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Polarography
Polarography is a subclass of
voltammetry where the working
electrode is a dropping mercury
electrode (DME).
It is current versus potential are recorded
when gradual changing current is take
place when current applied to cell.
A cell containing :
 Solution of interest (electroactive
substance)
 Stable reference electrode. e.g : calomel
electrode.
 Small area of indicator electrode (DME)
 Auxiliary or counter electrode .
Mercury
pool
 Hg will dropped in stable flow rate 5- 30
drops/min.
 Volts applied 50 – 200 mv/min
 Drop life 2 – 12 sec.
 Potential range (+ 0.4) – (-2) V
Advantage of Hg electrode
 As the Hg capillary very narrow so, able to
analyse very small volume of analyte.
 Surface of electrode is very reproducible .
 Surface area of electrode can be calculated
from the weight of drops.
Disadvantage
 Limited potential (+0.4) – (-2) V.
 Capillary is very small so easily to
bloked .
Qualitative polarogram
Polarographic spectrum
Limiting
current
Diffusio
n
current
residual
current
Quantitative polarogram
Factors affecting diffusion
current
(Ilkovic equation)
ίd = 708 n C D½ m ⅔ t⅙
 n : change in valency
 C : concentration
 D : diffusion coefficient.
 m: flow rate of mercury dropping.
 t : life time of mercury drop.

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Polarography