Kinetics and mechanism of oxidation of allyl alchohol by chloramine-T in hydrochloric acid medium

1974 ◽  
Vol 27 (6) ◽  
pp. 1203 ◽  
Author(s):  
DS Mahadevappa ◽  
HMK Naidu
Keyword(s):  
Hydrochloric Acid ◽  
Allyl Alcohol ◽  
Hypochlorous Acid ◽  
Ion Concentration ◽  
Slow Step ◽  
Hydrogen Ion Concentration ◽  
Hydrochloric Acid Medium ◽  
Entropy Of Activation ◽  
Chloramine T ◽  
Kinetics Of

The kinetics of oxidation of allyl alcohol by chloramine-T in presence of hydrochloric acid (0.04-0.13M ) has been studied at O�C. The reaction shows first-order dependence on chloramine-T and hydrogen ion concentration and is independent of the concentration of alcohol. The energy and entropy of activation of the reaction have been found to be 12.3 kcal mol-1 and -33.2 e.u. respectively.Ionic strength has very little influence on the rate of reaction. A mechanism in terms of a fast interaction between allyl alcohol and hypochlorous acid formed by the hydrolysis of N-chloro-p-toluenesulphonamide in a slow step is proposed.

scholarly journals Kinetics of oxidation of allyl alcohol by chloramine-T in hydrochloric acid medium: effect of high acid concentrations

1975 ◽  
Vol 28 (4) ◽  
pp. 899 ◽  
Author(s):  
DS Mahadevappa ◽  
HMK Naidu
Keyword(s):  
Hydrochloric Acid ◽  
Allyl Alcohol ◽  
Alcohol Concentration ◽  
Medium Effect ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Hydrochloric Acid Medium ◽  
Entropy Of Activation ◽  
Chloramine T ◽  
Kinetics Of

The kinetics of oxidation of allyl alcohol by chloramine-T in presence of hydrochloric acid(0.15-0.29M) has been studied. At 0�C the rate is first order with respect to chloramine-T, second order in [H+] and independent of the alcohol concentration. The energy of activation and entropy of activation of the reaction have been found to be 55.6 kJ mol -1 and -153 J K-1 respectively. A mechanism is proposed.

Kinetics and Mechanism of Oxidation of Alizarin Yellow R Dye by Chloramine-T in Hydrochloric Acid Medium. A Spectrophotmetric Study

2018 ◽  
Vol 4 (10) ◽  
Author(s):  
Fathyah Omar Abdulsalam ◽  
Dr. Asha Iyengar T.
Keyword(s):  
Hydrochloric Acid ◽  
Activation Parameters ◽  
Oxidation Products ◽  
First Order ◽  
Alizarin Yellow ◽  
Hydrochloric Acid Medium ◽  
Alizarin Yellow R ◽  
Chloramine T ◽  
Kinetics Of ◽  
Hcl Medium

Kinetics of oxidative decolorization of alizarin yellow R (AYR) by chloramine-T (CAT) in hydrochloric acid (HCl) medium at 304 K has been investigated spectrophotometrically at λmax520 nm. The reaction showed first-order rate dependence on [CAT] and [AYR]o and fractional order dependence on [HCl]. Stoichiometry of the reaction was found to be 1:1 with respect to the substrate and oxidant respectively. The oxidation products were identified by spectral analysis. Variation of ionic strength had no effect on the rate. Addition of p-toluene sulphonamide (PTS) did not retard the rate of the reaction. Activation parameters have been computed. Probable mechanism and the relevant rate law have been deduced for the observed kinetic results.

Oxidation of ascorbic acid by osmium(VIII)

1970 ◽  
Vol 48 (7) ◽  
pp. 1148-1150 ◽  
Author(s):  
U. S. Mehrotra ◽  
S. P. Mushran
Keyword(s):  
Ascorbic Acid ◽  
Ionic Strength ◽  
Hydrochloric Acid ◽  
Negligible Effect ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Kcal Mole ◽  
Hydrogen Ion Concentration ◽  
Influence Of Temperature ◽  
Entropy Of Activation

Reduction of osmium(VIII) by ascorbic acid has been studied in the presence of hydrochloric acid. The reaction is found to be directly proportional to the concentration of ascorbic acid and osmium(VIII) and to the reciprocal of the hydrogen ion concentration. In the proposed mechanism, the reacting species have been shown to be perperosmic acid and ascorbate ion; this was supported by the negligible effect of the ionic strength. Influence of temperature was studied in the range 25–40 °C, and the energy and entropy of activation were calculated as 14.1 ± 0.2 kcal mole−1 and −8.6 ± 0.1 e.u., respectively. Osmium(IV) was found to be a product of the reaction.

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

1972 ◽  
Vol 27 (10) ◽  
pp. 1161-1163 ◽  
Author(s):  
S. P. Mushran ◽  
R. Sanehi ◽  
M. C. Agraval
Keyword(s):  
Acidic Medium ◽  
Present Note ◽  
Alkaline Media ◽  
Alkaline Solutions ◽  
Slow Step ◽  
First Order ◽  
Chloramine T ◽  
Kinetics Of ◽  
Catalyzed Oxidation ◽  
High Redox Potential

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.

scholarly journals Kinetics of Oxidation of Some Amino Acids by N-Chlorosaccharin in Aqueous Acetic Acid Medium

2004 ◽  
Vol 1 (2) ◽  
pp. 127-131 ◽  
Author(s):  
N. A. Mohamed Farook ◽  
R. Prabaharan ◽  
S. Rahini ◽  
R. Senthil Kumar ◽  
G. Rajamahendran ◽  
...  
Keyword(s):  
Amino Acids ◽  
Acetic Acid ◽  
Acid Medium ◽  
Hypochlorous Acid ◽  
Activation Parameters ◽  
Slow Step ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
Kinetics Of

The kinetics of oxidation of some amino acids namely, glycine, alanine, aspartic acid, arginine, and histidine, (AA) byN-chlorosaccharin (NCSA) in aqueous acetic acid medium in the presence of perchloric acid have been investigated. The observed rate of oxidation is first order in [AA], [NCSA] and of inverse fractional order in [H+]. The main product of the oxidation is the corresponding aldehyde. The ionic strength on the reaction rate has no significant effect. The effect of changing the dielectric constant of the medium on the rate indicates the reaction to be of dipole-dipole type. Hypochlorous acid has been postulated as the reactive oxidizing species. The reaction constants involved in the mechanism are derived. The activation parameters are computed with respect to slow step of the mechanism.

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