Kinetics and Mechanism of Acid-Catalyzed Decomposition of 1,3-Bis(4-methylphenyl)triazene in Hexane-Organic Acid Medium

1996 ◽  
Vol 61 (3) ◽  
pp. 355-363 ◽  
Author(s):  
Miroslav Ludwig ◽  
Miriam Kabíčková
Keyword(s):  
Kinetic Model ◽  
Organic Acid ◽  
Acid Medium ◽  
Rate Constant ◽  
Fourth Order ◽  
Kinetics And Mechanism ◽  
Acid Catalyzed ◽  
Kinetics Of

The kinetics of acid-catalyzed decomposition of 1,3-bis(4-methylphenyl)triazene have been studied in mixtures of hexane and organic acid of various ratios using acetic, isovaleric, and pivalic acids as the catalysts. In all the cases, a monotonously increasing dependence of the observed rate constant upon mol fraction of the acid has been found. The results obtained are discussed with the help of the classic third- and fourth-order functions by Margules and the respective kinetic model. The main catalyzing particle appears to be the dimer of the respective acid, the reaction probably going via a complex formed by two molecules of acid and one molecule of the triazene.

Effect of Medium on Acid-Catalyzed Decomposition of N-(Phenylazo)-Substituted Nitrogen Heterocycles

1999 ◽  
Vol 64 (10) ◽  
pp. 1654-1672 ◽  
Author(s):  
Miroslav Ludwig ◽  
Iva Bednářová ◽  
Patrik Pařík
Keyword(s):  
Rate Constant ◽  
Principal Component ◽  
Catalyst Particle ◽  
Pivalic Acid ◽  
Linear Regression Method ◽  
Catalytic Rate Constant ◽  
Rate Limiting Step ◽  
Acid Catalyzed ◽  
Rate Limiting ◽  
Kinetics Of

Four N-(phenylazo)-substituted saturated nitrogen heterocyclics were synthesized and their structure was confirmed by 1H and 13C NMR spectroscopy. The kinetics of their acid-catalyzed decomposition were studied at various concentrations of the catalyst (pivalic acid) in 40, 30, and 20% (v/v) aqueous ethanol at 25 °C. The values obtained for the observed rate constants were processed by the non-linear regression method according to the suggested kinetic models and by the method of principal component analysis (PCA). The interpretation of the results has shown that the acid-catalyzed decomposition of the heterocyclics under the conditions used proceeds by the mechanism of general acid catalysis, the proton being the dominant catalyst particle of the rate-limiting step. The decrease in the observed rate constant at higher concentrations of the catalyst was explained by the formation of a non-reactive complex composed of the undissociated acid and the respective N-(phenylazo)heterocycle. The effect of medium and steric effect of the heterocyclic moiety on the values of catalytic rate constant are discussed.

Synthesis and Kinetics of a Green Surfactant Alkyl Glucamines

2012 ◽  
Vol 518-523 ◽  
pp. 675-678
Author(s):  
He Ping Li ◽  
Jin Ping Wei ◽  
Hong Xia Huang ◽  
Shun Hua Xiao ◽  
Cai Li Yu ◽  
...  
Keyword(s):  
Kinetic Model ◽  
Organic Acid ◽  
Reaction Temperature ◽  
Correlation Coefficients ◽  
Statistical Test ◽  
Green Surfactant ◽  
Kinetics Of

Using glucose and N-butylamines as the main feedstocks in the normol pressure, a novel green surfactant alkyl glucamines was synthesized through hydroammonolysis reaction in the presence of recombination macromolecule organic acid as catalyst. The synthesis technical of alkyl glucamines was studied systematically. The results showed that the conversion was more than 65% when the quantity ratio of glucose to amine was 1︰4, pH was 8.5 around, reaction temperature was 50°C for 60h about. The reaction mechamnism and kinetics of glucose hydroammonolysis was discussed simultaneously. The kinetic model on the synthesis of alkyl glucamines was built： ＝ －0.0117 t －1.3502. The correlation coefficients of the model were gained precisely, and the model was credible by the statistical test and experiment.

Solvent effects on kinetics and mechanism of acid-catalyzed decomposition of 1,3-bis(4-methylphenyl)-triazene II. Reactions in aprotic solvents

1990 ◽  
Vol 55 (1) ◽  
pp. 156-164 ◽  
Author(s):  
Oldřich Pytela ◽  
Taťjana Nevěčná ◽  
Miroslav Ludwig
Keyword(s):  
Rate Constant ◽  
Acid Catalyst ◽  
Kinetics And Mechanism ◽  
Aprotic Solvents ◽  
Catalytic Rate Constant ◽  
Negative Effect ◽  
Acid Catalyzed ◽  
Catalytic Rate ◽  
Positive Effect ◽  
Solvent Acidity

The effect of aprotic solvents (hexane, cyclohexane, dichloromethane, 1,2-dichloroethane, benzene, acetonitrile, acetone, 1,2-dimethoxyethane, ethyl acetate, dioxane) on kinetics and mechanism of acid-catalyzed decomposition of 1,3-bis(4-methylphenyl)triazene has been studied with trichloroacetic acid as the acid catalyst. It has been found that beside the non-dissociated monomer of the acid also its dimer acts as the catalytic species. With regard to the results obtained in protic solvents (the catalysis by proton and general acid) three cases can be encountered of the dependence of observed rate constant on analytical concentration of the acid. The effect of solvents (inclusive of the protic ones) on the catalytic rate constant of the reaction with the non-dissociated monomer of acid is best interpreted by the equation suggested by Koppel and Palm and by the solvent scale suggested by us earlier. The solvent acidity and polarity have positive effect, whereas its basicity has negative effect. The catalytic rate constant of the reaction with the acid dimer decreases with increasing solvent basicity and polarity, due predominantly to the decrease in the equilibrium constant of dimerization.

Kinetics of rouleaux formation using TV image analyzer. II. Rat erythrocytes

1983 ◽  
Vol 245 (2) ◽  
pp. H259-H264 ◽  
Author(s):  
T. Shiga ◽  
K. Imaizumi ◽  
N. Maeda ◽  
K. Kon
Keyword(s):  
Kinetic Model ◽  
Rate Constant ◽  
Three Dimensional ◽  
Erythrocyte Aggregation ◽  
Image Analyzer ◽  
One Dimensional ◽  
Specific Pathogen ◽  
Time Courses ◽  
Kinetics Of ◽  
Rouleaux Formation

With the use of a rheoscope combined with a TV image analyzer, the kinetics of specific pathogen-free rat erythrocyte aggregation was studied. Under certain conditions (gamma 7.5 s-1, hematocrit 0.36%, in own plasma, at 25 degrees C) one-dimensional aggregates (rouleaux) were formed without the development of three-dimensional aggregates, perhaps because of very low concentration of gamma-globulin. The observed phenomena could be explained by 1) the erythrocyte sedimentation and 2) the rouleaux formation. The time courses, of the biphasic change in erythrocyte count and of the increments in total area and in the area/count, were successfully simulated by a kinetic model of linear polymerization, assuming a sedimentation rate constant and an association rate constant. Further, a Poissonlike distribution of the length of rouleaux was shown, as predicted theoretically on the basis of the same kinetic model.

Kinetics of the Ce3+/BrO2-Reaction in Sulfuric Acid Medium

1985 ◽  
Vol 40 (4) ◽  
pp. 368-372 ◽  
Author(s):  
H. D. Försterling ◽  
H. J. Lamberz ◽  
H. Schreiber
Keyword(s):  
Sulfuric Acid ◽  
Acid Solution ◽  
Acid Medium ◽  
Rate Constant ◽  
Constant Concentration ◽  
First Order ◽  
Sulfuric Acid Medium ◽  
First Order Kinetics ◽  
Belousov Zhabotinsky Reaction ◽  
Kinetics Of

The reaction of Ce3+ with BrO2 in sulfuric acid solution (which is the starting step in the inorganic reaction subset of the Belousov-Zhabotinsky-reaction) is followed spectroscopically in a reaction mixture containing BrO2 at constant concentration. From first order kinetics (Br02 in excess) the rate constant for this reaction is evaluated.

Lumping Kinetics of Asphaltene Hydrocracking over NiMo/γ-Al2O3

2011 ◽  
Vol 396-398 ◽  
pp. 806-810
Author(s):  
Ying Xian Zhao ◽  
Da Li ◽  
Xiao Lin
Keyword(s):  
Experimental Data ◽  
Kinetic Model ◽  
Rate Constant ◽  
Suggested Model ◽  
Reaction Paths ◽  
Kinetic Feature ◽  
Kinetics Of

Catalytic hydrocracking of asphaltene over Ni-Mo/γ-Al2O3 was conducted in a microbatch reactor at 693 K. A kinetic model with four lumps (asphaltene, liquid, gas and coke) containing five reaction paths was developed. The fitting of experimental data validated the suggested model and determined the rate constant of each individual reactions, to give the insight to the kinetic feature of asphaltene catalytic hydrocracking

Kinetics and Mechanism of Oxidation of Aliphatic Primary Alcohols with 1-Chlorobenzimidazole in Aqueous Acetic Acid Medium

2016 ◽  
Vol 230 (8) ◽  
Author(s):  
Muthusamy Rukmangathan ◽  
Vetrivel Santhoshkumar ◽  
Balasubramanian Ramkumar
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Kinetics And Mechanism ◽  
Aqueous Acetic Acid ◽  
Primary Alcohols ◽  
Acetic Acid Medium ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

AbstractThe kinetics of oxidation of a few aliphatic primary alcohols with 1-chlorobenzimidazole (CBI) was studied in aqueous acetic acid medium. The reactions were found to be first order each with respect to the concentrations of CBI and alcohol. The added HClO

Kinetics and mechanism of the oxidation of mercury by peroxidase

1985 ◽  
Vol 63 (11) ◽  
pp. 2940-2944 ◽  
Author(s):  
Donald C. Wigfield ◽  
Season Tse
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Horseradish Peroxidase ◽  
Rate Constant ◽  
Order Rate Constant ◽  
Kinetics And Mechanism ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Iron Heme ◽  
Kinetics Of

The kinetics of oxidation of zero-valent mercury by the horseradish peroxidase system are reported. The reaction is first order in mercury and first order in peroxidase compound 1, and appear to obey these kinetics to completion of the reaction. The second order rate constant is 8.58 × 105 M−1 min−1 at 23 °C. The data are consistent with a simple two-electron transfer from mercury to the iron–heme system of peroxidase with the enzyme acting as a chemical oxidant that is continually being regenerated by reaction with hydrogen peroxide.

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