A few basics of Electrochemistry

Faradaic Current and non-Faradaic current.

Two types of process can conduct charge across an electrode-solution interface. One type involves a
direct transfer of electrons at one of the electrodes via an oxidation reaction and simultaneously may
transfer electron via reduction to the other electrode. Process of these types are termed as Faradaic
process because those are governed by Faraday’s laws, which states that amount of mass deposited is
proportional to the current. This current is known as Faradaic Current.

Under certain condition a range voltages may be applied to a cell which do not produce Faradaic
process in one or both the electrodes. Faradaic process may be prevented either because electrons do
not have sufficient energy to pass over the potential barrier at the electrode-solution interface
(Thermodynamic reasons) or because electron transfer rate is not fast enough in the time scale of the
experiment (Kinetic reasons). Under these condition, conduction of alternating currents may still take
place. With such currents reversal of the charge relationship occurs with each half cycle as first
negative and the positive charges are attracted alternatively to the electrode surface. Electrical energy
from the external voltage source is consumed and converted to the heat by the friction associated
with the motion of ions. Another way to look at the consumption of energy is that when the voltage
changes, the ions in the double layer have to re-arrange and adjust to the new potential and this
reaarangement requires energy. Thus each electrode surface behaves one plate of capacitor, whose
capacitance is large (several hundreds to several thousand microfarads per square centimeter). This
capacitative current increase with frequency and with electrode area; By controlling these variables, it
is possible to adjust condition that essentially all of the alternating current in a cell is carried across
the electrode interface by this non-Faradaic process.

Capacitor
C=Q/V

A capacitance of 1 Farad means one Coulomb of charge in each conductor causes a voltage of 1 volt
across the device.

Ideally Polarizable and non-polarizable electrode.

Ideally polarizable electrode (also ideal polarizable electrode or ideally polarized electrode),
in electrochemistry, is an electrode characterized by an absence of net current between the two
sides of the electrical double layer, i.e., no faradic current between the electrode surface and the
electrolyte. Any transient current that may be flowing is considered non-faradaic.[1] Ideally
polarizable electrode is contrasted with ideally non-polarizable electrode, for which a faradic
current can freely pass (without polarization). A polarizable electrode ideally has no DC current
flow between the electrode and the surrounding electrolyte. It shows a very large change in
potential upon passage of small current. The electrode/electrolyte interface behaves like a
capacitor.

A non-polarizable electrode has no polarization, that is, current flows freely. Its potential does
not change from its equilibrium potential upon application of current. The reason for this
behavior is that the electrode reaction is extremely fast (has an almost infinite exchange current
density). The electrode-electrolyte interface behaves like a resistor.

The classical examples of the two ideal types of electrodes, polarizable and non-polarizable, are
the platinum electrodes and the silver/silver chloride, respectively.[2]

The concept of the ideal polarizability has been first introduced by F.O. Koenig in 1934.[1]

References
1.
 Vladimir Sergeevich Bagot'skiĭ, "Fundamentals Of Electrochemistry",John Wiley & Sons,
2006, p. 178. ISBN:9780471700586

2.  Neuman, M. R. “Biopotential Electrodes.”, The Biomedical Engineering Handbook:

Second Edition, CRC Press LLC, 2000, ISBN:9781420049510 Allen J. Bard, Larry R.
Faulkner, "Electrochemical methods; Fundamentals and Applications", John Wiley &
Sons, 2001, ISBN:0-471-04372-9

Diffusion current

Arising from the gradient of charged species concentration. Obeys Ficks Law

dρ
J=−qD
dx

Ohmic current or drift current arising from applied electric field J=qpμE

Amperometry

Hydroxy Quinolin