The electrochemical behavior of flavin adenine dinucleotide in neutral solutions

1988 ◽  
Vol 66 (1) ◽  
pp. 86-96 ◽  
Author(s):  
V. I. Birss ◽  
H. Elzanowska ◽  
R. A. Turner

A detailed investigation of the electrochemical behavior of flavin adenine dinucleotide (FAD) in neutral solutions has been carried out at Hg and glassy carbon electrodes. At FAD concentrations of about 10−4 M, cyclic voltammetry (CV) shows a pair of anodic and cathodic peaks having a peak separation at low sweep rates indicative of a two-electron transfer process and yielding a formal redox potential for FAD of −0.206 ± 0.003 V vs. NHE at pH 7. Evidence for FAD adsorption was obtained in experiments at high sweep rates, from the effect of time of exposure of the electrode surface to FAD in solution and from the effect of the potential limits on the cyclic voltammetric response. The process of FAD adsorption was studied in detail in dilute FAD solutions (ca 10−6 M) using a hanging mercury drop electrode and the techniques of CV and ac voltammetry. Three distinct stages of FAD adsorption were observed and a model of the orientation of FAD on the electrode surface as a function of time and potential is presented. In addition, the kinetics of oxidation and reduction of adsorbed FAD was studied for each of the stages of FAD deposition, and a surface standard rate constant of ca. 40 s−1 was obtained for Stages II and III of FAD adsorption.

1989 ◽  
Vol 54 (10) ◽  
pp. 2638-2643
Author(s):  
David I. Balanchivadze ◽  
Tamara R. Chelidze ◽  
Jondo J. Japaridze

The effect of bifunctional alcohols ethylene glycol (EG) and 1,2-propylene glycol (1,2 PG) on the kinetic parameters for the irreversible chromate ion reduction were investigated by polarographic and coulometric methods of analysis. The electroreduction of chromate ion in neutral bifunctional alcohol solutions proceeds according to the scheme: Cr(VI)–Cr(III)–Cr(II) and the values of the standard rate constant k*0 decrease in the order H2O > EG > 1,2 PG. The values of real activation energy, Q, activation energy of diffusion, QD, and frequency factor log A° have been calculated. The obtained values of QD as well as Q proved the diffusion nature of limiting current. The values of the frequency factor log A° decrease in the order H2O > EG > 1,2 PG, which points to a less favourable orientation of the electroactive ions at the electrode surface in glycols.


1990 ◽  
Vol 87 ◽  
pp. 1597-1607 ◽  
Author(s):  
L Benedetti ◽  
M Borsari ◽  
C Fontanesi ◽  
G Battistuzzi Gavioli

1987 ◽  
Vol 52 (6) ◽  
pp. 1386-1396 ◽  
Author(s):  
Ján Mocák ◽  
Michal Németh ◽  
Mieczyslaw Lapkowski ◽  
Jerzy W. Strojek

A spectrocoulometric macrocell with a direct-view optical probe was designed and constructed, where the optical signal is transferred by light-conducting glass or quartz fibres permitting to work at wavelengths above 410 or 300 nm. The method of measurement on the proposed equipment is described; it was tested in the study of the mechanism and kinetics of oxidation of Fe(bipy)32+ ions (bipy = 2,2'-bipyridyl) with the use of potentiostatic coulometric electrolysis with open-circuit relaxation at a suitable time. The primary product of electrolysis, Fe(bipy)33+, undergoes a follow-up hydrolytic reaction with the formation of a binuclear complex. The rate constant of the reaction of the first order involves the contributions, kBi, from all bases present in solution; the corresponding values for H2O, OH-, bipy, and CH3COO- ions at a ionic strength 0·5 mol dm-3 and 25 °C were determined as kOH = (5·0 ± 0·6) . 105 mol-1 dm3 s-1, kbipy = (1·3 ± 0·2) . 10-1 mol-1 dm3 s-1, kAc = (5·8 ± 1·0) . 10-2 mol-1 dm3 s-1, and kH2O is not significant with respect to experimental errors.


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.


1982 ◽  
Vol 47 (8) ◽  
pp. 2087-2096 ◽  
Author(s):  
Bohumil Bernauer ◽  
Antonín Šimeček ◽  
Jan Vosolsobě

A two dimensional model of a tabular reactor with the catalytically active wall has been proposed in which several exothermic catalytic reactions take place. The derived dimensionless equations enable evaluation of concentration and temperature profiles on the surface of the active component. The resulting nonlinear parabolic equations have been solved by the method of orthogonal collocations.


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