T.Y.B.Sc. 1.3 Amperometric TitrationsPPT

Satish Pradhan Dnyanasadhana College, Thane.
Department of Chemistry
T.Y.B.Sc. Analytical Chemistry
Paper-IV Sem-VI
Amperometric Titrations
By
Dr.Bhagure G.R.
1
Contents
1.3 Amperometric titrations (04L)
1.3.1 Comparison between Amperometry and
voltammetry.
1.3.2 Basic principle of amperometry
1.3.3 Rotating platinum electrode: Instrumentation,
advantages and limitations.
1.3.4 Amperometric titrations: Examples and titration
curves.
1.3.5 Applications, advantages and limitations
2
Rotating Platinum electrode
Flange inward to inward to prevent
Glass tubing mercuring from being thrown out
Copper Wire
Mercury
reservoir
Hole Stem to make electrical

contact mercury reservoir
Platinum Wire
Direction of rotation
3
Diffusion current is directly proportional to
concentration
4
Diffusion
Current
uA
20 40 60 80 100 Concentration
5
Principle of Amperometric titrations
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. Some advantages
of amperometric titrations may be mentioned:
6
Principle of Amperometric titrations
Titrand Titrant Product
Out of these three one is reducible

7
Titrand is reducible but Titrant and
product not .
Titrand Titrant
Pb+2 SO4-2 Product
The titration can be performed at fixed

potential -0.8 Volt v/s saturated calomel
8
1. Titrand is reducible but titrant and
product not:
• 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.
9
A) Ttrand is reducible but titrant and product not.
Ex.Pb+2 v/s SO4-2 at constant

potential -0.18 V (SCE)
Diffusion current
Equivalence point
Volume of Titrant added
10
Titrant is reducible but Titrand and
product not .
Titrant
Titrand
Mg+2
8- hydroxy Product
quinoline .
The titration can be performed At

constant potential of -1.6 volt. v/s saturated
calomel 11
2. Titrant is reducible but titrand and
product not :
• When solution containing Mg+2 ion is titrated
against with the reducible species such as 8-
hydroxy quinoline . At constant potential of -1.6
volt. In this titration the current is steady till the
end point because Mg+2 ion does not undergoes
reduction. Beyond the end point the 8- hydroxy
quinoline undergoes reduction. As its concentration
increases diffusion current also increases.
12
B) Titrant is reducible but titrand and product not
Ex.Mg+2 v/s 8-Hydroxy quinoline
-1.6 V(SCE)
Diffusion current
Equivalence point
13
Titrand and titrant both are reducible but
product not
Titrand Titrant
Pb+2 K2Cr2O7.
Product
The titration is performed at potential of

-0.8 Volt v/s SCE
14
3. Titrand and titrant both are reducible but product not :
• When solution containing Pb+2 ion is

titrated against K2Cr2O7. The titration is
performed at potential of -0.8 Volt v/s SCE .
Diffusion current is decreases due to
removal of Pb+2 ion. The current is
minimum at the end point. On further
addition of the titrant the current once
again increases. V shaped curve is obtained.
15
C) Ttrand and titrant both are reducible but product not Ex.Pb+2 v/s K2Cr207 at constant
potential -0.8 V (SCE)
Diffusion current
Equivalence point
16
Advantages of Amperometric Titration
• Method is accurate and equivalence point is obtained
1 by means of graph
• The electrode surface is continuously renewed ,current

2 values are reproducible.
• Amperometric titrations can be carried out at

dilutions at which Potentiometry, or ordinary
3 titrations method can not work
• Readings near the end points are not of importance in
this method , so precipitations titrations can be
4 carried out.
17
Disadvantages of Amperometric Titration
• Considerable time is required to remove dissolved
oxygen before and during the titration
1
• The titrations can be carried out at potentials more

negative than 2 volts since hydrogen will be evolved.
2
• Co precipitations can give inaccurate

3 results.
18
Thank you
19

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Satish Pradhan Dnyanasadhana College, Thane.

Hole Stem to make electrical

Titrand Titrant Product

Out of these three one is reducible

The titration can be performed at fixed

Ex.Pb+2 v/s SO4-2 at constant

Volume of Titrant added

The titration can be performed At

Volume of Titrant added

The titration is performed at potential of

• When solution containing Pb+2 ion is

Volume of Titrant added

• The electrode surface is continuously renewed ,current

• Amperometric titrations can be carried out at

• The titrations can be carried out at potentials more

• Co precipitations can give inaccurate

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