scholarly journals Kinetic Treatment of the Reaction of Fructose and N-Bromosuccinimide in Cationic/Anionic/Nonionic Micelles

2014 ◽  
Vol 2014 ◽  
pp. 1-10
Author(s):  
Minu Singh

The kinetics of oxidation of fructose by N-bromosuccinimide in acidic medium in the absence and presence of cationic, anionic, and nonionic surfactants has been measured iodometrically under pseudo-first-order condition. The oxidation kinetics of fructose by N-bromosuccinimide shows a first-order dependence on N-bromosuccinimide, fractional order dependence on fructose, and negative fractional order dependence on sulfuric acid. The kinetics is treated using Berezin’s micellar model that was previously used for the catalysis and inhibition of the reaction. The determined stoichiometric ratio was 1 : 1 (fructose : N-bromosuccinimide). The variation of Hg(OAC)2 and succinimide (reaction product) has insignificant effect on reaction rate. Effects of surfactants, added acrylonitrile, added salts, and solvent composition variation have been studied. Activation parameters for the reaction have been evaluated from Arrhenius plot by studying the reaction at different temperatures. The rate law has been derived on the basis of obtained data. A plausible mechanism has been proposed from the results of kinetic studies, reaction stoichiometry, and product analysis.

2014 ◽  
Vol 2014 ◽  
pp. 1-9 ◽  
Author(s):  
Minu Singh

Kinetics and mechanism of micellar catalyzed N-bromosuccinimide oxidation of dextrose in H2SO4 medium was investigated under pseudo-first-order condition temperature of 40°C. The results of the reactions studied over a wide range of experimental conditions show that NBS shows a first order dependence, fractional order, on dextrose and negative fractional order dependence on sulfuric acid. The determined stoichiometric ratio was 1 : 1 (dextrose : N-bromosuccinimide). The variation of Hg(OAC)2 and succinimide (reaction product) has insignificant effect on reaction rate. Effects of surfactants, added acrylonitrile, added salts, and solvent composition variation have been studied. The Arrhenius activation energy and other thermodynamic activation parameters are evaluated. The rate law has been derived on the basis of obtained data. A plausible mechanism has been proposed from the results of kinetic studies, reaction stoichiometry, and product analysis. The role of anionic and nonionic micelle was best explained by the Berezin’s model.


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.


Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan

The kinetics of Oxidation of Phenol and aniline by quinolinium Chlorochromate (QCC) in aqueous acetic acid medium leads to the formation of quinone and azobenzene respectively. The reactions are first order with respect to both Phenol and aniline. The reaction is first order with respect to quinolinium chlorochromate (QCC) and is catalyzed by hydrogen ion. The hydrogen-ion dependence has the form: kobs = a+b [H+]. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The reaction does not induced the polymerization of acrylonitrile. The retardation of the rate by the addition of Mn2+ ions confirms that a two electron transfer process is involved in the reaction. The reaction rates have been determined at different temperatures and the activation parameters have been calculated. From the above observations kinetic results a probable mechanism have been proposed.


2019 ◽  
Vol 44 (4) ◽  
pp. 307-315 ◽  
Author(s):  
Xueya Dai ◽  
Hua Song ◽  
Hualin Song ◽  
Jing Gong ◽  
Feng Li ◽  
...  

A nickel phosphide hydrodeoxygenation catalyst (Ni2P-O/MCM-41) was prepared using a new synthetic method. The as-prepared catalyst was evaluated in the hydrodeoxygenation of benzofuran, and the effects of reaction temperature, pressure, and the H2/liquid ratio were investigated. A pseudo first-order model was employed to describe the reaction kinetics of benzofuran hydrodeoxygenation over the Ni2P-O/MCM-41 catalyst. The reaction rate constants ( k1– k5) at different temperatures were determined according to this model. At 533 K, the conversion of 2-ethylphenol in to ethylbenzene began to increase dramatically, and the yield of O-free product, ethylcyclohexane, started to increase rapidly. At 573 K, 3.0 MPa, and a H2/liquid ratio of 500 (V/V), the conversion of benzofuran over Ni2P-O/MCM-41 reached 93%, and the combined yield of O-free products was 91%. Contact time analysis indicated that demethylation was not favored over the Ni2P-O/MCM-41 catalyst.


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.


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.


1992 ◽  
Vol 70 (10) ◽  
pp. 2515-2519 ◽  
Author(s):  
Sharifa S. Alkaabi ◽  
Ahmad S. Shawali

The kinetics of the reactions of a series of (Z)-4-arylidene-2-phenyl-5(4H)oxazolones 1 with n-butylamine and piperidine were studied spectrophotometrically in dioxane, ethanol, and cyclohexane under pseudo-first-order conditions and at different temperatures. The relation k1(obs) = k2[amine] + k3[amine]2 was found applicable for all reactions studied in either dioxane or ethanol. However, in cyclohexane the n-butylaminolysis of 1 followed only third-order kinetics k1(obs) = k3[n-BuNH2]2. The kinetics of the reaction of 1 with n-butylamine in the presence of catalytic amounts of triethylamine in dioxane followed the equation: k1(obs)k2 = [n-BuNH2] + k3[n-BuNH2]2[Formula: see text] [Et3N]. The rate constants k2 and k3 correlated well with the Hammett equation and the corresponding activation parameters were determined. The results were interpreted in terms of a mechanism involving solvent- and amine-catalyzed processes.


2011 ◽  
Vol 8 (4) ◽  
pp. 1728-1733 ◽  
Author(s):  
N. M. I. Alhaji ◽  
S. Sofiya Lawrence Mary

The kinetics of oxidation of isoleucine withN-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.


1973 ◽  
Vol 28 (7-8) ◽  
pp. 483-485 ◽  
Author(s):  
Ram Sanehi ◽  
R. M. Mehrotra ◽  
S. P. Mushran

The kinetics of the oxidation of ethylene diamine tetra acetic acid (EDTA) by chloramine-T in acidic media has been investigated. The reaction shows first order dependence in chloramine-T and the order in hydrogen ion and substrate is fractional. On the basis of kinetic results a plausible mechanism is suggested. Activation parameters have also been calculated.


2018 ◽  
Vol 6 (2) ◽  
pp. 163
Author(s):  
Bharati Behera ◽  
Jashoda Behera

The kinetics of the electron transfer reaction of NADH with Cis-[Co(en)2(H2O)2]3+ has been studied over the range 1.0 ≤ 102 [NADH] ≤ 3.0 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 200C ≤ t ≤ 350C in aqueous medium. The rate of electron transfer reaction was found to be first-order dependence each in [NADH]T and Cis-[Co(en)2(H2O)2]3+T. The products of the reaction were found to be NAD+ and Co(II). The corresponding activation parameters of the electron transfer reactions were found to be as ΔH#=27.55 kJ mol-1 and  ΔS#= -189.35 JK-1mol-1. 


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