Lal Bahadur Nagar, India
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Singh A.K.,Government Vytpg Autonomous College | Jain B.,Government Vytpg Autonomous College | Katre Y.,Kalyan Mahavidyalaya
Research on Chemical Intermediates | Year: 2012

The kinetics of Iridium (III) catalyzed oxidation of D-glucose [D-glu] has been studied by N-bromophthalimide [NBP] in the acidic medium (pH 1.3) at 303 K. The reaction followed first-order kinetics with respect to [NBP] from 0.5×10 -4 to 4.0×10 -4 mol dm -3. The results indicate the first-order kinetics in [iridium(III)] chloride at lower concentrations from 0.75×10 -6 to 5.8×10 -6 mol dm -3 tends towards a zero order at its higher concentrations (up to 13.36×10 -6 mol dm -3). Zero-order kinetics with respect to [D-glu] from 2.0×10 -3 to 20.0×10 -3 mol dm -3 was observed throughout its variation. A positive effect on the oxidation rate was observed for [Cl-] from 0.2×10 -5 to 2.4×10 -5 mol dm -3 and the rate of reaction decreased with increase in dielectric constant (decreasing acetic acid from 35 to 15%) of the medium. A negative effect was observed on the reaction rate for [H +] from 1.5×10 -2 to 12.0×10 -2 mol dm -3. Addition of reduced product of oxidant, i.e., phthalimide from 1.0×10 -4 to 8.0×10 -4 mol dm -3 did not show a significant effect on the oxidation velocity. Rate of reaction increased with increase in ionic strength from 0.2×10-1 to 4.0×10 -1 mol dm -3 of the medium, i.e., increase in [KNO 3]; the rate of reaction was increased. From the linear Arrhenius plot of log k 1 versus 1/T, the activation energy (Ea = 50.91 kJ mol -1) was calculated. With the help of the energy of activation, parameters such as enthalpy of activation -(Delta;H # = 48.39 kJ mol -1), entropy of activation -(Delta;S # = -321.63 JK mol -1), Gibbs free energy of activation -(Delta;G # = 145.84 kJ mol -1) and frequency factor (Log A = -3.97) were also calculated. A suitable mechanism in conformity with kinetic observations was proposed to explain reaction stoichiometry and product analysis. © Springer Science+Business Media B.V. 2011.


Singh A.K.,Government V Y T Pg Autonomous College | Sachdev N.,Shri Shankaracharya Mahavidyalaya | Katre Y.,Kalyan Mahavidyalaya | Singh S.P.,Osaka University
Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry | Year: 2010

Kinetics of oxidation of D-glucose (D-Glu) by N-bromopthalimide (NBP, C8H4O2NBr) in presence of [RuCl 2(H2O)3OH] as a homogenous catalyst in perchloric acid medium has been investigated. The kinetic results indicate that the reaction was first order on [NBP] and zero order on [D-Glu]. The reaction followed first-order kinetics with respect to Ru(III) chloride in its lower concentration range and tends to zero-order at its higher concentration. Negative effect of [H+] and [Cl-] ions on the rate of oxidation were observed, whereas change of ionic strength (μ) of the medium had no effect on the oxidation velocity. The values of rate constants observed at five different temperatures (298, 303, 308, 313, 318 K) were utilized to calculate the activation parameters. Formic acid and arabinonic acid have been identified as the main oxidation products of the reaction. A plausible mechanism from the results of kinetic studies, reaction stoichiometry, and product analysis has been proposed. Copyright © Taylor & Francis Group, LLC.


Singh A.K.,Government Vytpg Autonomous College | Shrivastava A.,Shri Shankaracharya Group of Institute | Katre Y.,Kalyan Mahavidyalaya
Journal of Saudi Chemical Society | Year: 2013

The kinetic and mechanistic studies of Ru(III) and Ir(III) homogeneously catalyzed oxidation of d-fructose (d-fru) by N-bromophthalimide (NBP) in the presence of aqueous perchloric acid medium have been made at 303 K using mercuric acetate as Br- ion scavenger. The stoichiometry and the oxidation products in both catalysts were found to be the same. The determined stoichiometric ratio was found to be 1:2 ([d-fru]:[NBP]). Arabinonic and formic acids were obtained as the major oxidized products of both the reactions. The kinetics of the reaction were studied as a function of temperature, ionic strength, concentration of the salt, concentration of the added reaction product, and the dielectric constant of the medium to learn the mechanistic aspects of the reaction. Possible mechanisms are proposed, which are consistent with the kinetics, stoichiometry and products of the reaction. © 2013.


Singh A.K.,Government V Y T Pg Autonomous College Durg Cg | Shrivastava D.R.,Dr Khoobchand Baghel Government Arts And Science Pg Autonomous College | Katre Y.,Kalyan Mahavidyalaya
Journal of Dispersion Science and Technology | Year: 2012

The kinetics of oxidation of the Norfloxacin (NOR) by sodium salt of p-toluene sulphonamide (chloramine-T) has been studied in presence of an anionic surfactant, that is, sodium dodecylsulphate (SDS) in perchloric acid medium at 308 K. The reactions show first order, fractional order and inverse fractional order dependence of rate with respect to NOR, chloramines-T and perchloric acid, respectively. Dilute micelle-forming anionic surfactant slightly speed the reaction but the reaction rate decreases sharply with increasing surfactant concentration. The kinetic data have been rationalized in terms of various micelle kinetic models and binding parameters have been evaluated. The addition of reduced product of the oxidant (phthalimide) has decreased the rate of reaction. The rate of reaction also decreased with increase in salt concentrations. Effect of ionic strength and solvent polarity of the medium on the rate of reaction were studied. The oxidation products were identified by GC-MS analysis. Investigations of the reaction at different temperatures allowed the determination of the activation parameters with respect to the slow step of proposed mechanism. © 2012 Copyright Taylor and Francis Group, LLC.


Singh A.K.,Government Vyt Pg Autonomous College Durg Cg | Sachdev N.,Government Vyt Pg Autonomous College Durg Cg | Shrivastava D.R.,Science Pg Autonomous College | Katre Y.,Kalyan Mahavidyalaya | And 3 more authors.
Journal of Molecular Catalysis A: Chemical | Year: 2012

Present work reports influence of micellar media (CTAB) upon the oxidative degradation of fluoroquinolone family drug norfloxacin (NOR). The reaction has been studied at constant temperature (308 K). The stoichiometry of the reaction was found to be 1:4 and oxidation products were identified by LC-MS technique and other spectral studies. The reaction exhibited first-order-dependence on chloramine-T [CAT] and fractional-order dependence on [NOR]. The rate constant was independent of cationic micelles of cetyltrimethylammonium bromide [CTAB] at lower concentrations followed by a rapid increase in rate constant to a maximum and further gradual decrease in rate constant at higher CTAB was observed. In the presence of CTAB, both the oxidant and substrate are distributed between the aqueous and the micellar pseudo phases and then react to give the product. Compensation between water structure destruction and substrate-micelle interaction plays an important role in the presence of CTAB. The rate constants were obtained and the applicability of Piszkiewicz's, Raghvan-Srinivasan's and pseudo phase models allowed us to obtain the reactivity constants in the aqueous pseudo phase and in the micellar pseudo phase (k2w and k2m) and the binding constants of the reactants to the micellar phase (K 1, K 2). The effects of inorganic salts i.e. [SO 4 2-], [HSO 4 -], [Cl -] and [Br -] on reaction rate have also been studied. © 2012 Elsevier B.V. All rights reserved.


Singh A.K.,Government V Y T Pg Autonomous College Durg Cg | Jain B.,Government V Y T Pg Autonomous College Durg Cg | Negi R.,Government V Y T Pg Autonomous College Durg Cg | Katre Y.,Kalyan Mahavidyalaya | And 2 more authors.
Transition Metal Chemistry | Year: 2010

The kinetics of ruthenium(III) chloride-catalyzed oxidation of glycine by N-bromophthalimide (NBP) was studied in aqueous perchloric acid at 35 °C. The results showed first- and zero-order behavior with respect to NBP and Gly, respectively. Ru(III) showed a catalytic effect on the reaction which followed first-order kinetics with respect to [Ru(III)] at a low concentration range and tended to zero order at high concentration range. The rates decreased with increase in the proton concentration, while chloride positively influenced the rate of the reaction. Two moles of NBP were required to oxidize one mole of Gly, and the products were identified as phthali-mide (NHP), HCN, CO2, and Br-. Neither added NHP nor Br- influenced the reaction rate. Ionic strength and dielectric constant of the medium had no significant effect on the rate. Activation parameters were determined by studying the reaction at different temperatures. A reaction scheme of the catalytic oxidation is proposed. © Springer Science+Business Media B.V. 2010.


Katre Y.,Kalyan Mahavidyalaya | Singh M.,Kalyan Mahavidyalaya | Singh A.K.,P.A. College
Tenside, Surfactants, Detergents | Year: 2010

The kinetics of oxidation of dextrose by N-bromosuccinimide (NBS) has been investigated in the presence of cationic cetyltrimethylammonium bromide (CTAB) surfactant in sulfuric acid (H2SO4) medium. Similarly in absence of CTAB solution, the reaction followed fractional-, first-, and negative fractional-order kinetics with respect to [dextrose], [NBS] and [H 2SO4], respectively. Although the reaction mechanism remained unaltered by micelles, a typical kψ-[CTAB] profile was observed, that is, with a progressive increase in [CTAB], the reaction rate increased, reached a maximum value, and then decreased. The results are treated quantitatively in terms of Berezin's model. Activation parameters were also evaluated and a negative value of ΔAS# shows the formation of well-structured activated complex. The influence of salts on the reaction rates has also been seen. On the basis of product analysis, a pertinent mechanism is proposed. © Carl Hanser Publisher, Munich.


Katre Y.,Kalyan Mahavidyalaya | Mudliar S.R.,Kalyan Mahavidyalaya | Joshi G.K.,Kalyan Mahavidyalaya | Singh A.K.,P.A. College
Journal of Dispersion Science and Technology | Year: 2012

The kinetics of micellar catalyzed oxidation of oxalic acid [OA] by N-bromophthalimide was studied in the presence of perchloric acid at 308 K. The orders of reaction with respect to [Oxalic acid], [oxidant], and [H +] were found to be fractional, first and negative fractional order respectively. Cationic micelles of cetyltrimethylammonium bromide increased the reaction rate. The effect of phthalimide, mercuric acetate and inorganic salts, that is, [Cl -][Br -] has also been done. The rate reaction decreases with increasing dielectric constant of the medium. The results are treated quantitatively in terms of Piszkiewicz and Berezin models. The rate constant (K obs), cooperatively index (n), binding constant (k s + k o), and corresponding activation parameters (E a, ΔH #, ΔS #, and ΔG #) were determined. A suitable mechanism consistent with the experimental finding has been proposed. © 2012 Copyright Taylor and Francis Group, LLC.

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