Oxidation of aromatic secondary and tertiary amines by peroxydisulphate. A kinetic study

1971 ◽  
Vol 24 (8) ◽  
pp. 1633 ◽  
Author(s):  
A Sabesan ◽  
N Venkatasubramanian
Keyword(s):  
Transition State ◽  
Kinetic Study ◽  
Tertiary Amines ◽  
Steric Strain ◽  
First Order ◽  
Kinetics Of

The kinetics of the oxidation of aromatic secondary and tertiary amines by peroxydisulphate ion under aqueous basic conditions have been investigated. The reaction is first order in amine and first order in S2O82- ion. The order of the reactivity is found to be: N-methylaniline > N,N-dimethylaniline > aniline and N-ethylaniline > N,N-diethylaniline > aniline, and among each class: N-methylaniline > N-ethylaniline and N,N-dimethylaniline > N,N-diethylaniline. This reactivity is explained on the basis of a steric strain in the transition state super- imposed over the usual polar effects.

Cleavage of the Sulfur–Sulfur Bond in 2,4-Dinitrophenyl-4-substituted-phenyl Disulfides by trans-[IrCl(CO) (PPh3)2]. A Kinetic Study

1973 ◽  
Vol 51 (22) ◽  
pp. 3790-3794 ◽  
Author(s):  
Chiu T. Lam ◽  
Caesar V. Senoff
Keyword(s):  
Transition State ◽  
Kinetic Study ◽  
Sulfur Atom ◽  
Activation Parameters ◽  
Initial Step ◽  
Second Order ◽  
Nucleophilic Attack ◽  
Kinetics Of ◽  
Sulfur Bond

The kinetics of the reaction between trans-[IrCl(CO)(PPh3)2] and a series of 2,4-dinitrophenyl-4-substituted-phenyl disulfides, YC6H4SSC6H3(NO2)2 (Y = Br, F, H, CH3, or CH3O) have been investigated in toluene between 70 and 90°. These reactions were found to follow simple second order kinetics, rate = k2[IrCl(CO)(PPh3)2][YC6H4SSC6H3(NO2)2]. The rates of reaction were also found to be insensitive to the nature of the para substituent, Y. This fact together with the observed activation parameters, ΔH≠ ~ 17 kcal mol−1 and ΔS≠ ~ − 19 cal mol−1 deg−1, have been interpreted as indicating that the initial step in these reactions involves a nucleophilic attack by the iridium atom at the sulfur atom bonded to the 2,4-dinitrophenyl group, followed by the formation of a three-centered transition state. An overall mechanism for these reactions is presented and discussed.

Kinetic Study of the Adsorption of Dye onto Cotton in SDS-CTAB Reverse Micelles

2015 ◽  
Vol 723 ◽  
pp. 591-595
Author(s):  
Zu Lan Liu ◽  
Lan Qian Li ◽  
Yi Ping Liu ◽  
Ming Lu
Keyword(s):  
Kinetic Study ◽  
Adsorption Kinetics ◽  
Reverse Micelles ◽  
Adsorption Kinetic ◽  
Order Kinetic ◽  
First Order ◽  
Reactive Blue 19 ◽  
Order Kinetic Model ◽  
Pseudo First Order ◽  
Kinetics Of

Adsorption kinetic study of C.I. reactive blue 19 onto cotton was carried out in SDS-CTAB reverse micelles. The data of adsorption kinetics were examined using pseudo first-and second-order kinetic models. It was found that the adsorption kinetics of dye on cotton with diffusion controlling follows the pseudo first-order kinetic model.

scholarly journals Nonenzymatic NADH-Dependent Reduction of Keggin-Type 12-Tungstocobaltate(III) in Aqueous Medium

2011 ◽  
Vol 8 (3) ◽  
pp. 1152-1157
Author(s):  
Prabla Kumari ◽  
Alaka Das ◽  
Dillip Kumar Baral ◽  
A. K. Pattanaik ◽  
P. Mohanty
Keyword(s):  
Electron Transfer ◽  
Transition State ◽  
Aqueous Medium ◽  
Transfer Reaction ◽  
Activation Parameters ◽  
Electron Transfer Reaction ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
First Order ◽  
Kinetics Of

The kinetics of the electron transfer reaction of NADH with 12-tungstocobaltate(III) has been studied over the range 5.07 ≤ 104[NADH] ≤ 15.22 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 20 ≤ t ≤ 35oC in aqueous medium. The electron transfer reaction showed first-order dependence each in [NADH]Tand [12-tungstocobaltate(III)]T. The products of the reaction were found to be NAD+and 12-tungstocobaltate(II). The activation parameters ΔH#(kJ mol-1) and ΔS#(JK-1mol-1) of the electron transfer reactions were found to be 64.4±1.8 and -48.86±6.0. Negative value of ΔS#is an indicative of an ordered transition state for the electron transfer reaction.

scholarly journals Reductive Cleavage of Acetals and Ketals by Borane. Part II. The Kinetics of the Reaction

1975 ◽  
Vol 53 (19) ◽  
pp. 2818-2821 ◽  
Author(s):  
Henry I. Bolker ◽  
Bruce I. Fleming
Keyword(s):  
Transition State ◽  
High Order ◽  
Reductive Cleavage ◽  
Hydrogen Atoms ◽  
Third Order ◽  
Subsequent Formation ◽  
First Order ◽  
Kinetics Of

The reductive cleavage of acetals with borane in tetrahydrofuran was found to be first order in acetal and close to third order in borane. The high order in borane may be due to the participation of three BH3 units in the transition state with subsequent formation of a B2H7− ion. All the hydrogen atoms of borane are available for the reduction of excess acetal at 30 °C.

Acetoxylation by aryliodoso acetates. II. Kinetics of the reaction of phenyliodoso acetate with aceto-p-toluidide

1958 ◽  
Vol 11 (1) ◽  
pp. 34
Author(s):  
WD Johnson ◽  
NV Riggs
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Transition State ◽  
Arrhenius Equation ◽  
First Order ◽  
Temperature Range ◽  
Polar Transition ◽  
Kinetics Of

The reaction of phenyliodoso acetate and aceto-p-toluidide in acetic acid is first order in each reactant and measured rates fit the Arrhenius equation in the temperature range 15-45 �C. Addition of water to the solvent markedly accelerates the reaction, whereas addition of benzene lowers the rate and acetic anhydride has little effect. A polar transition state is indicated.

scholarly journals Kinetic Study of Aluminum Sulphate and Ammonium Aluminum Sulphate Coagulants in Wastewater Treatment

2007 ◽  
Vol 3 (3) ◽  
pp. 222-228
Author(s):  
Lugard Ukiwe ◽  
C.I.A. Nwoko ◽  
Okere-Chijioke M
Keyword(s):  
Wastewater Treatment ◽  
Kinetic Study ◽  
Kinetic Parameters ◽  
Rate Constant ◽  
General Trend ◽  
First Order ◽  
Coagulation Performance ◽  
Aluminum Sulphate ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

An investigation into the kinetics of two inorganic coagulant namely: aluminum sulphate octadecahydrate (Al2(SO4)3.18H2O) an ammonium aluminum sulphate dodecahydrate (NH4Al(SO4)2.12H2O) was studied to determine the effect of certain kinetic parameters on coagulation performance of the above mentioned coagulants. Results of analysis obtained revealed that the rate constant (k) for Al2(SO4)3.18H2O was 5.727s-1, while that for NH4Al(SO4)2.12H2O was 2.282s-1. However, the order of the reaction (xn) of Al2(SO4)3.18H2O and NH4Al(SO4)2.12H2O with the wastewater was 1.0 and 1.0, respectively, indicating that both reactions were first order. Considering the mechanism of the reaction, the general trend observed indicated that the Al2(SO4)3.18H2O reaction was thrice as fast as the NH4Al(SO4)2.12H2O reaction. This fact together with the larger value of k for Al2(SO4)3.18H2O obtained in the experiment lend credence to the widely held believe that Al2(SO4)3.18H2O is a more effective coagulant than NH4Al(SO4)2.12H2O in wastewater treatment.

The kinetic study of the addition of tetrachloromethane to styrene in the presence of copper complexes

1987 ◽  
Vol 52 (7) ◽  
pp. 1758-1763 ◽  
Author(s):  
Li Gwang Hun ◽  
Lubomír Nondek
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Kinetic Study ◽  
Copper Complexes ◽  
Catalytic Mechanism ◽  
First Order ◽  
First Order Kinetics ◽  
Experimental Activation Energy ◽  
Pseudo First Order ◽  
Kinetics Of

Kinetics of the addition of tetrachloromethane to styrene catalyzed by copper-amine complexes was studied. The pseudo-first order kinetics in respect to styrene and the catalyst was observed at an excess of tetrachloromethane. The reaction mechanism involving a catalytic cycle compatible with the kinetic observations is proposed. The experimental activation energy, being about 104 kJ mol-1, indicates a catalytic mechanism.

Kinetic study of addition of nitrogen and phosphorus donors bis(maleonitriledithiolate)cobalt(III)

1970 ◽  
Vol 48 (17) ◽  
pp. 2776-2778 ◽  
Author(s):  
Hon. Gee. Tsiang ◽  
C. H. Langford
Keyword(s):  
Kinetic Study ◽  
Adduct Formation ◽  
Axial Position ◽  
Nitrogen And Phosphorus ◽  
First Order ◽  
Square Planar ◽  
Dimeric Form ◽  
Kinetics Of ◽  
The Way

Kinetics of adduct formation of the dimeric form of bis(maleonitriledithiolate)cobalt(III) with pyridine, triphenylphosphine, triphenylarsine, and 1,10-phenanthroline are reported. Rates are first order in ligand and half order in complex dimer in acetone. This suggests addition of the fifth ligand to an uncoordinated axial position of the square planar species as rate controlling. A (presumably) five coordinate intermediate can be detected kinetically on the way to six coordination in the reaction with 1,10-phenanthrioline and its rearrangement to an octahedral six coordinate chelate is slow. All these results may be interpreted in terms of the significant delocalized π bonding in the square planar dithiolene complexes.

THE KINETICS OF THE TERTIARY-AMINE-CATALYZED REACTION OF ORGANIC ISOCYANATES WITH THIOLS

1960 ◽  
Vol 38 (12) ◽  
pp. 2418-2424 ◽  
Author(s):  
Yoshio Iwakura ◽  
Hisao Okada
Keyword(s):  
Reaction Mechanism ◽  
Tertiary Amine ◽  
Relative Rate ◽  
Catalytic Action ◽  
Tertiary Amines ◽  
First Order ◽  
Kinetics Of

The kinetics of the reactions of isocyanates with thiols in the presence of tertiary amines were examined. The rate of the reaction was of the first order with respect to the concentration of isocyanate, thiol, and tertiary amine. The catalytic action of tertiary amines decreased in the order of triethylenediamine, triethylamine, diethylcyclohexylamine, tributylamine, N-methylmorpholine, pyridine, and quinoline. The relative rate of the reaction of phenylisocyanate with thiols decreased in the order of phenylmethanethiol, 1,4-butanedithiol, 1-butanethiol, 1-dodecanethiol, and thiophenol. The reaction took place more smoothly in strong ionizing solvents. These facts can be explained by the reaction mechanism indicated by the equations [6] to [8].

scholarly journals Ruthenium (VI) Catalysed Oxidation of Diols by Alkaline Hexacyanoferrate(III) ion – a Kinetic Study

2001 ◽  
Vol 2001 (5) ◽  
pp. 182-184 ◽  
Author(s):  
Kunj Behari ◽  
Roli Srivastava ◽  
Veena
Keyword(s):  
Reaction Mechanism ◽  
Ionic Strength ◽  
Kinetic Study ◽  
Zero Order ◽  
Reduced Form ◽  
Aqueous Alkaline Medium ◽  
First Order ◽  
Order Dependence ◽  
Catalysed Oxidation ◽  
Kinetics Of

The kinetics of Ru(VI) catalysed oxidation of 1,5 pentane diol; 1,6-hexane-diol, 1-pentanol and 1-hexanol by hexacyanoferrate (III) ion in an aqueous alkaline medium at constant ionic strength shows zero order dependence on hexacyanoferrate (III) and first order dependence on Ru(VI) and substrate. The result suggest that a complex is formed between Ru(VI) and diol, which slowly decomposes to give a reduced form of ruthenium, which is reoxidised to Ru(VI) in a fast step be alkaline hexacyanoferrate(III). A plausible reaction mechanism is proposed.

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