The overall electrochemical cell experimental considerations

The electrochemical cell is coupled to a three-electrode potentiostatted form of instrumentation. If a two-electrode (working and reference) system were to be used, the current would have to flow through the reference electrode, thus risking instability in the reference potential. Furthermore, in a two-electrode system, the IR drop could be substantial. In contrast, in the three-electrode potentiostatted system, the current is forced to flow through the counter electrode, thereby avoiding problems with the reference electrode. Additionally, much of the IR drop is compensated by the potentiostat circuitry (Macdonald, 1977), which drives the potential between the working and counter electrode to a value which compensates the majority of this potential loss. However, the use of a potentiostat does not remove all of the IRu drop, since uncompensated resistance remains due to solution resistance between the tip of the reference and working electrodes, and 

Data obtained using these reference couples may be compared with analytical solutions for the peak current, limiting current or voltammetric waveshape (see Sections 3 and 4). Non-compliance of experiment and theory is indicative of malfunctioning instrumentation, poor experimental design (i.e. an unacceptably large uncompensated solution resistance) or a faulty electrode. 

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The two major classes of voltammetric technique 4 Evaluation of reaction mechanisms 6 General concepts of voltammetry 6 Electrodes roles and experimental considerations 8 The overall electrochemical cell experimental considerations 12 Presentation of voltammetric data 14 Faradaic and non-Faradaic currents 15 Electrode processes 17 Electron transfer 22 Homogeneous chemical kinetics 22 Electrochemical and chemical reversibility 25 Cyclic voltammetry 27 A basic description 27 Simple electron-transfer processes 29 Mechanistic examples 35... 

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