Determination of Electrochemical Electron‐Transfer Reaction Standard Rate Constants at Nanoelectrodes: Standard Rate Constants for Ferrocenylmethyltrimethylammonium(III)/(II) and Hexacyanoferrate(III)/(II)

2008 ◽  
Vol 20 (13) ◽  
pp. 1490-1494 ◽  
Author(s):  
Yan Zhang ◽  
Jianzhang Zhou ◽  
Lingling Lin ◽  
Zhonghua Lin
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Standard Rate

scholarly journals Simulation of Alternative Differential Multi-pulse Voltammetry. Evaluation of the Electrochemical Reversibility by the Voltammogram Symmetry

2019 ◽  
Vol 92 (1) ◽  
pp. 95-102
Author(s):  
Dijana Jadreško
Keyword(s):  
Electron Transfer ◽  
Transfer Reaction ◽  
Electrode Reaction ◽  
Electron Transfer Reaction ◽  
Electrode Reactions ◽  
Electrochemical Reversibility ◽  
Kinetically Controlled ◽  
Standard Rate ◽  
Pulse Voltammetry ◽  
Standard Rate Constant

A theoretical analysis of reversible and kinetically controlled electrode reactions in conditions of alternative differential multi-pulse voltammetry (ADMPV) is presented. The degree of reversibility, as well as symmetry of the electron transfer reaction, can be estimated by visual inspection of the ADMP voltammogram. The values of electron transfer coefficient and the standard rate constant of a simple electrode reaction Ox + ne− ⇄ Red, can be determined from the slope of linear dependence of the peak currents ratio on the logarithm of pulse duration. The criteria for recognition of reversible and kinetically controlled electrode reactions by alternative differential multi-pulse voltammetry are given.

scholarly journals A method for extracting rate constants from initial rates of stopped-flow kinetic data: application to a physiological electron-transfer reaction

1993 ◽  
Vol 294 (1) ◽  
pp. 211-213 ◽  
Author(s):  
H B Brooks ◽  
V L Davidson
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Kinetic Data ◽  
Transfer Reaction ◽  
Dissociation Constants ◽  
Accurate Method ◽  
Electron Transfer Reaction ◽  
Stopped Flow ◽  
Methylamine Dehydrogenase ◽  
Substrate Complex

The most commonly used methods for analysis of stopped-flow kinetic data require performing a series of measurements in which one reactant is varied at concentrations significantly greater than the concentration of the other reactant. For enzyme-catalysed reactions this may not be possible, because the dissociation constants for the enzyme-substrate complex are often of the same order of magnitude as the high concentrations of enzyme that must frequently be used in stopped-flow studies. An alternative method of data analysis is presented which allows the determination of microscopic rate constants from initial rates of stopped-flow kinetic data in which substrate is varied in a range of concentrations approximately the same as the enzyme. This method also provides a simple and accurate method for determining k4, the rate of the reverse reaction. This method has been used to describe a physiological electron transfer reaction between a quinoprotein, methylamine dehydrogenase, and a copper protein, amicyanin. At 20 degrees C, the rate of the electron-transfer reaction from methylamine dehydrogenase to amicyanin was 24 s-1, and the dissociation constant for complex-formation was 1.9 microM.

Possible use of chronopotentiometry at the interface between two immiscible liquid phases to the studies of homogeneous chemical reactions

1985 ◽  
Vol 50 (8) ◽  
pp. 1636-1641
Author(s):  
Emanuel Makrlík
Keyword(s):  
Electron Transfer ◽  
Chemical Reactions ◽  
Transfer Reaction ◽  
Electron Transfer Reaction ◽  
Immiscible Liquid ◽  
Liquid Phases ◽  
Homogeneous Chemical ◽  
The Given ◽  
Galvanostatic Conditions

The theoretical potential-time dependence corresponding to the electron transfer reaction proceeding at the interface between two immiscible liquid phases with the redox pairs O1/R1 in the aqueous (aq) phase and O2/R2 in the non-aqueous (non) phase, that is complicated by the reaction R1(aq) + Z(aq) → O1(aq) in the aqueous phase, has been derived under the galvanostatic conditions. Moreover, a method for the determination of the formal rate constant kf for the given homogeneous chemical reaction is proposed.

Determination of electrochemical heterogeneous electron-transfer reaction rates from steady-state measurements at ultramicroelectrodes

1986 ◽  
Vol 58 (14) ◽  
pp. 2961-2964 ◽  
Author(s):  
Andrea. Russell ◽  
Kari. Repka ◽  
Timothy. Dibble ◽  
Jamal. Ghoroghchian ◽  
Jerry J. Smith ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Steady State ◽  
Transfer Reaction ◽  
Reaction Rates ◽  
Electron Transfer Reaction ◽  
Heterogeneous Electron Transfer

Effects of potassium ion on the electron-transfer reaction between Fe(CN)64− and TCNQ or chloranil

1978 ◽  
Vol 56 (16) ◽  
pp. 2216-2220 ◽  
Author(s):  
Sadayuki Matsuda ◽  
Akihiko Yamagishi
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Transfer Reaction ◽  
Temperature Jump ◽  
Ion Pairing ◽  
Electron Transfer Reaction ◽  
Potassium Ion ◽  
The Other ◽  
Transfer Reactions ◽  
Forward Rate

The effects of potassium ion on the electron-transfer reactions between Fe(CN)64− and 7,7,8,8-tetracyanoquinodimethane (TCNQ) or chloranil (QCl4) were studied with temperature-jump equipment; [Formula: see text]. The solvent was a 1:1 (v/v) mixture of acetonitrile–water. In both Systems, the forward rate constants (kr) were unaffected by the addition of KCl; kf(Fe(CN)64−/TCNQ) = (2.9 ± 0.2) × 106 M−1 s−1, and kr(Fe(CN)64−/QCl4) = (5.2 ± 0.4) × 104 M−1 s−1 On the other hand, the backward rate constants (kb) increased with the increase of the KCl concentration. The results are interpreted in terms of ion-pairing equilibria of Fe(CN)64− and Fe(CN)63−.

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