Supporting Electrolyte
When performing electroanalytical experiments, it is conventional to add a large quantity of inert salt to the solution — this artificially added salt is called supporting electrolyte. The purpose of the supporting electrolyte is to increase the conductivity of the solution, and hence to eliminate the electric field from the electrolyte.
A negligible electric field provides two advantages for electroanalysis:
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The voltage due to the resistance of the electrolyte when the cell draws current (“ohmic drop”) is minimal. Therefore, the potential difference applied across the electrochemical cell is localized at the electrode–electrolyte interfaces, and so the activation overpotential perceived by the redox couple at this interface is almost exactly proportional to the applied cell voltage. The kinetic behavior of the electrochemical cell then has no explicit dependence on the magnitude of the drawn current.
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The contribution of migration to the transport of charged chemical species is negligible compared to the contribution of diffusion (and of convection, in a forced flow). Therefore the transport properties of the system are linearized, and they do not depend on the magnitude of the drawn current.
These properties greatly simplify the design and analysis of electroanalytical experiments. Therefore, the use of a supporting electrolyte is very common in electrochemical sensing and electroanalysis.
The amount of supporting electrolyte required for the assumption of zero electric field to be sound is dependent on the system. Typically it becomes valid when the concentration of inert salt exceeds the concentration of analyte by a factor of 10–100, but this is not always the case.
Even for the conductivities of electrolyte solutions in the presence of excess supporting electrolyte, the electric field is not negligible if significant current density is drawn. Electroanalysis typically draws small currents because the purpose is measurement. In processes where an electrochemical reaction is driven — such as electrolysis, electrodeposition, batteries, and fuel cells — current densities are typically much larger, so that the desired extent of reaction is achieved in a reasonable time. Under these conditions, significant electric fields are likely and other charge conservation models should be used instead of the Electroanalysis option.