scholarly journals Simulated Data for Simple Electrochemical Determination of Rate Constants for Homogeneous Electron Transfer (SET) Reactions and Competition Parameter for Second-Order Follow-up Reactions. II. Coupling and Second SET Reaction between Mediator and Reduced Form of the Substrate.

1987 ◽  
Vol 41a ◽  
pp. 391-402 ◽  
Author(s):  
Steen U. Pedersen ◽  
Knut Maartmann-Moe ◽  
Sine Larsen ◽  
Erik Pedersen ◽  
L. Niinistö
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Simulated Data ◽  
Electrochemical Determination ◽  
Second Order ◽  
Reduced Form ◽  
Competition Parameter

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

Studies of Reactions between Flavins and Quinones, Mercaptans, and Enolates

1972 ◽  
Vol 27 (9) ◽  
pp. 1016-1020 ◽  
Author(s):  
Morton J. Gibian ◽  
D. Lauriston Elliott ◽  
Charles Kelly ◽  
Brad Borge ◽  
Kirklen Kupecz
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Redox Reaction ◽  
Radical Anion ◽  
Second Order ◽  
Ph Values ◽  
Order Rate

A. Equilibrium and second-order rate constants have been measured for the redox reaction between phthaloquinone and dihydroriboflavin (and its reverse) at a number of pH values. The equilibria and kinetic determinations are in agreement. No intermediates could be found in the reaction, and it is proposed that with this and other quinones electron transfer occurs within a complex of the flavin and hydroquinone (or dihydroflavin and quinone). B. A survey of the reaction between mercaptans and flavins is reported, as well as data showing that with mercaptoethanol the reaction is reversible, the disulfide and reduced flavin giving mercaptan and flavin. C. The reaction of alkylphenone enolates with isoalloxazine is described. This reaction leads t 50% isoalloxazine radical anion and an adduct of the enolate with the ketone. A possible route for this process is discussed.

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