scholarly journals Kinetics and Mechanism of Micellar Catalyzed Oxidation of Dextrose by N-Bromosuccinimide in H2SO4 Medium

2014 ◽  
Vol 2014 ◽  
pp. 1-9 ◽  
Author(s):  
Minu Singh
Keyword(s):  
Fractional Order ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Kinetics And Mechanism ◽  
Stoichiometric Ratio ◽  
Product Analysis ◽  
Experimental Conditions ◽  
First Order ◽  
Order Dependence ◽  
Wide Range

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.

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
Keyword(s):  
Fractional Order ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Stoichiometric Ratio ◽  
Product Analysis ◽  
First Order ◽  
Order Dependence ◽  
Different Temperatures ◽  
Reaction Stoichiometry ◽  
Kinetics Of

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.

scholarly journals Kinetics and Mechanism of Electron Transfer to Heptavalent Manganese byDL-Aspartic Acid in Alkaline Aqueous and Micellar Media

2013 ◽  
Vol 2013 ◽  
pp. 1-7 ◽  
Author(s):  
M. Sanjana ◽  
A. K. Patnaik ◽  
S. K. Badamali ◽  
P. Mohanty
Keyword(s):  
Electron Transfer ◽  
Spectral Analysis ◽  
Aspartic Acid ◽  
Sodium Dodecyl ◽  
Activation Parameters ◽  
Kinetics And Mechanism ◽  
Micellar Media ◽  
First Order ◽  
Order Dependence ◽  
Sphere Mechanism

The kinetics and mechanism of the electron transfer ofdl-Aspartic acid (Asp) by Mn (VII) in alkaline medium has been studied spectrophotometrically over the range2.0≤103[Asp]≤5.0 mol dm−3;0.01≤[OH-]≤0.05 mol dm−3;298≤T≤318 K andI=0.05 mol dm−3(KNO3). The reaction exhibits first-order dependence in[MnO4-]Tbut shows fractional-order dependence in both[Asp]Tand[OH−]T. The reaction was studied in the presence of sodium dodecyl sulfate (SDS); an increase in the rate with the increase in the micellar concentration was observed. The products were characterized by spectral analysis. A mechanism involving free radicals is proposed. Asp bindsMnO4-to form a complex that subsequently decomposes to products. Activation parametersΔH° (kJ mol−1) andΔS° (JK−1 mol−1) for the reaction are5.62±0.35and−227.65±1.1, respectively. The negative value ofΔS° indicates that oxidation occurs via inner sphere mechanism.

Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions

1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan
Keyword(s):  
Ionic Strength ◽  
Fractional Order ◽  
Activation Parameters ◽  
Order Reaction ◽  
First Order Reaction ◽  
Intermediate Complex ◽  
Constant Ionic Strength ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

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.

Kinetic Studies of [4n+2]π-Thermal Cyclodimerization of 1-(3-Pyridazinyl)-3-oxidopyridinium Betaines

1992 ◽  
Vol 57 (9) ◽  
pp. 1951-1959 ◽  
Author(s):  
Madlene L. Iskander ◽  
Samia A. El-Abbady ◽  
Alyaa A. Shalaby ◽  
Ahmed H. Moustafa
Keyword(s):  
Energy Gap ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Cyclic Transition ◽  
Concerted Mechanism ◽  
First Order ◽  
Thermodynamic Activation Parameters ◽  
Cyclic Transition State ◽  
Complete Dissociation ◽  
Homo Lumo

The reactivity of the base induced cyclodimerization of 1-(6-arylpyridazin-3-yl)-3-oxidopyridinium chlorides in a pericyclic process have been investigated kinetically at λ 380 nm. The reaction was found to be second order with respect to the liberated betaine and zero order with respect to the base. On the other hand dedimerization (monomer formation) was found to be first order. It was shown that dimerization is favoured at low temperature, whereas dedimerization process is favoured at relatively high temperature (ca 70 °C). Solvent effects on the reaction rate have been found to follow the order ethanol > chloroform ≈ 1,2-dichloroethane. Complete dissociation was accomplished only in 1,2-dichloroethane at ca 70 °C. The thermodynamic activation parameters have been calculated by a standard method. Thus, ∆G# has been found to be independent on substituents and solvents. The high negative values of ∆S# supports the cyclic transition state which is in favour with the concerted mechanism. MO calculations using SCF-PPP approximation method indicated low HOMO-LUMO energy gap of the investigated betaines.

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.

scholarly journals Kinetics and Mechanism of Oxidation oft-Butylbenzylamine by Diperiodatoargentate(III) in Aqueous Alkali

2012 ◽  
Vol 9 (1) ◽  
pp. 203-210 ◽  
Author(s):  
Mahantesh A. Angadi ◽  
Suresh M. Tuwar
Keyword(s):  
Kinetic Studies ◽  
Active Species ◽  
Alkali Concentration ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Middle Range ◽  
Wide Range ◽  
Rate Of Reaction ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

t-Butylbenzylamine (t-BA) is used as a free base in the synthesis of salbutamol drug. Its mechanism of oxidation was proposed from kinetic studies. The kinetics of oxidation oft-butylbenzylamine by diperiodatoargentate(III) (DPA) was studied spectrophotometrically by monitoring decrease in absorbance of DPA. The reaction was found to be first order each in [DPA] and [t-BA]. The effect of alkali concentration in a wide range on rate of reaction was studied. The rate of reaction was found to be increased with increase in [OH–] in the lower range of [OH–], decreasing effect in the middle range and at higher range again increasing effect on rate of reaction was observed. The added periodate retarded the rate of reaction. The polymerization test revealed that oxidation was occurred with the intervention free radical. A suitable mechanism was proposed for a middle range of [OH–]. The active species of silver(III) periodate for all the three different stages of [OH–] are assayed. Rate law was derived and verified. The oxidative product oft-BA was characterized by LC-ESI-MS spectra.

Kinetics and mechanism of aminolysis of (Z)-4-arylidene-2-phenyl-5(4H)oxazolones

1992 ◽  
Vol 70 (10) ◽  
pp. 2515-2519 ◽  
Author(s):  
Sharifa S. Alkaabi ◽  
Ahmad S. Shawali
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Order Conditions ◽  
Kinetics And Mechanism ◽  
Hammett Equation ◽  
Third Order ◽  
First Order ◽  
Different Temperatures ◽  
Pseudo First Order ◽  
Kinetics Of

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.

Kinetics and mechanism of covalent addition of S(IV) species to the acridinium cation

1996 ◽  
Vol 74 (3) ◽  
pp. 365-370 ◽  
Author(s):  
Maria P. Ros ◽  
Jesus Thomas ◽  
Guillermo Crovetto ◽  
Juan Llor
Keyword(s):  
Rate Constants ◽  
Carbonyl Compounds ◽  
Nonlinear Least Squares ◽  
Kinetics And Mechanism ◽  
Experimental Conditions ◽  
Ph Profile ◽  
First Order ◽  
Constant Ph ◽  
Ph Range ◽  
Experimental Values

The reaction of acridine with S(IV) species (SO2•H2O, HSO3−, and SO32−) to form the adduct acridine–S(IV) has been studied spectrophotometrically throughout the pH range 2.6–8 in aqueous solutions. The observed pseudo-first-order rate constants, kobs, were determined at 25 °C and ionic strength I = 0.11 M, and the pH profile of the rate reached a maximum at pH ≈ 6.1. At constant pH the kobs values were a linear function of the total S(IV) concentration with slopes that increased significantly with pH. These data are consistent with the rate-determining attack of SO3H− and SO32− upon the C-9 of the acridinium cation. A nonlinear least-squares fitting of the experimental values to the model equation, within the overall pH region studied, yields the pH-independent rate constants k1 = 3.7 ± 0.1 and k2 = (6.24 ± 0.04) × 104 M−1 s−1 for the attack of these two species, respectively. The experimental results agree very well with the kinetic model. Due to the experimental conditions used we did not detect any possible pseudobase formation in the pH range studied. The reactivity of the S(IV) species with acridine follows the order: [Formula: see text] The value obtained for the ratio k1/k2 is similar to the results given for other addition reactions of S(IV) species to the double bond of carbonyl compounds such as benzaldehyde and formaldehyde. Key words: covalent addition, acridine, acridine – S(IV) adducts, kinetics and mechanism.

Kinetic Studies of Gold Recovery from Diluted Chloride Aqueous Solutions Using Activated Carbon Organosorb 10 CO

2016 ◽  
Vol 69 (3) ◽  
pp. 254 ◽  
Author(s):  
Marek Wojnicki ◽  
Ewa Rudnik ◽  
Magdalena Luty-Błocho ◽  
Robert P. Socha ◽  
Zbigniew Pędzich ◽  
...  
Keyword(s):  
Activated Carbon ◽  
Acidic Solution ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Reaction Model ◽  
Surface Functional Groups ◽  
Complex Ions ◽  
First Order ◽  
Material Theory

The kinetic studies of gold(iii) chloride complex ions recovery from acidic solution using activated carbon (AC) were carried out using spectrophotometry. AC samples were characterized in terms of surface area, porosity, and zeta potential. The surface functional groups were also identified. It was found that adsorption of AuCl4– onto AC was followed by reduction of the ions to the metallic form. The process obeyed the first order reaction model, but the reaction was controlled by diffusion. Arrhenius and Eyring–Polanyi equations were used for determination of the activation parameters. Distribution of gold across the AC pellets was also determined and discussed according to the porous material theory.

Kinetic studies of Dakin oxidation of o- and p-hydroxyacetophenones

1977 ◽  
Vol 55 (1) ◽  
pp. 102-110 ◽  
Author(s):  
M. B. Hocking ◽  
J. H. Ong
Keyword(s):  
Hydrogen Peroxide ◽  
Fractional Order ◽  
Rate Constants ◽  
Kinetic Studies ◽  
Second Order ◽  
Simple Test ◽  
Alkaline Hydrogen Peroxide ◽  
Para Isomer ◽  
First Order ◽  
Pseudo First Order

Rates of oxidation of aqueous o-, and p-hydroxyacetophenone with alkaline hydrogen peroxide to yield catechol and hydroquinone, respectively, have been followed spectrophotometri-cally. Both ketones showed smooth pseudo first-order behaviour, the ortho isomer yielding rate constants in the range 2.6 to 6.6 × 10−2 min−1 at 0 °C, and the para isomer of 0.73 to 7.10 × 10−2 min−1 at 35 °C for the concentrations of hydrogen peroxide and base used. The order in hydrogen peroxide was, unexpectedly, found to be 1.4. A simple test established that this fractional order was probably not the result of hydrogen peroxide involvement in simultaneous first- and second-order processes of differing rates. Other plausible pathways to explain this are proposed.

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