IN-SITU SPECTROSCOPY IN THE PRESENCE OF CONVECTIVE FLOW UNDER STEADY-STATE CONDITIONS - A UNIFIED MATHEMATICAL FORMALISM

A generalized mathematical treatment is presented that enables a quant itative analysis of various in situ spectroscopic experiments involvin g detection of solution-phase species generated at the surface of rota ting disk and ring-disk, channel, and tube-type electrodes under stead y state. This theory is valid for experimental conditions easily reali zable in the laboratory and is only applicable to first-order irrevers ible heterogeneous electron-transfer processes without complications d erived from homogeneous phase reactions. Illustrations of the advantag es of this formalism are provided, including a rederivation of equatio ns obtained by other authors, an analytic route to the solution of the rotating disk-transparent ring electrode, and various aspects df norm al incidence reflection absorption spectroscopy at rotating ring and r ing-disk electrodes. The results were in excellent agreement with thos e of other workers (when available), and in some cases, yielded better accuracy than solutions generated by digital simulation techniques re ported in the literature.