The silver(I)-copper reaction in acetonitrile-water mixtures

1984 ◽  
Vol 37 (5) ◽  
pp. 903 ◽  
Author(s):  
FJ Hughes ◽  
IM Ritchie ◽  
P Singh
Keyword(s):  
Reaction Rate ◽  
Rotation Speed ◽  
Kinetic Studies ◽  
Polarization Curves ◽  
Limiting Current ◽  
Slow Step ◽  
Surface Roughening ◽  
Kinetic Rate ◽  
Diffusion Controlled ◽  
Good Agreement

An electrochemical and kinetic study of the silver(I)-copper displacement (cementation) reaction in acidified acetonitrile-water mixtures is reported. The cathodic polarization curves for the reduction of silver(I) were found to be those of a fast electrochemical reaction. From the variation of limiting current with rotation speed, the diffusion coefficient of silver(I) as a function of acetonitrile concen- tration was determined. The anodic oxidation of copper gave a Tafel slope of 60 mV per decade of current and was rotation-speed-dependent. It is suggested that the slow step in the reaction mechanism is the diffusion of copper(I) from the electrode surface. At all acetonitrile concentrations investigated, the two polarization curves intersected at a point where the current is fixed by the diffusion of silver(I); this suggests that the displacement reaction will be diffusion-controlled, which was confirmed by kinetic studies. Provided the silver deposit was not too thick, there was good agreement between the measured kinetic rate and that calculated from the silver(I) limiting-current measurements. However, when the deposit became too thick, some increase in reaction rate due to surface roughening was observed.

scholarly journals An Investigation of Direct Hydrocarbon (Propane) Fuel Cell Performance Using Mathematical Modeling

2018 ◽  
Vol 2018 ◽  
pp. 1-18
Author(s):  
Bhavana Parackal ◽  
Hamidreza Khakdaman ◽  
Yves Bourgault ◽  
Marten Ternan
Keyword(s):  
Fuel Cells ◽  
Current Density ◽  
Reaction Rate ◽  
Gas Diffusion ◽  
Proton Exchange ◽  
Polarization Curves ◽  
Limiting Current ◽  
Fuel Cell Performance ◽  
Limiting Current Density ◽  
Current Densities

An improved mathematical model was used to extend polarization curves for direct propane fuel cells (DPFCs) to larger current densities than could be obtained with any of the previous models. DPFC performance was then evaluated using eleven different variables. The variables related to transport phenomena had little effect on DPFC polarization curves. The variables that had the greatest influence on DPFC polarization curves were all related to reaction rate phenomena. Reaction rate phenomena were dominant over the entire DPFC polarization curve up to 100 mA/cm2, which is a value that approaches the limiting current densities of DPFCs. Previously it was known that DPFCs are much different than hydrogen proton exchange membrane fuel cells (PEMFCs). This is the first work to show the reason for that difference. Reaction rate phenomena are dominant in DPFCs up to the limiting current density. In contrast the dominant phenomenon in hydrogen PEMFCs changes from reaction rate phenomena to proton migration through the electrolyte and to gas diffusion at the cathode as the current density increases up to the limiting current density.

scholarly journals Effects of the Size, the Number, and the Spatial Arrangement of Reactive Patches on a Sphere on Diffusion-Limited Reaction Kinetics: A Comprehensive Study

2020 ◽  
Vol 21 (3) ◽  
pp. 997 ◽  
Author(s):  
Changsun Eun
Keyword(s):  
Reaction Kinetics ◽  
Rate Constant ◽  
Brownian Dynamics ◽  
Kinetic Studies ◽  
Spatial Arrangement ◽  
The Finite Element Method ◽  
Diffusion Limited ◽  
Diffusion Controlled ◽  
Kinetics Of ◽  
Good Agreement

We investigate how the size, the number, and the spatial arrangement of identical nonoverlapping reactive patches on a sphere influence the overall reaction kinetics of bimolecular diffusion-limited (or diffusion-controlled) reactions that occur between the patches and the reactants diffusing around the sphere. First, in the arrangement of two patches, it is known that the overall rate constant increases as the two patches become more separated from each other but decreases when they become closer to each other. In this work, we further study the dependence of the patch arrangement on the kinetics with three and four patches using the finite element method (FEM). In addition to the patch arrangement, the kinetics is also dependent on the number and size of the patches. Therefore, we study such dependences by calculating the overall rate constants using the FEM for various cases, especially for large-sized patches, and this study is complementary to the kinetic studies that were performed by Brownian dynamics (BD) simulation methods for small-sized patches. The numerical FEM and BD simulation results are compared with the results from various kinetic theories to evaluate the accuracies of the theories. Remarkably, this comparison indicates that our theory, which was recently developed based on the curvature-dependent kinetic theory, shows good agreement with the FEM and BD numerical results. From this validation, we use our theory to further study the variation of the overall rate constant when the patches are arbitrarily arranged on a sphere. Our theory also confirms that to maximize the overall rate constant, we need to break large-sized patches into smaller-sized patches and arrange them to be maximally separated to reduce their competition.

scholarly journals Understanding the reaction mechanism of the regioselective piperidinolysis of aryl 1-(2,4-dinitronaphthyl) ethers in DMSO: Kinetic and DFT studies

2021 ◽  
Vol 46 ◽  
pp. 146867832110274
Author(s):  
Yasmen M Moghazy ◽  
Nagwa MM Hamada ◽  
Magda F Fathalla ◽  
Yasser R Elmarassi ◽  
Ezzat A Hamed ◽  
...  
Keyword(s):  
Carbon Atom ◽  
Density Functional ◽  
Function Analysis ◽  
Density Functional Theory Method ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Nucleophilic Attack ◽  
Common Mechanism ◽  
Slow Step ◽  
Rate Determining Step

Reactions of aryl 1-(2,4-dinitronaphthyl) ethers with piperidine in dimethyl sulfoxide at 25oC resulted in substitution of the aryloxy group at the ipso carbon atom. The reaction was measured spectrophotochemically and the kinetic studies suggested that the titled reaction is accurately third order. The mechanism is began by fast nucleophilic attack of piperidine on C1 to form zwitterion intermediate (I) followed by deprotonation of zwitterion intermediate (I) to the Meisenheimer ion (II) in a slow step, that is, SB catalysis. The regular variation of activation parameters suggested that the reaction proceeded through a common mechanism. The Hammett equation using reaction constant σo values and Brønsted coefficient value showed that the reaction is poorly dependent on aryloxy substituent and the reaction was significantly associative and Meisenheimer intermediate-like. The mechanism of piperidinolysis has been theoretically investigated using density functional theory method using B3LYP/6-311G(d,p) computational level. The combination between experimental and computational studies predicts what mechanism is followed either through uncatalyzed or catalyzed reaction pathways, that is, SB and SB-GA. The global parameters of the reactants, the proposed activated complexes, and the local Fukui function analysis explained that C1 carbon atom is the most electrophilic center of ether. Also, kinetics and theoretical calculation of activation energies indicated that the mechanism of the piperidinolysis passed through a two-step mechanism and the proton transfer process was the rate determining step.

scholarly journals Modelling and Simulation of the Radiant Field in an Annular Heterogeneous Photoreactor Using a Four-Flux Model

2018 ◽  
Vol 2018 ◽  
pp. 1-16 ◽  
Author(s):  
O. Alvarado-Rolon ◽  
R. Natividad ◽  
R. Romero ◽  
L. Hurtado ◽  
A. Ramírez-Serrano
Keyword(s):  
Photocatalytic Oxidation ◽  
Reaction Rate ◽  
Comsol Multiphysics ◽  
Discrete Ordinate Method ◽  
Discrete Ordinate ◽  
Cylindrical Coordinates ◽  
Volumetric Rate ◽  
Flux Model ◽  
Reaction Rate Equation ◽  
Good Agreement

This work focuses on modeling and simulating the absorption and scattering of radiation in a photocatalytic annular reactor. To achieve so, a model based on four fluxes (FFM) of radiation in cylindrical coordinates to describe the radiant field is assessed. This model allows calculating the local volumetric rate energy absorption (LVREA) profiles when the reaction space of the reactors is not a thin film. The obtained results were compared to radiation experimental data from other authors and with the results obtained by discrete ordinate method (DOM) carried out with the Heat Transfer Module of Comsol Multiphysics® 4.4. The FFM showed a good agreement with the results of Monte Carlo method (MC) and the six-flux model (SFM). Through this model, the LVREA is obtained, which is an important parameter to establish the reaction rate equation. In this study, the photocatalytic oxidation of benzyl alcohol to benzaldehyde was carried out, and the kinetic equation for this process was obtained. To perform the simulation, the commercial software COMSOL Multiphysics v. 4.4 was employed.

Photocatalytic Degradation of Methyl Orange by TiO2/Schorl Photocatalyst: Kinetics and Thermodynamics

2015 ◽  
Vol 713-715 ◽  
pp. 2789-2792
Author(s):  
Huan Yan Xu ◽  
Xue Li ◽  
Yan Li ◽  
Ping Li ◽  
Wei Chao Liu
Keyword(s):  
Methyl Orange ◽  
Reaction Rate ◽  
Reaction Kinetic ◽  
Kinetic Studies ◽  
Reaction Rate Constant ◽  
Order Reaction ◽  
Solution Ph ◽  
Kinetics And Thermodynamics ◽  
Hoff Equation ◽  
Degradation Of Methyl Orange

An active dye, Methyl Orange (MO) was employed as the target pollutant to evaluate the photocatalytic activity of TiO2/schorl composite and the kinetics and thermodynamics of this process was emphasized in this work. Langmuir–Hinshelwood kinetic model was employed for the kinetic studies and the results revealed that the process of MO photocatalytic discoloration by TiO2/schorl composite followed one order reaction kinetic equation under different conditions. The reaction rate constant (k) increased with initial MO concentration decreasing. When the catalyst dosage or solution pH increased,kvalues increased and then decreased. The possible reasons for these phenomena were discussed. Finally, the thermodynamic parameters ΔG, ΔH, ΔSwere obtained by the classical Van't Hoff equation.

scholarly journals Release Kinetic Studies of Stevia rebaudiana Extract Capsules from Sodium Alginate and Inulin by Ionotropic Gelation

2018 ◽  
Vol 2018 ◽  
pp. 1-8
Author(s):  
Juan Pablo Quintal Martínez ◽  
Jorge Carlos Ruiz Ruiz ◽  
Maira Rubí Segura Campos
Keyword(s):  
Sodium Alginate ◽  
Release Kinetics ◽  
Stevia Rebaudiana ◽  
Kinetic Studies ◽  
Release Kinetic ◽  
Steviol Glycosides ◽  
Ionotropic Gelation ◽  
Diffusion Controlled ◽  
Release Analysis

This study was oriented towards encapsulation of S. rebaudiana extract and the study of its release kinetics. The desired encapsulation was achieved by the ionotropic gelation method using sodium alginate and inulin of polymeric constituents. Characterization of the capsules was performed by micrometric properties, encapsulation efficiency, in vitro extract release analysis, and biological activity of released extract. The in vitro release profiles from different capsules were applied on different kinetic models. The prepared capsules were found spherical in shape with diameters ranging from 2.07 to 2.63 mm, having the encapsulation efficiencies of 43.77% and 56.53% for phenolic compounds and steviol glycosides, respectively. The best-fit model with the highest correlation coefficient was observed in the Ritger–Peppas model, indicating diffusion controlled principle. The release exponent n value obtained from the Korsmeyer–Peppas model varied between 0.2273 and 1.1719, confirming that the mechanism of S. rebaudiana extract bioactive compounds release was diffusion controlled.

Stirring Effect on the Belousov-Zhabotinsky Oscillating Chemical Reactions in a Batch. Experimental and Modelling

2010 ◽  
Vol 65 (1-2) ◽  
pp. 132-140 ◽  
Author(s):  
Yevhen Yu. Kalishyn ◽  
Małgorzata Rachwalska ◽  
Peter E. Strizhak
Keyword(s):  
Kinetic Scheme ◽  
Hopf Bifurcations ◽  
Hydrodynamic Turbulence ◽  
Stirring Rate ◽  
Diffusion Controlled ◽  
Stirring Effect ◽  
Delayed Bifurcations ◽  
Diffusion Controlled Reaction ◽  
Transient Oscillations ◽  
Good Agreement

AbstractWe have studied the stirring effect on the time-delayed bifurcations of transient oscillations in the Belousov-Zhabotinsky (BZ) oscillating chemical reaction in a closed system. Experiments show that oscillations disappear through the time-delayed Hopf bifurcations, whose parameters depend on the stirring rate. The explanation of the stirring effect is based on the theories of diffusion-controlled reactions and hydrodynamic turbulence. We show that an increase of the stirring rate leads to an increase of the rate constant for the diffusion-controlled reaction. We propose a kinetic scheme that describes the effect observed in the experiments. A good agreement between the experimental data and the simulations is obtained.

scholarly journals The Effect of Surface Roughness on Diffusion and Chemical Reaction Controlled Limiting Currents on a Rotating Cylinder Electrode in Deaerated Solutions with and Without CO2

CORROSION ◽  
10.5006/2552 ◽  
2018 ◽  
Vol 74 (9) ◽  
pp. 971-983 ◽  
Author(s):  
M. Al-Khateeb ◽  
R. Barker ◽  
A. Neville ◽  
H.M. Thompson
Keyword(s):  
Mass Transfer ◽  
Surface Roughness ◽  
Sherwood Number ◽  
Schmidt Number ◽  
Rotating Cylinder ◽  
Operating Conditions ◽  
Limiting Current ◽  
Surface Roughening ◽  
Rotating Cylinder Electrode ◽  
Effect Of Surface

The influence of surface roughness on mass transfer on a rotating cylinder electrode apparatus is investigated experimentally for a roughness pattern consisting of grooves parallel to the direction of fluid flow. Mass transfer from four different samples, with roughness values of 0.5 μm, 6 μm, 20 μm, and 34 μm, is measured using the limiting current technique for a range of rotational speeds in NaCl solutions saturated with N2 at pH = 3 and 4. Comparison with available correlations for the Sherwood number in literature (which are independent of surface roughness and are either for specific or arbitrary roughness patterns) shows that H+ mass transfer only correlates well for particular levels of roughness and that their accuracy can be increased if a correlation is utilized which is a function of surface roughening. A new correlation for Sherwood number as a function of the Reynolds number, Schmidt number, and surface roughness is proposed which agrees well with the mass transfer observed from all of the rough surface cases considered for this particular roughness pattern. Complementary experiments in CO2 environments were used to assess the combined limiting current associated with H+ and H2CO3 reduction (with the latter occurring via the buffering effect and being associated with the slow CO2 hydration step). Although the increase in sample roughness clearly leads to an increase in the rate of H+ mass transfer, in the CO2 environments considered, surface roughness is found to have no significant influence on the limiting current contribution from H2CO3, which can therefore be determined from Vetter’s equation across this range of operating conditions.

From the Understanding of the Reaction Mechanism Towards Optimizing the Deposition Rate and Optoelectronic Properties of a-Si:H

1989 ◽  
Vol 149 ◽  
Author(s):  
S. Veprek ◽  
M. Heintze ◽  
R. Bayer ◽  
N. Jurčik-Rajman
Keyword(s):  
Reaction Mechanism ◽  
Surface Coverage ◽  
Kinetic Studies ◽  
Reactive Intermediates ◽  
Sticking Coefficient ◽  
High Quality ◽  
Rate Determining Step ◽  
Homogeneous Good ◽  
Good Agreement

ABSTRACTWe present new results of kinetic studies of the deposition of high quality a-Si:H which strongly support the reaction mechanism suggested in our earlier papers: 1. SiH4 → SiH2; 2. SiH2 + SiS4 → Si2H6 (SiH2 + Si2H6 → Si3H6); 3. Si2H6 → 2a-Si:H (Si3H8 → 3a-Si:H). The “SiH3 mechanism”, as promoted by several workers, is in contradiction with these experimental facts.The di- and trisilane, which have a much higher reactive sticking coefficient than monosilane, play the role of reactive intermediates which facilitate the heterogeneous decomposition of silicon carrying species at the surface of the growing film. The values of the reactive sticking coefficient of Si2H6 and Si3H8 depend on the surface coverage by chemisorbed hydrogen; they increase with decreasing surface coverage. Under the conditions of the growth of high quality a-Si:H films the reactive sticking coefficient of disilane amounts to 10−4 to 10−2 which is in a good agreement with recent data of other authors.The rate determining step of the growth of high quality a-Si:H films is the desorption of hydrogen from the surface of the growing film. This can be strongly enhanced by ion bombardment at impact energy of <100 eV. In this way, homogeneous, good quality films were deposited at rates up to 1800 Angströms/min, and there is a well justified hope that this rate can be further increased.

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