scholarly journals Phenomenological Inferences on the Kinetics of a Mechanically Activated Knoevenagel Condensation: Understanding the “Snowball” Kinetic Effect in Ball Milling

Molecules ◽  
2019 ◽  
Vol 24 (19) ◽  
pp. 3600 ◽  
Author(s):  
Maria Carta ◽  
Stuart L. James ◽  
Francesco Delogu

We focus on understanding the kinetics of a mechanically activated Knoevenagel condensation conducted in a ball mill, that is characterized by sigmoidal kinetics and the formation of a rubber-like cohesive intermediate state coating the milling ball. The previously described experimental findings are explained using a phenomenological kinetic model. It is assumed that reactants transform into products already at the very first collision of the ball with the wall of the jar. The portion of reactants that are transformed into products during each oscillation is taken to be a fraction of the amount of material that is trapped between the ball and the wall of the jar. This quantity is greater when the reaction mixture transforms from its initial powder form to the rubber-like cohesive coating on the ball. Further, the amount of reactants processed in each collision varies proportionally with the total area of the layer coating the ball. The total area of this coating layer is predicted to vary with the third power of time, thus accounting for the observed dramatic increase of the reaction rate. Supporting experiments, performed using a polyvinyl acetate adhesive as a nonreactive but cohesive material, confirm that the coating around the ball grows with the third power of time.

2011 ◽  
Vol 255-260 ◽  
pp. 2987-2993 ◽  
Author(s):  
Shi Fei Hu ◽  
Xiao Yan Ma ◽  
Hong Yu Wang ◽  
Jun Li ◽  
Jing Huang ◽  
...  

Metabolites of alga that will induce disgusting odor into drinking water such as geosmin, 2-methylisoborneol and dimethyl trisulfide, etc. attracted more and more scholar’s attention recently. Dimethyl trisulfide was newly noticed to be criminal of some water supply accidents of unpleasant odor in our country and was found removed effectively by oxidation agents. Batch tests were carried out in this research to investigate reaction kinetics of dimethyl trisulfide oxidized by potassium ferrate in water. Results showed that dimethyl trisulfide can be removed by potassium ferrate and the rate of decomposition followed third-order kinetics, the third-order reaction rate constant k= 6.57×10L/ (s·mg).


Author(s):  
M.A. Egyan ◽  

The article shows studies characterizing the quality of the squeeze: the mechanical composition of the squeeze is determined, the structural moisture of each component is determined, the sugar content in the formed process of sedimentation of the juice and its acidity are determined refractometrically. The kinetics of anthocyanins extraction was determined in two ways, the solids content in the extract was calculated, and the reaction rate constants of the extraction process and the efficiency coefficient of ultrasonic amplification of the extraction process speed were calculated.


2019 ◽  
Author(s):  
Milad Narimani ◽  
Gabriel da Silva

Glyphosate (GP) is a widely used herbicide worldwide, yet accumulation of GP and its main byproduct, aminomethylphosphonic acid (AMPA), in soil and water has raised concerns about its potential effects to human health. Thermal treatment processes are one option for decontaminating material containing GP and AMPA, yet the thermal decomposition chemistry of these compounds remains poorly understood. Here, we have revealed the thermal decomposition mechanism of GP and AMPA by applying computational chemistry and reaction rate theory methods. <br>


1989 ◽  
Vol 21 (6-7) ◽  
pp. 435-442 ◽  
Author(s):  
B. Döll

Silica suspensions (pH = 6.8) and three different cationic polymers were used to study the kinetics of charge neutralization by polyelectrolyte adsorption. The experiments were performed in a continuous flow pipe reactor under steady state turbulent flow conditions. The charge neutralization was monitored by electrophoretic mobility (EPM) measurements of the suspended particles as a function of time after polyelectrolyte audition. The results show the dependency of the destabilization reaction rate on flow and polymer characteristics.


1981 ◽  
Vol 46 (3) ◽  
pp. 693-700 ◽  
Author(s):  
Milan Strašák ◽  
Jaroslav Majer

The kinetics of oxidation of alkenes by thallic sulphate in aqueous solutions, involving the two reaction steps-the hydroxythallation and the dethallation - was studied, and the effect of salts on the kinetics was examined; this made it possible to specify more precisely the reaction mechanism and to suggest a qualitative model of the reaction coordinate. It was found that in homogeneous as well as in heterogeneous reaction conditions, the reaction can be accelerated appreciably by adding tetraalkylammonium salts. These salts not only operate as catalysts of the phase transfer, but also exert a significant kinetic effect, which can be explained with a simplification in terms of a stabilization of the transition state of the reaction.


1986 ◽  
Vol 51 (12) ◽  
pp. 2786-2797
Author(s):  
František Grambal ◽  
Jan Lasovský

Kinetics of formation of 1,2,4-oxadiazoles from 24 substitution derivatives of O-benzoylbenzamidoxime have been studied in sulphuric acid and aqueous ethanol media. It has been found that this medium requires introduction of the Hammett H0 function instead of the pH scale beginning as low as from 0.1% solutions of mineral acids. Effects of the acid concentration, ionic strength, and temperature on the reaction rate and on the kinetic isotope effect have been followed. From these dependences and from polar effects of substituents it was concluded that along with the cyclization to 1,2,4-oxadiazoles there proceeds hydrolysis to benzamidoxime and benzoic acid. The reaction is thermodynamically controlled by the acid-base equilibrium of the O-benzylated benzamidoximes.


1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.


1990 ◽  
Vol 55 (2) ◽  
pp. 345-353 ◽  
Author(s):  
Ivan Halaša ◽  
Milica Miadoková

The authors investigated periodic potential changes measured on oriented sections of Al single crystals during spontaneous dissolution in dilute aqueous solutions of KOH, with the aim to find optimum conditions for the formation of potential oscillations. It was found that this phenomenon is related with the kinetics of the reaction investigated, whose rate also changed periodically. The mechanism of the oscillations is discussed in view of the experimental findings.


1976 ◽  
Vol 29 (2) ◽  
pp. 443 ◽  
Author(s):  
MA Haleem ◽  
MA Hakeem

Kinetic data are reported for the decarboxylation of β-resorcylic acid in resorcinol and catechol for the first time. The reaction is first order. The observation supports the view that the decomposition proceeds through an intermediate complex mechanism. The parameters of the absolute reaction rate equation are calculated.


2012 ◽  
Vol 610-613 ◽  
pp. 1980-1985 ◽  
Author(s):  
Hong Jian Xu ◽  
Shu Fang Wang ◽  
Wei Guo Pan ◽  
Rui Tang Guo

The limestone-lime washing technology is the most widely used WFGD process, which normally we adopt to control the discharge of SO2 caused by coal’s combustion. Through the research on the oxidation kinetics of sulfite in this paper, it is indicated that macroscopic chemical reaction which responses to rate of sulfite is 1/2. And the results of orthogonal test can be concluded that: to the extent influence of oxidization reaction rate, the influences of temperature is the most significant, and influences of stirred speed is nearly negligible. The optimized operation factors may be shown as that temperature is controlled at 40°C, air ventilation is at 88ml/min,pH is 4.5 and stir speed is 500 r/min.


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