The Effects of Adsorbed Ions on Simple Electrode Reactions. II. The Reduction Of Chromium(III) Ion in The Presence of TolueneP-Sulfonate Anions

1974 ◽  
Vol 52 (18) ◽  
pp. 3165-3169 ◽  
Author(s):  
Kamaruzzaman Alias ◽  
W. Ronald Fawcett
Keyword(s):  
Double Layer ◽  
Mercury Electrode ◽  
Diffuse Layer ◽  
Reaction Site ◽  
Electrode Reactions ◽  
Reaction Acceleration ◽  
Kinetics Of ◽  
Outer Helmholtz Plane

The kinetics of electroreduction of Cr3+ ion have been studied at a mercury electrode both in the absence and in the presence of chemisorbed toluene p-sulfonate ions. The rate of the reaction was considerably accelerated in the presence of the chemisorbed anions. Analysis of the data has shown that the reaction acceleration can be accounted for on the basis of Frumkin's theory for double layer effects suggesting that the reaction site is at the outer Helmholtz plane or close to it in the diffuse layer.

Discreteness-of-charge effects in electrode kinetics. III. The electroreduction of aquopentamminochromium(III) cation in the presence of specifically adsorbed iodide anions

1984 ◽  
Vol 62 (8) ◽  
pp. 1497-1501 ◽  
Author(s):  
W. Ronald Fawcett ◽  
Kveta Markušová
Keyword(s):  
Ionic Strength ◽  
Electrode Kinetics ◽  
Reaction Site ◽  
Charge Effects ◽  
Iodide Concentration ◽  
Rate Acceleration ◽  
Rate Of Reaction ◽  
Layer Effect ◽  
Kinetics Of ◽  
Outer Helmholtz Plane

The kinetics of electroreduction of the aquopentamminochromium(III) cation have been studied at a Hg electrode in acidified aqueous solutions of NaI+ NaClO4 with an ionic strength of 0.25 M. The rate of reaction increased with increase in iodide concentration due to the accelerating effect of this anion when it is adsorbed on the electrode. Analysis of the double layer effect indicates that the rate acceleration is greater than that predicted by the Frumkin theory chiefly because the reaction site is closer to the electrode than to the outer Helmholtz plane.

Electrode kinetics of the system V(III)/V(II) in aqueous dimethylsulphoxide

1991 ◽  
Vol 56 (1) ◽  
pp. 90-95 ◽  
Author(s):  
Libuše Kišová ◽  
Libor Reichstädter ◽  
Jaro Komenda
Keyword(s):  
Organic Solvent ◽  
Double Layer ◽  
Rate Constants ◽  
Electrode Surface ◽  
Reaction Rate ◽  
Mercury Electrode ◽  
Electrode Reaction ◽  
Electrode Kinetics ◽  
Kinetics Of ◽  
Lower Basicity

The rate constants for the reduction of V(III) and oxidation of V(II) were measured on a mercury electrode in water and water-dimethylsulphoxide mixtures. Their dependance on the concentration of DMSO differs from that in mixtures of water with an organic solvent of lower basicity. This can be attributed to the existence of different solvates of vanadium in solutions and to different values of the rate constant for these solvates on the electrode surface at different coverages with the organic component. The influence of DMSO both in the primary solvation sphere and in the electrode double layer on the electrode reaction rate is discussed.

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