scholarly journals Kinetics and Mechanism of Oxidation of Isobutylamine and 1,4-Butanediamine by Potassium Ferrate

2011 ◽  
Vol 8 (3) ◽  
pp. 1371-1377
Author(s):  
Shan Jinhuan ◽  
Yang Yafeng

The kinetics of oxidation of isobutylamine and 1,4-butanediamine by home-made potassium ferrate(VI) at different conditions has been studied spectrophotometrically in the temperature range of 288.2 -303.2 K. The results show first order dependence on potassium ferrate(VI) and on each reductant. The observed rate constant (kobs) decreases with the increase of [OH-], the reaction was negative fraction order with respect to [OH-]. A plausible mechanism was 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 were calculated.

2011 ◽  
Vol 8 (2) ◽  
pp. 903-909 ◽  
Author(s):  
Shan Jinhuan ◽  
Zhang Jiying

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.


2005 ◽  
Vol 70 (4) ◽  
pp. 585-592 ◽  
Author(s):  
J.H. Shan ◽  
S.Y. Huo ◽  
S.G. Shen ◽  
H.W. Sun

The kinetics of oxidation of 1,2-propanediol and 1,2,3-propanetriol by dihydroxyditelluratoargentate(III) (DDA) were studied spectrophotometrically between 298.2 K and 313.2 K in alkaline medium. The reaction rate showed first order dependence on DDA and 1 < nap < 2 order on the reductant. It was found that the pseudo-first order rate constant kobs increased with increasing concentration of OH-1 and decreasing concentration of TeO42-. There is a negative salt effect and no free radicals were detected. In view of this, the dihydroxymonotelluratoargentate(III) species is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed and the rate equations derived from the mechanism can explain all the experimental results. The activation parameters, as well as the rate constants of the rate-determining step were calculated.


2013 ◽  
Vol 2013 ◽  
pp. 1-4
Author(s):  
Jinhuan Shan ◽  
Caihong Yin

The kinetics of oxidation of triethylene glycol and tetraethylene glycol by ditelluratoargentate (III) (DTA) in alkaline liquids has been studied spectrophotometrically in the temperature range of 293.2 K–313.2 K. The reaction rate showed first-order dependence in DTA and fractional order with respect to triethylene glycol or tetraethylene glycol. It was found that the pseudo-first-order rate constant(kobs)increased with an increase in concentration of OH−and a decrease in concentration ofH4TeO6 2−. There was a negative salt effect and no free radicals were detected. A plausible mechanism involving a two-electron transfer was proposed, and the rate equations derived from the mechanism explained all the experimental results and observations. The activation parameters along with the rate constants of the rate-determining step were calculated.


1985 ◽  
Vol 63 (12) ◽  
pp. 3317-3321 ◽  
Author(s):  
M. M. Girgis ◽  
S. A. El-Shatoury ◽  
Z. H. Khalil

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.


2009 ◽  
Vol 6 (1) ◽  
pp. 93-98 ◽  
Author(s):  
Annapurna Nowduri ◽  
Kalyan Kumar Adari ◽  
Nageswara Rao Gollapalli ◽  
Vani Parvataneni

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.


2011 ◽  
Vol 8 (1) ◽  
pp. 159-166 ◽  
Author(s):  
N. M. I. Alhaj ◽  
A. M. Uduman Mohideen ◽  
S. Sofia Lawrence Mary

The kinetics of oxidation of (phenylthio)acetic acid (PTAA) withN-chlorosaccharin (NCSA) have been studied potentiometrically in 80:20 (v/v) acetonitrile-water medium at 298 K. The reaction is first-order each with respect to PTAA and NCSA and shows a negative dependence on [H+]. NCSA itself is shown to be the active oxidizing species. Effects of ionic strength variation, added saccharin, added acrylonitrile, added NaCl and solvent composition variation have been studied. Effect of substituents on the reaction rate has been analysed by employing various (p-sustituted phenylthio)acetic acids. The electron-releasing substituent in the phenyl ring of PTAA accelerates the reaction rate while the electron-withdrawing substituent retards the rate. The excellently linear Hammett plot yields a large negative ρ value, supporting the involvement a chlorosulphonium ion intermediate in the rate-determining step.


2008 ◽  
Vol 2008 ◽  
pp. 1-4 ◽  
Author(s):  
Changying Song ◽  
Lei Chen ◽  
Jinhuan Shan

Kinetics and mechanism of oxidation of leucine and alanine by Ag(III) complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III) complex and amino acids (leucine, alanine). The second-order rate constant, k−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.


1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan

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.


2001 ◽  
Vol 56 (3) ◽  
pp. 281-286 ◽  
Author(s):  
Ceyhan Kayran ◽  
Eser Okan

Abstract The kinetics of the thermal substitution of norbornadiene (nbd) by 2,2'-bipyridine (2,2'-bipy) in (CO)4Mo(C7H9) was studied by quantitative FT-IR and UV-VIS spectroscopy. The reaction rate exhibits first-order dependence on the concentration of the starting complex, and the observed rate constant depends on the concentration of both leaving nbd and entering 2,2'-bipy ligand. The mechanism was found to be consistent with the previously proposed one, where the rate determining step is the cleavage of one of the two Mo-olefin bonds. The reaction was performed at four different temperatures (35 -50 °C) and the evaluation of the kinetic data gives the activation parameters which now support states.


Author(s):  
Dayo Felix Latona ◽  
Adewumi Oluwasogo Dada

The reaction was studied via pseudo-first-order kinetics using a UV-1800 Shimadzu spectrophotometer with a thermostated cell compartment and interfaced with a computer. The reaction showed first order with respect to malachite green and sugar and hydroxyl ion concentrations. However, the reaction was independent of ionic strength and showed no dependence on the salt effect, indicating an inner sphere mechanism for the reaction. There was no polymerization of the reaction mixture with acrylonitrile, indicating the absence of radicals in the course of the reaction. Michaelis-Menten plot indicated the presence of a reaction intermediate in the rate-determining step. The activation parameters of the reaction have been calculated and products were elucidated by FTIR spectroscopy. The stoichiometry of the reaction is 1:1. A mechanism consistent with the above facts has been suggested.


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