THE KINETICS OF REACTION OF 2,2-DIPHENYL-1-PICRYLHYDRAZYL WITH PHENOLS

1961 ◽  
Vol 39 (8) ◽  
pp. 1588-1594 ◽  
Author(s):  
J. S. Hogg ◽  
D. H. Lohmann ◽  
K. E. Russell
Keyword(s):  
Hydrogen Atom ◽  
Steric Hindrance ◽  
Hydrogen Abstraction ◽  
Phenoxy Radical ◽  
First Order ◽  
Rate Determining Step ◽  
Kinetics Of Reaction ◽  
Kinetics Of

The kinetics of reaction between 2,2-diphenyl-1-picrylhydrazyl (DPPH) and a wide variety of phenols have been studied. The rate of disappearance of DPPH is of first order with respect to both the DPPH and the reacting phenol. The rates of reaction can be roughly correlated with the Hammett σ value of the phenol substituent in the range −0.4 < σ < 0.2, a ρ value of −6 being obtained. t-Butyl groups in both ortho positions of the phenol give rise to steric hindrance, the reduction in rate being largely due to a reduction in the A factor. Hydrogen abstraction from the less reactive phenols is strongly retarded by the product, 2,2-diphenyl-1-picrylhydrazine.The rate-determining step probably involves the abstraction of a hydrogen atom from the phenol by the DPPH to give diphenylpicrylhydrazine and a phenoxy radical. The retardation by diphenylpicrylhydrazine is readily explained if this primary step is reversible.

scholarly journals KINETICS OF REACTION BETWEEN MALACHITE GREEN AND HYDROXYL ION IN THE PRESENCE OF REDUCING SUGARS

2015 ◽  
Vol 23 (23) ◽  
pp. 61-72
Author(s):  
Dayo Felix Latona ◽  
Adewumi Oluwasogo Dada
Keyword(s):  
Malachite Green ◽  
Activation Parameters ◽  
Cell Compartment ◽  
First Order ◽  
Rate Determining Step ◽  
First Order Kinetics ◽  
Hydroxyl Ion ◽  
Kinetics Of Reaction ◽  
Kinetics Of ◽  
Sphere Mechanism

The reaction was studied via pseudo-first-order kinetics using a UV-1800 Shimadzu spectrophotometer with a thermostated cell compartment and interfaced with a computer. The reaction showed first order with respect to malachite green and sugar and hydroxyl ion concentrations. However, the reaction was independent of ionic strength and showed no dependence on the salt effect, indicating an inner sphere mechanism for the reaction. There was no polymerization of the reaction mixture with acrylonitrile, indicating the absence of radicals in the course of the reaction. Michaelis-Menten plot indicated the presence of a reaction intermediate in the rate-determining step. The activation parameters of the reaction have been calculated and products were elucidated by FTIR spectroscopy. The stoichiometry of the reaction is 1:1. A mechanism consistent with the above facts has been suggested.

Study on Kinetics of Reaction between ZrNi5 and Water Vapor

2012 ◽  
Vol 581-582 ◽  
pp. 694-697
Author(s):  
Yong Yao ◽  
De Li Luo ◽  
Zhi Yong Huang ◽  
Jiang Feng Song
Keyword(s):  
Water Vapor ◽  
Reaction Rate ◽  
Arrhenius Equation ◽  
Tritiated Water ◽  
First Order ◽  
Order Chemical Reaction ◽  
First Order Chemical Reaction ◽  
Kinetics Of Reaction ◽  
Reaction Activation Energy ◽  
Kinetics Of

In order to evaluate the feasibility of tritium recovery from tritiated water by thermochemical decomposition using ZrNi5, the kinetics of reaction between ZrNi5 and water vapor was studied by thermogravimetric method in the temperature range from 673K to 823K. The result shows that reaction rate increased significantly with the increasing of temperature and H2O concentration; the reaction mechanism for ZrNi5 can be described by the first-order chemical reaction, and the reaction is first order for H2O concentration. The reaction activation energy of ZrNi5 is 55.8kJ/mol calculated from the Arrhenius equation.

The kinetics of isomerization of allylbenzene homogeneously catalysed by palladium(II) in acetic acid

1973 ◽  
Vol 26 (12) ◽  
pp. 2635 ◽  
Author(s):  
BI Cruikshank ◽  
NR Davies
Keyword(s):  
Acetic Acid ◽  
Catalytic Activity ◽  
Experimental Evidence ◽  
Active Catalyst ◽  
Bimolecular Reaction ◽  
Equilibrium System ◽  
Constant Concentration ◽  
First Order ◽  
Rate Determining Step ◽  
Kinetics Of

The changes in the kinetics observed during the isomerization of allylbenzene catalysed by palladium(II) are interpreted in terms of the slow formation of a hydrido complex of palladium(II) which subsequently attains a constant concentration in an equilibrium system. The kinetics during these phases are shown to be consistent with first-order dependence on the concentration of an active catalyst formed in a bimolecular reaction from a mononuclear palladium(II) complex and with a regenerative hydrido-π-alkene-σ-alkyl mechanism of isomerization. The hypothesis that a further stage in the kinetics reflects a change in the rate determining step to one involving alkene displacement from the catalyst is supported by the experimental evidence. The concentration of active catalyst is shown not to fall appreciably until all the allylbenzene has undergone isomerization, but thereafter there is a slow reduction of catalytic activity which is not completely restored by the addition of further allylbenzene. It is suggested that the slow formation of a π-allylic complex is responsible.

Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 3. Reaction of Methanol with Hydrogen Atom, Methyl, and Hydroxyl Radicals

1999 ◽  
Vol 103 (19) ◽  
pp. 3750-3765 ◽  
Author(s):  
Jerzy T. Jodkowski ◽  
Marie-Thérèse Rayez ◽  
Jean-Claude Rayez ◽  
Tibor Bérces ◽  
Sándor Dóbé
Keyword(s):  
Hydrogen Atom ◽  
Hydroxyl Radicals ◽  
Theoretical Study ◽  
Hydrogen Abstraction ◽  
Kinetics Of

THE REACTION OF 2,2-DIPHENYL-1-PICRYLHYDRAZYL WITH SECONDARY AMINES

1958 ◽  
Vol 36 (12) ◽  
pp. 1729-1734 ◽  
Author(s):  
J. E. Hazell ◽  
K. E. Russell
Keyword(s):  
Secondary Amine ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Major Product ◽  
The Other ◽  
Secondary Amines ◽  
First Order ◽  
Kinetics Of

The reaction of DPPH (2,2-diphenyl-1-picrylhydrazyl) with N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, diphenylamine, and methylaniline has been studied and has been shown to be primarily a hydrogen abstraction process. Two moles DPPH react with 1–1.15 moles secondary amine to give 1.7–1.8 moles 2,2-diphenyl-1-picrylhydrazine and further products.The reaction between DPPH and N-phenyl-1-naphthylamine is first order with respect to each reactant. The reaction of DPPH with the other amines is retarded by the major product 2,2-diphenyl-1-picrylhydrazine and the kinetics of the over-all reaction are complex. However second-order rate constants and activation energies have been obtained using initial rates of reaction. Possible reaction mechanisms are discussed.

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 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.

Reactions of free radicals with aromatic compounds in the gaseous phase. II. Kinetics of the reaction of methyl radicals with phenol

1965 ◽  
Vol 18 (1) ◽  
pp. 20 ◽  
Author(s):  
MFR Mulcahy ◽  
DJ Williams
Keyword(s):  
Free Radicals ◽  
Gaseous Phase ◽  
Hydrogen Abstraction ◽  
High Reactivity ◽  
Phenoxy Radical ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Kinetics Of Formation ◽  
Phenolic Substances ◽  
Kinetics Of

Knowledge of the reactivity of phenols towards simple free radicals is needed to throw light on the behaviour of the phenolic substances involved in the pyrolysis of coal and other organic materials. In the present investigation the reaction between methyl radicals and phenol vapour has been studied a t total pressures from 0.5 to 3 cmHg and temperatures from 445 to 547°K, the concentrations of methyl radicals and phenol being varied from 2 × 10-12 to 4 × 10-11 and 1 × 10-8 to 8 × 10-7 mole cm-3 respectively. The main products identified by gas chromatography were methane and o- and p-cresol, together with a little anisole and 2,4- and 2,6-dimethylphenol. The cresols are produced via hydrogen abstraction Diagram followed by combination of a methyl radical at a ring position of the phenoxy radical either ortho or para to the oxygen atom, e.g. in the case of the para position: Diagram The kinetics can be explained by postulating (a) that the keto forms of the cresols (methylcyclohexadienones) formed initially by reaction (6) have a finite lifetime in the gaseous phase and (b) that these molecules, which contain a tertiary hydrogen atom α to a system of a carbonyl bond and two carbon-carbon double bonds, partly undergo hydrogen abstraction by methyl radicals before they are able to enolize: CH3· + (HCH3 = C6H4 = O → CH4 + CH3C6H4O· The mechanism is consistent with the kinetics of formation of methane, the distribu- tion of the free electron in the phenoxy radical, the formation of o- and p-cresols as major products, the kinetics of formation of the cresols, and the high reactivity of the intermediate product towards methyl radicals.

Correlation analysis of reactivity in the addition of substituted benzylamines to β-nitrostyrene

1996 ◽  
Vol 74 (4) ◽  
pp. 625-629 ◽  
Author(s):  
Neeta Jalani ◽  
Seema Kothari ◽  
Kalyan K. Banerji
Keyword(s):  
Activation Energy ◽  
Correlation Analysis ◽  
Rate Constant ◽  
Steric Hindrance ◽  
Nucleophilic Addition ◽  
Regression Coefficients ◽  
Nucleophilic Attack ◽  
Arrhenius Activation Energy ◽  
First Order ◽  
Kinetics Of

The kinetics of addition of a number of ortho-, meta-, and para-substituted benzylamines to β-nitrostyrene (NS) in acetonitrile have been studied. The reaction is first order with respect to NS. The order with respect to the amine is higher than one. It has been shown that the reaction follows two mechanistic pathways, uncatalyzed and catalyzed by the amine. The Arrhenius activation energy for the catalyzed path is negative, indicating the presence of a pre-equilibrium (k1, k−1) leading to the formation of a zwitterion. The values of the rate constant, k1, for the nucleophilic attack have been determined for 28 benzylamines. The rate constant k1 was subjected to correlation analysis using Charton's LDR and LDRS equations. The polar regression coefficients are negative, indicating the formation of a cationic species in the transition state. The reaction is subject to steric hindrance by ortho substituents. Key words: nucleophilic addition, benzylamines, correlation analysis, kinetics, alkene.

Enantioselective hydrosilylation of tert-butyl phenyl ketone by diphenylsilane catalysed by [Rh{(-)-DIOP}2]+ClO4-

1980 ◽  
Vol 45 (10) ◽  
pp. 2808-2816 ◽  
Author(s):  
Ivan Kolb ◽  
Jiří Hetflejš
Keyword(s):  
Reaction Rates ◽  
Reaction Model ◽  
Rhodium Complex ◽  
Initial Reaction ◽  
Chiral Ligand ◽  
Title Reaction ◽  
First Order ◽  
Rate Determining Step ◽  
Phenyl Ketone ◽  
Kinetics Of

Kinetics of the title reaction has been studied by the method of initial reaction rates. In the presence of free chiral ligand the hydrosilylation was found to be first order in the catalyst and in the ketone and fractional order in the organosilicon hydride. The rate data and the results of spectroscopic study of interaction of diphenylsilane with the rhodium complex have been interpreted in terms of a reaction model involving formation of the corresponding cationic silyl(hydrido)rhodium complex followed by interaction of the ketone with this complex in the rate determining step. The results are confronted with those obtained for the analogous reaction catalysed by [Rh(1,5-COD)(-)-DIOP]+ClO4-.

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