Photogalvanic cells: Part X. The transparent disc electrode and the iron-thionine system

The kinetics of the iron-thionine system have been investigated using the transparent rotating disc electrode and flash electrolysis. Using the transparent disc electrode, from the results for the variation of photocurrent with rotation speed and irradiance, we can find the quantum efficiency for the production of semithionine, the efficiency for producing leucothionine from semithionine and the rate constant for the back reaction of leucothionine with Fe(III). This rate constant is also determined from the flash electrolysis experiments. The values of the kinetic parameters are found to be in good agreement with values determined by analysis of the photostationary state, flash photolysis and ac modulation at a transparent disc electrode. The relative merits of the different techniques for investigating photogalvanic systems are discussed.