADH reactions are consistent with a compulsory-order mechanism with the rate-limiting step being the dissociation of the product enzyme–NAD+ complex. In contrast the results for the alcohol–NAD+ reactions indicate that some dissociation of coenzyme from the active enzyme–NAD+–alcohol ternary complexes must occur and that the mechanism is not strictly compulsory-order. The rate-limiting step in ethanol oxidation is the dissociation of the product enzyme–NADH complex but with the other alcohols it is probably the catalytic interconversion of ternary complexes. 3. The rate constants describing the combination of NAD+ and NADH with the enzyme and the dissociations of these coenzymes from binary complexes with the enzyme were measured.

scholarly journals Kinetics study of hydrazodicarbonamide synthesis reaction

2013 ◽  
Vol 19 (2) ◽  
pp. 273-279 ◽  
Author(s):  
Gh. Bakeri ◽  
M. Rahimnejad
Keyword(s):  
Reaction Rate ◽  
Second Step ◽  
Kinetics Study ◽  
Synthesis Reaction ◽  
Formation Reaction ◽  
Reaction Rate Constants ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting ◽  
Kinetics Of

In this study, the kinetics of hydrazodicarbonamide (HDCA) synthesis reaction was investigated. Hydrazodicarbonamide is prepared by reaction of urea and hydrazine in acidic medium. Synthesis of HDCA from urea and hydrazine is a two steps reaction. In the first step, semicarbazide is synthesized from the reaction of one mole of urea and one mole of hydrazine and in the second step, semicarbazide reacts with urea to produce hydrazodicarbonamide. By controlling the temperature and pH in the reaction, hydrazine concentration and the amount of produced hydrazodicarbonamide were measured and using these data, reaction rate constants were calculated. Based on this study, it was found that the semicarbazide formation reaction from hydrazine is the rate limiting step. Rate of semicarbazide synthesis is -r1 = 0.1396 [NH2NH2]0.5810 and the rate of hydrazodicarbonamide synthesis is -r2 = 0.7715 [NH2NHCONH2]0.8430.

scholarly journals A mechanistic investigation of the oxidation of N,α-diphenylnitrones by dichloramine-T in aqueous acetonitrile medium - a non-linear Hammett plot

2009 ◽  
Vol 74 (5) ◽  
pp. 493-502
Author(s):  
S. Manivarman ◽  
G. Rajarajan ◽  
G. Manikandan ◽  
M. Sekar ◽  
J. Jayabharathi ◽  
...  
Keyword(s):  
Reaction Rate ◽  
The Other ◽  
Hammett Constant ◽  
Kinetics Of Oxidation ◽  
Aqueous Acetonitrile ◽  
First Order ◽  
Mechanistic Investigation ◽  
Non Linear ◽  
Kinetics Of ◽  
Acetonitrile Medium

The kinetics of oxidation of a number of meta- and para-substituted N,?-diphenylnitrones (nitrone) by dichloramine-T (DCT) was investigated in the presence of alkali in aqueous acetonitrile medium. The order with respect to DCT was one and to OH- an inverse fractional order. The reaction was first order with respect to nitrone. Both electron releasing and withdrawing substituents suppress the reaction rate. The observed rate constant for the substituents were plotted against the Hammett constant, ?, and a non-linear concave downward curve was obtained. The electron withdrawing substituents fall on one side of the curve, having a negative ? value and the electron releasing substituents fall on the other side, with a positive ? value. A mechanism is proposed and the derived rate law is in conformity with the observed results.

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

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

scholarly journals Kinetics and Mechanism of Oxidation ofL-Cystine by Hexacyanoferrate(III) in Alkaline Medium

2009 ◽  
Vol 6 (1) ◽  
pp. 93-98 ◽  
Author(s):  
Annapurna Nowduri ◽  
Kalyan Kumar Adari ◽  
Nageswara Rao Gollapalli ◽  
Vani Parvataneni
Keyword(s):  
Alkaline Medium ◽  
Oxidation Product ◽  
Experimental Results ◽  
Cysteic Acid ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Order Dependence ◽  
Plausible Mechanism ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

Kinetics of oxidation ofL-cystine by hexacyanoferrate(III) was studied in alkaline medium at 30 °C. The reaction was followed spectrophotometrically at λmax = 420 nm. The reaction was found to be first order dependence each on [HCF(III)] and [cystine]. It was found that the rate of the reaction increases with increase in [OH-]. The oxidation product of the reaction was found to be cysteic acid. A plausible mechanism has been proposed to account for the experimental results.

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