scholarly journals Oxidation of Tetracaine Hydrochloride by Chloramine-B in Acid Medium: Kinetic Modeling

2014 ◽  
Vol 2014 ◽  
pp. 1-8 ◽  
Author(s):  
Jayachamarajapura Pranesh Shubha ◽  
Puttaswamy
Keyword(s):  
Dielectric Constant ◽  
Free Acid ◽  
Activation Parameters ◽  
Local Anaesthetics ◽  
Oxidation Products ◽  
Rate Variation ◽  
First Order ◽  
Order Dependence ◽  
Different Temperatures ◽  
Plausible Mechanism

Tetracaine hydrochloride (TCH) is one of the potent local anaesthetics. A kinetic study of oxidation of tetracaine hydrochloride by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried in HClO4 medium at 303 K. The rate shows first-order dependence on [CAB]o, shows fractional–order dependence on [substrate]o, and is self-governing on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increased the rate. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction was found to be 1 : 5 and the oxidation products were identified by spectral analysis. The conjugate free acid C6H5SO2NHCl of CAB is postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanism and the related rate law has been deduced.

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.

Kinetics of the Oxidation of Ethylene Diamine Tetra Acetic Acid by Chloramine-T

1973 ◽  
Vol 28 (7-8) ◽  
pp. 483-485 ◽  
Author(s):  
Ram Sanehi ◽  
R. M. Mehrotra ◽  
S. P. Mushran
Keyword(s):  
Acetic Acid ◽  
Activation Parameters ◽  
Hydrogen Ion ◽  
Ethylene Diamine ◽  
Acidic Media ◽  
First Order ◽  
Order Dependence ◽  
Plausible Mechanism ◽  
Chloramine T ◽  
Kinetics Of

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.

Ruthenate Ion Catalysed Oxidation of D-galactose and D-xylose by Alkaline Solution of Sodium Metaperiodate: A Kinetic Study

2005 ◽  
Vol 2005 (5) ◽  
pp. 304-310 ◽  
Author(s):  
Ashok Kumar Singh ◽  
N. Chaurasia ◽  
Shahla Rahmani ◽  
Jaya Srivastava ◽  
Ajaya Kumar Singh
Keyword(s):  
Ionic Strength ◽  
Activation Parameters ◽  
Zero Order ◽  
Oxidation Products ◽  
General Mechanism ◽  
Sodium Metaperiodate ◽  
First Order ◽  
Order Dependence ◽  
Catalysed Oxidation ◽  
Low Concentrations

The kinetics of ruthenate ion (RuO42–)-catalysed oxidation of D-galactose (Gal) and D-xylose (Xyl) by alkaline species of periodate, H2IO63–, in an aqueous solution at constant ionic strength shows zero order dependence on reducing sugar and first order dependence on RuO42–. First-order dependence of the reaction on periodate and OH- at their low concentrations tends to zero order in their higher concentration range. A slight increase in the rate of reaction with increase in ionic strength of the medium has also been observed. Various activation parameters have been computed. Lyxonic acid and threonic acid, along with formic acid, were identified as the main oxidation products for Gal and Xyl, respectively. A general mechanism involving bidentate interaction of a species of IO4– with a reactive species of sugar has been proposed.

scholarly journals Exploration of Ruthenium (III) Chloride catalysis on oxidative conversion of aryloximes to arylaldehydes with bromamine-B: A kinetic and mechanistic approach

2021 ◽  
Vol 23 (05) ◽  
pp. 240-261
Author(s):  
Manjunatha A S ◽  
◽  
Anu Sukhdev ◽  
Putta Swamy ◽  
Shashi Dhara T S ◽  
...  
Keyword(s):  
Fractional Order ◽  
Reaction Times ◽  
Activation Parameters ◽  
Oxidation Products ◽  
Isokinetic Temperature ◽  
Experimental Conditions ◽  
Mechanistic Approach ◽  
Different Temperatures ◽  
Plausible Mechanism ◽  
Catalyzed Reactions

Conversion of aryloximes to corresponding arylaldehydes is an important oxidative transformation in synthetic chemistry. In the course of this research, optimum conditions for the facile oxidation of benzaldehyde oxime and p-substituted benzaldehyde oximes viz., p-hydroxybenzaldehyde oxime, p-methoxy benzaldehyde oxime, p-bromobenzaldehyde oxime and p-nitrobenzaldehyde oxime (aryloximes) with bromamine–B (BAB) catalyzed by ruthenium (III) chloride (RuCl3) in perchloric acid (HClO4) medium have been kinetically investigated at 303 K. All the five aryloximes follow identical kinetics with a first-order dependence of rate on [BAB]o, fractional-order each on [aryloximes]o and [RuCl3], and an inverse fractional-order on [H+]. Activation parameters have been evaluated. Oxidation products were characterized by spectral analysis. Under the identical set of experimental conditions, the kinetics of catalyzed reactions has been compared with uncatalyzed reactions and found that the catalyzed reactions are 4–6 folds faster. Isokinetic temperature is found to be 338 K. The catalytic constants (Kc) have been calculated at different temperatures and the values of activation parameters with respect to the catalyst have been evaluated. Spectroscopic evidence for the formation of 1:1 complex between BAB and RuCl3 has been obtained. The observed results have been explained by a plausible mechanism and the related rate law has been deduced. The present method offers many advantages including high conversion, short reaction times and the involvement of non-toxic reagents.

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 Reactivity of Phenol and Aniline towards Quinolinium Chloro Chromate: A Comparative Oxidation Kinetic Study

2015 ◽  
Vol 59 ◽  
pp. 81-92
Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan
Keyword(s):  
Oxidation Kinetic ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Reaction Rates ◽  
Hydrogen Ion ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
First Order ◽  
Different Temperatures ◽  
Kinetics Of

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.

Kinetics of the Substitution of Norbornadiene in Tetracarbonyl(norbomadiene)molybdenum(0) by 2,2'-Bipyridine

2001 ◽  
Vol 56 (3) ◽  
pp. 281-286 ◽  
Author(s):  
Ceyhan Kayran ◽  
Eser Okan
Keyword(s):  
Reaction Rate ◽  
Activation Parameters ◽  
Bipy Ligand ◽  
First Order ◽  
Rate Determining Step ◽  
Vis Spectroscopy ◽  
Different Temperatures ◽  
Ft Ir ◽  
Thermal Substitution ◽  
Kinetics Of

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.

Kinetic and thermodynamic study of Os(VIII) catalysed oxidation of glycine by ferrate(VI) in alkaline medium

2019 ◽  
Author(s):  
Chem Int
Keyword(s):  
Main Product ◽  
Activation Parameters ◽  
Basic Medium ◽  
First Order ◽  
Catalysed Oxidation ◽  
Rate Of Reaction ◽  
Different Temperatures ◽  
Experimental Findings ◽  
Kinetic And Thermodynamic Study ◽  
By Products

Kinetic and thermodynamic investigation on Os(VIII) catalysed oxidation of glycine by ferrate(VI) has been done in basic medium and in the temperature range 30– 450C. Rate of oxidation increases with increase in [FeO4]2- and [Os(VI)] and shows first order dependence. Rate of oxidation also increases with the increase in [S] but order is fractional. The rate decreases with an increase in pH. Rate of reaction is independent of [KCl], [KNO3] and change in ionic strength. The values of rate constant observed at four different temperatures were used to calculate the activation parameters. The energy of activation (ΔE*) of the reaction at pH 11 and temperature 350C was found to be 49.56 kJmol-1. [OsO4(H2O)2] and [FeO42−] are proposed to be the reactive species of Os(VIII) and Fe(VI) respectively in the present investigation. Formaldehyde is found to be main product of the reaction along with carbon dioxide and ammonia as by products. On the basis of experimental findings, a suitable mechanism consistent with the observed kinetics is proposed and a rate law has been derived on the basis of obtained data.

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.

scholarly journals Oxidation of Some Aliphatic Alcohols by Pyridinium Chlorochromate -Kinetics and Mechanism

2009 ◽  
Vol 6 (1) ◽  
pp. 237-246 ◽  
Author(s):  
Sapana Jain ◽  
B. L. Hiran ◽  
C. V. Bhatt
Keyword(s):  
Dielectric Constant ◽  
Carbonyl Compounds ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Hydrogen Ion ◽  
Pyridinium Chlorochromate ◽  
Secondary Alcohols ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

Kinetics of oxidation of some aliphatic primary and secondary alcoholsviz.,ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl butanol by pyridinium chlorochromate (PCC) have been studied in water- perchloric acid medium. The reaction shows first order dependence with respect to pyridinium chlorochromate [PCC] and hydrogen ion [H+]. The rate of oxidation decreases with increase in dielectric constant of solvent suggests ion-dipole interaction. Activation parameters have been evaluated. Products are carbonyl compounds and free radical absence was proved. A tentative mechanism has been proposed.

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