Langmuir, Vol.15, No.14, 4907-4915, 1999
Interference of adsorption, condensation, and double-layer charging in kinetic studies of film formation. 2. Nonconstant double-layer potential
The single-potential-step technique is a useful electrochemical method for kinetic studies of phase transitions on electrodes. Under ideal conditions the final potential acts in the double layer immediately after the potental step is finished. But in experiments due to the finite time constants of the different electrode processes, the processes take place simultaneously and therefore influence each another. The measured current response contains the different parts of current, like double-layer charging due to the potential step, adsorption, and condensation more or less distinguishable according to the cell and kinetic parameters. For the experimental conditions this means that the entire electrode process, including the above-mentioned processes, takes place with a variable local double-layer potential. To describe such "nonpotentiostatic'' conditions, the model of a coupled adsorption and nucleation and growth process (Part 1) is extended by a time dependent potential evolution, which again depends on the adsorption and condensation. Possible current transients were simulated with the help of the extended model and compared with the corresponding current transients in Part 1. Dependent on the cell resistance, the transients change their shape.