Kinetics of electrode processes. IV. General calculation of the current due to a linear system of electrode reactions involving at most one chemical reaction in solution

1953 ◽  
Vol 18 (2) ◽  
pp. 183-196 ◽  
Author(s):  
J. Koutecký
Keyword(s):  
Linear System ◽  
Chemical Reaction ◽  
Electrode Processes ◽  
Electrode Reactions ◽  
Kinetics Of ◽  
Reaction In Solution

Significance of effects of pressure on electrode reactions. Part III. Equilibrium processes at reference electrodes and the volume of H in Pd

1978 ◽  
Vol 56 (7) ◽  
pp. 915-924 ◽  
Author(s):  
Brian E. Conway ◽  
J. C. Currie
Keyword(s):  
Pressure Range ◽  
Volume Changes ◽  
Reference Electrodes ◽  
Pressure Coefficients ◽  
Electrode Processes ◽  
Elevated Pressures ◽  
Electrode Reactions ◽  
Equilibrium Processes ◽  
Pressure Bomb ◽  
Kinetics Of

For studies on effects of pressure on kinetics of electrode processes (Parts I, II), reversible reference electrodes suitable for use in a completely enclosed high-pressure bomb are required. The electrodes must exhibit reversible behaviour over the pressure range employed in the experiments, i.e., their changes of emf with increasing and decreasing changes of pressure must be reproducible and correspond to the respective volume changes in the reactions.A series of reversible reference electrodes is examined over a range of pressures up to ca. 2500 bars. The Pd–H/H+ and Ag, AgCl/Cl− reference electrodes are found to behave very satisfactorily at elevated pressures; the Pt,H2/H+ electrode is, however, less satisfactory, due to problems associated with dissolved H2.The results enable the volume of Pd–H and of H sorbed into Pd to be evaluated, together with estimates of the partial molar volume of H2 in aqueous HCl. These data enable the pressure-coefficients of metal–solution potential differences at individual reference electrodes to be evaluated. Such information is required for interpretation of effects of pressure on kinetics of electrode processes.

scholarly journals Theory of staircase cyclic voltammetry of two electrode reactions coupled by a chemical reaction

2019 ◽  
Vol 51 (3) ◽  
pp. 348-357
Author(s):  
Š. Komorsky-Lovrić ◽  
M. Lovrić
Keyword(s):  
Cyclic Voltammetry ◽  
Chemical Reaction ◽  
Forward Rate ◽  
Electrode Reactions ◽  
Reversible Chemical Reaction ◽  
Ece Mechanism ◽  
Forward Rate Constant ◽  
Thermodynamic And Kinetic Parameters ◽  
The Stability ◽  
Kinetics Of

Two reversible electrode reactions that are connected by either reversible or totally irreversible chemical reactions are theoretically analysed by staircase cyclic voltammetry. The dependence of peak potentials on the thermodynamic and kinetic parameters is calculated. If the mechanism is permanently in equilibrium, the stability constant of the reversible chemical reaction can be determined. Furthermore, the critical kinetic parameter is determined and its application to the measurement of the forward rate constant of the chemical reaction is demonstrated. Also, the influence of the kinetics of electrode reactions is discussed. Keywords: ECE mechanism; Cyclic voltammetry; Theory

scholarly journals The kinetics of electrode reactions. I and II

1938 ◽  
Vol 169 (937) ◽  
pp. 206-234 ◽  
Keyword(s):  
Electrode Potential ◽  
Surface Reaction ◽  
Reference Electrode ◽  
Electrode Reaction ◽  
Potential Difference ◽  
Concentration Difference ◽  
Electrode Processes ◽  
Electrode Reactions ◽  
Concentration Changes ◽  
Kinetics Of

In any surface reaction taking place in a Solution, it is clear that the concentration of the reactants in the vicinity of the surface must fall. If the concentration in the bulk of the solution remains constant, a steady state may finally be reached, in which the rate of replenishment of the solution in this region, from the bulk, is equal to the rate at which the reactant in question is used up. But, in general, such a state is only attained when the concentration at the surface is less than that in the rest of the solution. If the reaction considered is an electrode reaction, these concentration changes may affect the electrode potential. This question is therefore of importance in the study of overpotential, and of the kinetics of electrode processes generally. The overpotential at an electrode is defined as the potential difference between this electrode and a similar unpolarized reversible electrode in the same solution. In practice this reference electrode is usually situated outside the region affected by the concentration changes near the electrode at which the reaction is taking place. The measured potential difference between the two electrodes, i.e. the measured overpotential, may therefore include a term due to the concentration difference.

On the Role of Diffusion in the Oxidation of Fe, Ni, Co and the Fe-Sn Alloy by Calcium and Sodium Sulfates

2006 ◽  
Vol 258-260 ◽  
pp. 63-67
Author(s):  
V.M. Chumarev ◽  
V.P. Maryevich ◽  
V.A. Shashmurin
Keyword(s):  
Co Oxidation ◽  
Chemical Reaction ◽  
Diffusion Processes ◽  
Transport Processes ◽  
Diffusion Transport ◽  
Sodium Sulfates ◽  
Product Forms ◽  
Kinetics Of ◽  
Dominant Part

Diffusion processes play a dominant part in the macro kinetics of Fe, Ni and Co oxidation by calcium and sodium sulfates. Here, the reaction product forms a compact covering which spatially divides the reagents on the surface in the same way as in the oxidation and sulfidization of metals by oxygen and sulfur. Therefore, it is possible to assume in advance that interaction of metals with calcium and sodium sulfates will be determined not by the actual chemical reaction properly but by the diffusion transport processes.

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