Abstract
The rate constant for CCl 4 electroreduction on mercury, once corrected for diffuselayer effects according to Frumkin, still depends on the charge density q i due to specifically abdsorbed supporting ions. Thus, in the presence of the adsorbed anions Cl −, Br −, SCN − and N 3 −, the logarithm Φ of the rate constant corrected for diffuse-layer effects decreases linearly with | q i|. The slopes of the various Φ vs. q i plots are in fairly good agreement with the theoretical treatment of ref. 9, which accounts for the electrostatic interactions between the activated complex for the electrode reaction and the neighbouring adsorbed electroinactive ions within the compact layer. An analogous behaviour is observed in the reduction of CBr 4.
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