Electrode kinetics of the system V(III)/V(II) in aqueous dimethylsulphoxide

1991 ◽  
Vol 56 (1) ◽  
pp. 90-95 ◽  
Author(s):  
Libuše Kišová ◽  
Libor Reichstädter ◽  
Jaro Komenda
Keyword(s):  
Organic Solvent ◽  
Double Layer ◽  
Rate Constants ◽  
Electrode Surface ◽  
Reaction Rate ◽  
Mercury Electrode ◽  
Electrode Reaction ◽  
Electrode Kinetics ◽  
Kinetics Of ◽  
Lower Basicity

The rate constants for the reduction of V(III) and oxidation of V(II) were measured on a mercury electrode in water and water-dimethylsulphoxide mixtures. Their dependance on the concentration of DMSO differs from that in mixtures of water with an organic solvent of lower basicity. This can be attributed to the existence of different solvates of vanadium in solutions and to different values of the rate constant for these solvates on the electrode surface at different coverages with the organic component. The influence of DMSO both in the primary solvation sphere and in the electrode double layer on the electrode reaction rate is discussed.

Electrode Kinetics of the Ti(IV)/Ti(III) System in Water and in WaterDimethylformamide and WaterDimethyl Sulfoxide Mixed Solvents

1994 ◽  
Vol 59 (6) ◽  
pp. 1279-1286 ◽  
Author(s):  
Libuše Kišová ◽  
Šárka Šotková ◽  
Ivana Komendová
Keyword(s):  
Rate Constants ◽  
Transfer Rate ◽  
Catalytic Effect ◽  
Mixed Solvents ◽  
Electrode Reaction ◽  
Electrode Kinetics ◽  
Electron Transfer Rate ◽  
Standard Rate ◽  
Electrode Coverage ◽  
Kinetics Of

The electron transfer rate constants in the reduction of Ti4+ and oxidation of Ti3+ in water and in water DMF and water DMSO mixtures were determined by square-wave polarography and by analysis of the DC and pulse polarographic curves. The two reactions occur at different potentials due to the rapid consecutive transformation of the primary product of the electrode reaction. Thus the rate constants are no standard rate constants, and depend on the method employed. The effect of the organic co-solvent varies for both reactions as a consequence of dependence of the degree of electrode coverage on potential. Generally, the adsorbed organic substance exerts an accelerating catalytic effect.

The Effect of p-Toluidine on the Two-Step Electroreduction of Zn(II) in Water-Methanol and Water-Dimethylformamide

1999 ◽  
Vol 64 (4) ◽  
pp. 585-594 ◽  
Author(s):  
Barbara Marczewska
Keyword(s):  
Electron Transfer ◽  
Binary Mixtures ◽  
Rate Constant ◽  
Rate Constants ◽  
Electrode Surface ◽  
Mercury Electrode ◽  
Forward Rate ◽  
Solvent Molecules ◽  
Activated Complex

The acceleration effect of p-toluidine on the electroreduction of Zn(II) on the mercury electrode surface in binary mixtures water-methanol and water-dimethylformamide is discussed. The obtained apparent and true forward rate constants of Zn(II) reduction indicate that the rate constant of the first electron transfer increases in the presence of p-toluidine. The acceleration effect may probably be accounted for by the concept of the formation on the mercury electrode an activated complex, presumably composed of p-toluidine and solvent molecules.

scholarly journals Kinetic Monte Carlo simulation of the growth of CdSe nanocrystals

2021 ◽  
Vol 134 (1) ◽  
pp. 7-23
Author(s):  
S.M. Asadov ◽  
Keyword(s):  
Monte Carlo ◽  
Rate Constants ◽  
Reaction Rate ◽  
Kinetic Monte Carlo ◽  
Cdse Nanocrystals ◽  
Modified Model ◽  
Early Maturation ◽  
Reaction Rate Constants ◽  
Colloidal Crystallization ◽  
Kinetics Of

This article is devoted to modeling the kinetics of colloidal crystallization of cadmium selenide (CdSe) nanoparticles (NPs). The kinetic equation is modified, considering the contributions of the reaction rate constants of individual stages. It includes the reaction rate constants, thermodynamic and calculated parameters, and physical properties. There is used modified kinetic model based on the crystallization equation. There are considered the contributions of adsorption, desorption, and migration of nucleated particles at different times. Modified model assumes that, upon crystallization of NPs CdSe, monomer units depend on the frequency of attachment and detachment transitions of the monomer–CdSe complex. In this case, the transformation of the precursor into a monomer, the formation of an effective monomer and nucleation pass into the growth stage of (NC CdSe) nanocrystals with a seeded mass. In the process, the resulting nanocluster will continue to grow due to early maturation, aging, and subsequent growth into larger NC CdSe. The Kinetic Monte Carlo method (KMC) is used to approximate the model of the nucleation–growth of NC considering different contributions to the reaction rate constants. The modified model with the use of KMC allows to describe the dependences of the kinetic rate constants on the average radius of nanoparticles as a function of time, concentration, and distribution of NC CdSe at a given time. There are described conditions for the formation of NPs CdSe with an evolutionary distribution function of NC CdSe in size space. The results of modeling the kinetics of colloidal crystallization of CdSe can be used to control nucleation rate and growth of NPs CdSe, as well as similar systems in the formation of high-quality NC.

Theory of alternating current polarography. III. Frequency of alternating field and reaction rate

1955 ◽  
Vol 8 (3) ◽  
pp. 322 ◽  
Author(s):  
B Breyer ◽  
HH Bauer ◽  
S Hacobian
Keyword(s):  
Rate Constants ◽  
Reaction Rate ◽  
Electrode Reaction ◽  
Alternating Current ◽  
First Order ◽  
Electrode Reactions ◽  
Polarographic Current

The equation of the A.C. polarographic current for processes where the frequency of the alternating field is comparable with the rate of the electrode reaction is derived. Relative values of equilibrium rate constants of some first order electrode reactions are evaluated experimentally.

Kinetik der Reaktion von 2.4-Dinitrofluorbenzol mit Imidazol-, SH- und Imidazol-SH-Verbindungen / Kinetics of the Reaction of 2,4-dinitro-1-fluorobenzene with Imidazole-, SH- and Imidazole-SH-compounds

1971 ◽  
Vol 26 (10) ◽  
pp. 1010-1016 ◽  
Author(s):  
Renate Voigt ◽  
Helmut Wenck ◽  
Friedhelm Schneider
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Reaction Rate ◽  
Ph Dependence ◽  
First Order ◽  
Molecular Transfer ◽  
Thiolate Anion ◽  
Nucleophilic Reactivity ◽  
Kinetics Of ◽  
Lindley Equation

First order rate constants of the reaction of a series of SH-, imidazole- and imidazole/SH-compounds with FDNB as well as their pH- and temperature dependence were determined. Some of the tested imidazole/SH-compounds exhibit a higher nucleophilic reactivity as is expected on the basis of their pKSH-values. This enhanced reactivity is caused by an activation of the SH-groups by a neighbouring imidazole residue. The pH-independent rate constants were calculated using the Lindley equation.The kinetics of DNP-transfer from DNP-imidazole to SH-compounds were investigated. The pH-dependence of the reaction displays a maximum curve. Donor in this reaction is the DNP-imidazolecation and acceptor the thiolate anion.The reaction rate of FDNB with imidazole derivatives is two to three orders of magnitude slower than with SH-compounds.No inter- or intra-molecular transfer of the DNP-residue from sulfure to imidazole takes place.

Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

1982 ◽  
Vol 47 (7) ◽  
pp. 1773-1779 ◽  
Author(s):  
T. P. Radhakrishnan ◽  
A. K. Sundaram
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Outer Sphere ◽  
Electrode Reaction ◽  
Transfer Reactions ◽  
Cyclic Voltammetric ◽  
Edta Solution ◽  
Kinetics Of ◽  
Activated Complex ◽  
Good Agreement

The paper is a detailed study of the cyclic voltammetric behaviour of Eu3+ at HMDE in molar solutions of KCl, KBr, KI, KSCN and in 0.1M-EDTA solution with an indigenously built equipment. The computed values of the rate constants at various scan rates show good agreement with those reported by other electrochemical methods. In addition, the results indicate participation of a bridged activated complex in the electron-transfer step, the rate constants showing the trend SCN- > I- > Br- > Cl- usually observed for bridging order of these anions in homogeneous electron-transfer reactions. The results for Eu-EDTA system, however, indicate involvement of an outer sphere activated complex in the electrode reaction.

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