0000000000383217
AUTHOR
E. Laviron
The pseudostationary mercury electrode
Abstract A detailed study of the pseudostationary mercury electrode is presented, based on its use in LSV. Delay times ( t 1 ) as short as 20 ms can be employed; the drop area is still given by its classical expression, and minimization of the ohmic drop allows sweep rates of a few thousands of volts per second to be used. The conditions for pseudostationarity are given; the lower sweep rates utilizable are of the order of few tenths of volt per second. Reactant adsorption is considered, and zones where rehomogenization near the electrode surface is practically either 100 or 0% are defined in a plane log t 1 /log b O ( b O is the adsorption coefficient); the diffusional or surface character…
Electrochemical reactions with adsorption of the reactants and electrosorption. Simple analytical solutions for a Henry isotherm
Abstract A theoretical treatment of an electrochemical reaction O + ne− R with adsorption of the reactants is presented when the adsorption, at equilibrium, obeys a Henry isotherm. A simple analytical solution, valid for any degree of adsorption of O and or R, is established for a polarographic wave. In LSV, for slow sweep rates and weak adsorption, both the cathodic and anodic peaks have a ‘diffusional’ character; for high sweep rates and strong adsorption, they are both of a ‘surface’ nature. In the intermediate case, one peak has a ‘diffusional’ character (deposition process), while the other is of a ‘surface’ nature (redissolution process). Expressions of the peak potentials are given i…
Second harmonic ac polarography of strongly adsorbed electroactive species
Abstract The second harmonic ac current is calculated for the case of a quasi-reversible surface redox system: both species are strongly adsorbed according to a Langmuir isotherm and the kinetics of the process are controlled by the electron transfer. The current is measured with a phase-sensitive detector and the variation of the in-phase and quadrature components vs. the frequency leads to the surface rate constant ks. The experimental results obtained for benzo-(c)cinnoline are in good agreement with the theoretical predictions and with the results of impedance measurements. The advantages of the two methods are compared.
The electrochemical reduction of thioisonicotinamide in an aqueous medium
Abstract The electrochemical reduction of thioisonicotinamide NRCSNH 2 has been examined in an aqueous medium between H 0 =−1 and pH=13.7. As shown by cyclic voltammetry and polarography, a global 2e − reversible transfer is followed by two successive first-order chemical reactions and a 2e − , 2H + reduction (EC 1 C 2 E process). A mechanism is proposed, beginning with the 2e − reduction of NRCSNH 2 to the formal diionized form NRC − (SH)(NH 3 + ), the first chemical reaction, C 1 , being a formal proton transfer which yields the 4- gem aminosulfanylmethylpyridine; the rate constant of this reaction is 2×10 4 s −1 in acidic medium and diminishes in neutral medium. The second process, C 2 …
The reduction mechanism of the CO group.
A detailed study of the electrochemical reduction of benzil in aqueous medium between H0=−5 and pH 11 is presented. A global 2e−, 3H+ or 2e−, 2H+ surface reaction leads to cis and trans endiols. Analysis, using the theory of the square schemes with protonations at equilibrium, shows that in all the pH range the reaction is controlled by the second electron uptake, the paths being successively H+, e− and e−, H+. The electrochemical reaction is followed by surface isomerizations whose rate constants vary from 7 to 200 s−1 for the trans/cis and from 1 to 2000 s−1 for the cis/trans transformations.