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A power supply establishes the electric field that causes electrons to migrate in the ‘electrical’ portion of the circuit and ions to flow in the ‘ionic’ part (figure 1). It follows that the number of electrons flowing through the ‘electrical’ portion of the circuit is exactly balanced by the amount of ionic charge flowing through the skin.
The sum of the individual ionic charges flowing across the skin must equal the number of electrons ‘delivered’ by the power supply; in other words, there is ‘competition’ among all the ions present to carry the charge.
Furthermore, with respect to electromigration, only the ionized fraction of the analyte is extractable and this will depend on the relevant pKa...
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