Analytical aspects of absorption spectroelectrochemistry at a platinum electrode-I Study of metal ions.

An apparatus has been built with which the intensity of a light-beam passing at grazing incidence over a platinum electrode can be monitored. The absorption of light which occurs during the electrolysis of dilute aqueous metal ion solutions has been studied as a function of a number of parameters including wavelength, potential difference and concentration. The theories of metal deposition and processes occurring at the electrode surface and in the diffusion layer have been examined and a mechanism for the production of the absorbing species in terms of increase in pH of the catholyte is proposed. The analytical potential of the technique is discussed.