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On the basis of the results obtained by computer simulation as well as experimentally for poly (vinyl-ferrocene) and chemically derivatized nickel electrodes the influence of layer thickness, uncompensated ohmic resistance and slow heterogeneous charge transfer on the chronoamperometric response in discussed. It is shown that in several cases reliable charge-transport diffusion coefficient can be extracted from the experimental i-t-1/2 data only with the help of simulation technique by using appropriate relationships; since no Cottrell-line can be drawn or the slope of a straight line passing the origo and several points deviates from that one corresponding to the actual D(ct)2/1 c value.This is due to the fact that there is no such time interval where the influence of the uncompensated ohmic potential drop and/or the slow charge transfer no more exist and the fall of the current related to the finite thickness of the surface layer does not appear yet.
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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion