Amperometry
By
Dr Nagwa Abo El-maali
Amperometry
Amperometry is an electroanalytical technique
that measures current over time by applying a
constant anodic/cathodic potential.
It is used to detect electroactive species in a
solution based on the concentration of
oxidized/reduced species.
• From polarogram it can be seen that , the
diffusion current ( = limiting current - residual
current) is proportional to the concentration of
the electro-active material in the solution.
• If some of the electro-active material is
removed by interaction with reagent, the
diffusion current will decrease.
• This is the fundamental principle of amperometric
titrations.
• The observed diffusion current at a suitable
applied voltage is measured as a function of the
volume of the titrant added.
• The end point is the point of intersection of two
lines giving the change of current before and after
the equivalence point.
• When solution containing Pb+2 ion is titrated
against SO4-2 ion.
• A precipitate of PbSO4 is formed.
• The titration can be performed at fixed potential
-0.8 Volt v/s saturated calomel electrode.
• As titration is proceeds concentration of Pb+2 ion
decreases and diffusion current also decreases
till it becomes minimum at equivalence point.
• The diffusion current remains constant beyond
end point.
• The values of diffusion current is plotted
against the volume of titrant added.
• The resulting titration curves is straight line
leveling off at end point .
• The intersection of two extra plotted portions
of the curves gives the end point.
Amperometric sensors
Amperometric sensors are sensitive
analytical systems that measure current as
a result of an electroactive substance losing
(oxidation) or gaining (reduction) an
electron while undergoing an
electrochemical reaction.
Amperometric biosensors
• Amperometric biosensors function by the
production of a current when a potential is
applied between two electrodes. They generally
have response times, dynamic ranges and
sensitivities similar to the potentiometric
biosensors.
Applications
• A typical application for biosensor is the
determination of glucose concentrations by the
use of an immobilised glucose oxidase
membrane.
• The reaction results in a reduction of the
oxygen concentration as it diffuses through the
biocatalytic membrane to the cathode, this
being detected by a reduction in the current
between the electrodes.
