scholarly journals Kinetics and Mechanism of Oxidation of Triethylene Glycol and Tetraethylene Glycol by Ditelluratoargentate (III) in Alkaline Medium

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.

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.


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.


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.


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.


2020 ◽  
Vol 33 (1) ◽  
pp. 21-25
Author(s):  
RANJAN KUMAR PADHY ◽  
SREELEKHA DAS BHATTAMISRA

Effect of surfactant medium on the kinetics of oxidation of amino alcohol by cerium(IV) has been reported. Two amino alcohols namely, monoethanolamine (MEA) and triethanolamine (TEA) are chosen for kinetic study. Sizeable changes in reaction rate are noted only in presence of sodium lauryl sulphate (NaLS) as surfactant. Both the amino alcohols exhibit rate maxima at around the cmc of NaLS, beyond which the kψ-[NaLS] profile shows slow increase in rate constant with increasing NaLS concentration. Suitable model has been used to explain the kinetic pattern post CMC and from this the micelle-reactant binding constant values have been evaluated. From the temperature dependence study, the activation parameters for the oxidation reactions have been computed and these are compared against those obtained for aqueous medium. Based on all information, plausible mechanism for micellar catalysis has been presented.


1982 ◽  
Vol 47 (11) ◽  
pp. 2831-2837 ◽  
Author(s):  
Ľudovít Treindl ◽  
Vasil Dorovský

Oxidation of α-ketoglutaric acid with Ce(IV) ions in a solution of sulphuric acid is a reaction of the first order with respect to both Ce(IV) ions and substrate, is acid catalysed, and its rate is proportional to the reciprocal square of the equilibrium HSO4- concentration. From the temperature dependence of the rate constant in 1.5M-H2SO4, the activation parameters were determined as ΔH##f = 57 kJ/mol and ΔS##f = -45 J mol-1 K-1. The redox reaction proper consists apparently of two steps: in the first one, the enol form of α-ketoglutaric acid reacts with Ce(IV) ions with the formation of the corresponding radical; in the second one, the latter is oxidized further with Ce(IV) to give malonic and succinic acids. Conditions are indicated under which α-ketoglutaric acid serves as substrate for the Belousov-Zhabotinskii oscillation reaction in the presence of Ce(IV)-Ce(III) redox catalyst. Oscillations of Ce(IV) and Br2 concentrations, shifted in phase, can be recorded polarographically with a rotating platinum electrode.


CORROSION ◽  
1962 ◽  
Vol 18 (10) ◽  
pp. 382t-389t ◽  
Author(s):  
J. N. ONG ◽  
W. M. FASSELL

Abstract The oxidation of tungsten and molybdenum occurs by two consecutive reactions, forming first a suboxide then the trioxide. Tantalum and columbium oxidize by four simultaneous reactions: solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes giving rise to two different modifications of the pentoxide. By assuming that all reactions are first order complex chain reactions, rate equations are formulated giving the rate of oxidation as a function of pressure, temperature and time. Regression rate expressions for the metals tungsten, tantalum and columbium above 700 C are given as;; and, respectively. The rate is expressed in cm/hr, T is in degrees K and Po2 in atmospheres pressure of oxygen. 3.8.4, 2.1,1, 6.3.5, 6.3.16, 6.3.13


Sign in / Sign up

Export Citation Format

Share Document