Application of the Stationary Dropping-Mercury Electrode for Kinetic Studies

Application of the Stationary Dropping-Mercury Electrode for Kinetic Studies 

The S DME is also used to obtain kinetic information. Measturement at the foot of the polarographic wave, where the current is activation-controDed, can yield the most accurate I/E relationship achievable with any electrode, because of the very high reproducibility of the surface. Equations have also been developed that allow quantitative correction for mass-transport limitation up to higher currents (J 0.95 Id) along the polarographic wave, extending the region where the activation-controlled current can be evaluated. 

When the reaction being studied is relatively slow, the I/E relationship does not follow Eq. (4.20). This problem was treated by Koutecky, who was able to e3q ress the activation-controlled current I. in terms of a dimensionless parameter, x which is linearly related to the heterogeneous rate constant of the reaction  

---