Studies on the oxidative degradation of paracetamol by a μ-oxo-diiron(III) complex

2020 ◽  
Vol 98 (2) ◽  
pp. 98-105
Author(s):  
Bula Singh ◽  
Ranendu Sekhar Das
Keyword(s):  
Acetic Acid ◽  
Oxidative Degradation ◽  
Active Role ◽  
Order Reaction ◽  
Proton Abstraction ◽  
First Order ◽  
Initial Activation ◽  
Reaction Media ◽  
Kinetics Of ◽  
Reactivity Order

In higher organisms, metalloenzymes like cytochrome P450, containing a Fe(III) metal center, play an active role in metabolism of paracetamol (APAP). Here, we have chosen a mimicking μ-oxo-diiron complex, [Fe(III)2(μ-O)(phen)4(H2O)2]4+ (1, phen = 1,10-phenanthroline), to study spectrophotometrically the kinetics of the redox interactions with APAP. In acidic buffer media (pH = 3.4–5.1), APAP quantitatively reduces 1 following first-order reaction kinetics. Each molecule of 1 accepts two electrons from APAP and is reduced to ferroin [Fe(phen)3]2+. On oxidation, APAP produces N-acetyl-p-benzoquinone imine (NAPQI), which on hydrolysis results in a mixture of benzoquinone, quinone oxime, acetamide, and acetic acid. In reaction media due to successive deprotonations, 1 exists in equilibrium with the species [Fe(III)2(μ-O)(phen)4(H2O)(OH)]3+ (1a) and [Fe(III)2(μ-O)(phen)4(OH)2]2+ (1b) (pKa = 3.71 and 5.28, respectively). The kinetic analyses suggest for an unusual reactivity order as 1 < 1a ≫ 1b. The mechanistic possibilities suggest that although 1 is reduced by concerted electron transfer (ET) – proton transfer (PT) mechanism, 1a and 1b may be reduced by a concerted PT–ET mechanism where a slow proton-abstraction step is followed by a rapid ET process. It seems that the initial activation of the bridging μ-oxo group by a proton-abstraction results in the higher reactivity of 1a.

The Kinetics of Glucose Decomposition with Sulfate Reduction in the Anaerobic Fluidized Bed Reactor

1993 ◽  
Vol 28 (2) ◽  
pp. 135-144 ◽  
Author(s):  
S. Matsui ◽  
R. Ikemoto Yamamoto ◽  
Y. Tsuchiya ◽  
B. Inanc
Keyword(s):  
Sulfate Reduction ◽  
Fluidized Bed ◽  
Kinetic Equations ◽  
Fluidized Bed Reactor ◽  
Order Reaction ◽  
First Order Reaction ◽  
First Order ◽  
Glucose Decomposition ◽  
Reaction Equations ◽  
Kinetics Of

Using a fluidized bed reactor, experiments on glucose decomposition with and without sulfate reduction were conducted. Glucose in the reactor was mainly decomposed into lactate and ethanol. Lactate was mainly decomposed into propionate and acetate, while ethanol was decomposed into propionate, acetate, and hydrogen. Sulfate reduction was not involved in the decomposition of glucose, lactate, and ethanol, but was related to propionate and acetate decomposition. The stepwise reactions were modeled using either a Monod expression or first order reaction kinetics in respect to the reactions. The coefficients of the kinetic equations were determined experimentally. The modified Monod and first order reaction equations were effective at predicting concentrations of glucose, lactate, ethanol, propionate, acetate, and sulfate along the beight of the reactor. With sulfate reduction, propionate was decomposed into acetate, while without sulfate reduction, accumulation of propionate was observed in the reactor. Sulfate reduction accelerated propionate conversion into acetate by decreasing the hydrogen concentration.

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.

scholarly journals Kinetics and Mechanism of the Change of the 4-Nitrobenzylthio-System into 4,4′-Diformylazoxybenzene in Alkaline Dioxane-Water Media

1985 ◽  
Vol 40 (11) ◽  
pp. 1128-1132
Author(s):  
Y. Riad ◽  
Adel N. Asaad ◽  
G.-A. S. Gohar ◽  
A. A. Abdallah
Keyword(s):  
Acetic Acid ◽  
Sodium Hydroxide ◽  
Rate Constants ◽  
Main Product ◽  
Reaction Medium ◽  
Aqueous Dioxane ◽  
Proton Abstraction ◽  
First Order ◽  
Water Media ◽  
Different Temperatures

Sodium hydroxide reacts with α -(4-nitrobenzylthio)-acetic acid in aqueous-dioxane media to give 4,4'-diformylazoxybenzene as the main product besides 4,4'-dicarboxyazoxybenzene and a nitrone acid. This reaction was kinetically studied in presence of excess of alkali in different dioxane-water media at different temperatures. It started by a fast reversible a-proton abstraction step followed by two consecutive irreversible first-order steps forming two intermediates (α -hydroxy, 4-nitrosobenzylthio)-acetic acid and 4-nitrosobenzaldehyde. The latter underwent a Cannizzaro's reaction, the products of which changed in the reaction medium into 4,4'-diformylazoxybenzene and 4,4'-dicarboxyazoxybenzene. The rate constants and the thermodynamic parameters of the two consecutive steps were calculated and discussed. A mechanism was put forward for the formation of the nitrone acid.Other six 4-nitrobenzyl, aryl sulphides were qualitatively studied and they gave mainly 4,4'-diformylazoxybenzene beside 4,4'-dicarboxyazoxybenzene or its corresponding azo acid.

Bacteriophage Conjugates: The Effect of Coupling Reaction and Specific Antibodies on the Kinetics of Inactivation and Reactivation

1973 ◽  
Vol 28 (1-2) ◽  
pp. 83-90
Author(s):  
Horst Mossmann ◽  
Dietrich K. Hammer
Keyword(s):  
Bacteriophage T4 ◽  
Covalent Binding ◽  
Coupling Reaction ◽  
Order Reaction ◽  
Direct Plating ◽  
Specific Antibodies ◽  
Coupling Process ◽  
First Order ◽  
Kinetics Of ◽  
Critical Site

The reaction of bacteriophage T4 with 1-fluoro-2,4-dinitrobenzene resulted in a covalent binding of 2,4-dinitrophenyl (DNP) determinants to the phage. From the kinetics of inactivation reflecting the coupling process it is concluded that attachment of more than one DNP group to the critical site(s) of the phage is required for inactivation (multi-hit reaction). Contrary to this the neutralization of DNP-T4 by anti-DNP antibody turned out to be a first order reaction, until 80 %> neutralization fitting one-hit kinetics. If compared with native T4, the susceptibility of DNP-T4 to neutralization by anti-T4 antibody is considerably higher, indicating that attachment of DNP groups to T4 amplifies the sensitivity to neutralization by anti-T4. Comparing neutralization kinetics of DNP-T4 and native T4 by anti-DNP-T4 antibody it is suggested that native determinants and DNP groups, as well as determinants resulting from alteration due to the coupling process, all together may contribute as targets for neutralization. Three characteristics strengthen the view that the velocity of T4 conjugates in infecting the host strain is markedly decreased if compared with that of native T4: (a) considerable discrepancy between direct plating and decision technique (b) increasing variety of plaque size and (c) decreased velocity of the first step of reproduction. The kinetics of neutralization observed can be reconciled with a model proposed by Krummel and Uhr. The kinetics of reactivation of neutralized DNP-T4 by the presence cf DNP-BSA has been investigated and the problems involved in the reaction are discussed.

scholarly journals The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate

2000 ◽  
Vol 65 (12) ◽  
pp. 857-866
Author(s):  
Mladjen Micevic ◽  
Slobodan Petrovic
Keyword(s):  
Kinetic Data ◽  
Reaction Rate ◽  
Frequency Factor ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
Activation Entropy ◽  
Second Order Reaction ◽  
Third Order ◽  
First Order ◽  
Kinetics Of

The alcoholysis of 1,2,2-trimethylpropyl-methylfluorophosphonate (soman) was examined with a series of alkoxides and in corresponding alcohols: methanol, ethanol, 1-propanol, 2-propanol, 2-methoxyethanol and 2-ethoxyethanol. Soman reacts with the used alkoxides in a second order reaction, first order in each reactant. The kinetics of the reaction between 1,2,2-trimethylpropyl-methylfluorophosphonate and ethanol in the presence of diethylenetriamine was also examined. A third order reaction rate constant was calculated, first order in each reactant. The activation energy, frequency factor and activation entropy were determined on the basis of the kinetic data.

Direct Method for Determining Inorganic Phosphate in Serum with the "CentrifiChem"

1972 ◽  
Vol 18 (3) ◽  
pp. 263-265 ◽  
Author(s):  
John A Daly ◽  
Gerhard Ertingshausen
Keyword(s):  
Inorganic Phosphate ◽  
Direct Method ◽  
Order Reaction ◽  
First Order Reaction ◽  
First Order ◽  
Kinetics Of ◽  
A Direct Method

Abstract A direct method was developed for determining inorganic phosphate in serum, which requires only a single reagent addition. The method quantitates the unreduced phosphomolybdate heteropolyacid at 340 nm and is linear to at least 10 mg of phosphate per 100 ml. Only 10 µl of serum is required. The unique blanking capabilities of centrifugal analyzers permit the "on run" elimination of serum and reagent background absorbances, which are automatically subtracted. Data on precision, correlation, and recovery are presented. Kinetics of the reaction were studied, and theoretical limits of automatic blanking when applied to a first-order reaction are discussed.

Kinetics and Mechanism of Oxidation of Dimethyl Sulphoxide by Mono- and Di-Substituted N,N-Dichlorobenzenesulphonamides in Aqueous Acetic Acid

2003 ◽  
Vol 58 (8) ◽  
pp. 787-794 ◽  
Author(s):  
B.Thimme Gowda ◽  
K. L. Jayalakshmi ◽  
K. Jyothi
Keyword(s):  
Acetic Acid ◽  
Benzene Ring ◽  
Dimethyl Sulphoxide ◽  
Aqueous Acetic Acid ◽  
Isokinetic Temperature ◽  
Free Energies ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
First Order Kinetics ◽  
Kinetics Of

In an effort to introduce N,N-dichloroarylsulphonamides of different oxidising strengths, four mono- and five di-substituted N,N-dichlorobenzenesulphonamides are prepared, characterised and employed as oxidants for studying the kinetics of oxidation of dimethyl sulphoxide (DMSO) in 50% aqueous acetic acid. The reactions show first order kinetics in [oxidant], fractional to first order in [DMSO] and nearly zero order in [H+]. Increase in ionic strength of the medium slightly increases the rates, while decrease in dielectric constant of the medium decreases the rates. The results along with those of the oxidation of DMSO by N,N-dichlorobenzenesulphonamide and N,N-dichloro-4- methylbenzenesulphonamide have been analysed. Effective oxidising species of the oxidants employed in the present oxidations is Cl+ in different forms, released from the oxidants. Therefore the introduction of different substituent groups into the benzene ring of the oxidant is expected to affect the ability of the reagent to release Cl+ and hence its capacity to oxidise the substrate. Significant changes in the kinetic and thermodynamic data are observed in the present investigations with change of substituent in the benzene ring. The electron releasing groups such as CH3 inhibit the ease with which Cl+ is released from the oxidant, while electron-withdrawing groups such as Cl enhance this ability. The Hammett equation, log kobs = −3.19 + 1.05 σ , is found to be valid for oxidations by all the p-substituted N,N-dichlorobenzenesulphonamides. The substituent effect on the energy of activation, Ea and log A for the oxidations is also analysed. The enthalpies and free energies of activation correlate with an isokinetic temperature of 320 K.

Development of Torrefaction Kinetics for British Columbia Softwoods

2012 ◽  
Vol 10 (1) ◽  
Author(s):  
Jianghong Peng ◽  
Xiaotao T. Bi ◽  
Jim Lim ◽  
Shabab Sokhansanj
Keyword(s):  
British Columbia ◽  
Weight Loss ◽  
Kinetic Model ◽  
Residence Time ◽  
Order Reaction ◽  
First Order Reaction ◽  
Chemical Components ◽  
First Order ◽  
One Step ◽  
Kinetics Of

Torrefaction is a thermal treatment without air or oxygen in the temperature range of 473-573 K. The pyrolysis kinetics of three chemical components (cellulose, hemicelluloses, and lignin) and wood at low temperatures of relevance to torrefaction conditions have been reviewed. A series of thermogravimetric (TG) experiments have been carried out to study the intrinsic torrefaction kinetics of major chemical components and British Columbia (BC) softwoods. The weight loss during BC softwood torrefaction was found to be mainly associated with the decomposition of hemicelluloses, although there was also certain degree of decomposition of cellulose and lignin. The weight loss of the BC softwoods during torrefaction could be approximately estimated from the chemical composition of wood species and the weight loss data for torrefaction of pure cellulose, hemicelluloses, and lignin, respectively. Based on the fitting of the TG curves of BC softwoods and three chemical components, two different torrefaciton models were proposed. The simple one-step (single-stage) kinetic model with the first order reaction can predict the reaction data reasonably well over the long residence time, with the final sample weight being strongly related to the torrefaction temperature. A two-component and one-step first order reaction kinetic model, on the other hand, gave improved agreement with data over short residence time, and can be used to guide the design and optimization of torrefaction reactors over the weight loss range of 0 to 40% at the temperature range of 533-573 K, which covers the typical range of industrially relevant operations.

Kinetics of Cs adsorption/desorption on granite by a pseudo first order reaction model

2007 ◽  
Vol 275 (3) ◽  
pp. 555-562 ◽  
Author(s):  
Shih-Chin Tsai ◽  
Tsing-Hai Wang ◽  
Yuan-Yaw Wei ◽  
Wen-Chun Yeh ◽  
Yi-Lin Jan ◽  
...  
Keyword(s):  
Reaction Model ◽  
Order Reaction ◽  
First Order Reaction ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Pseudo First Order ◽  
Adsorption Desorption ◽  
Kinetics Of

Kinetics of metribuzin degradation by colloidal manganese dioxide in absence and presence of surfactants

2014 ◽  
Vol 68 (1) ◽  
Author(s):  
Qamruzzaman ◽  
Abu Nasar
Keyword(s):  
Sodium Dodecyl ◽  
Oxidative Degradation ◽  
Activation Parameters ◽  
Water Soluble ◽  
Ionic Surfactant ◽  
Ammonium Bromide ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Colloidal Mno2 ◽  
Kinetics Of

AbstractThe kinetics of the degradation of metribuzin by water-soluble colloidal MnO2 in acidic medium (HClO4) were studied spectrophotometrically in the absence and presence of surfactants. The experiments were performed under pseudo-first-order reaction conditions in respect of MnO2. The degradation was observed to be of the first order in respect of MnO2 while of fractional order for both metribuzin and HClO4. The rate constant for the degradation of metribuzin was observed to decrease as the concentration of MnO2 increased. The anionic surfactant, sodium dodecyl sulphate (SDS), was observed to be ineffective whereas the non-ionic surfactant, Triton X-100 (TX-100), accelerated the reaction rate. However, the cationic surfactant, cetyltrimethyl ammonium bromide (CTAB), caused flocculation with oppositely-charged colloidal MnO2; hence further study was not possible. The catalytic effect of TX-100 was discussed in the light of the available mathematical model. The kinetic data were exploited to generate the various activation parameters for the oxidative degradation of metribuzin by colloidal MnO2 in the absence as well as the presence of the non-ionic surfactant, TX-100.

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