ALTERNATING CURRENT POLAROGRAPHY - THEORETICAL PREDICTIONS FOR SYSTEMS WITH FIRST-ORDER CHEMICAL REACTIONS PRECEDING CHARGE TRANSFER STEP

Results of a detailed study of theoretical predictions for the fundamental harmonic ac polarographic response with systems involving rate control by diffusion, first-order preceding chemical reactions, and/or heterogeneous charge transfer kinetics are given. A theoretical formulation resulting from a rigorous solution of the expanding plane boundary value problem by the Matsuda method is the subject of investigation. The calculated ac polarographic behavior is examined for a wide range of kinetic conditions. The considerable sensitivity of the ac polarographic response to kinetic influences of the preceding chemical reaction is made apparent. Approaches to data analysis are discussed. © 1969, American Chemical Society. All rights reserved.