Amperometric titration

Presented by
Anas Jadoon Maida Zahid
Akbar khan Ramaza Bibi
Khadija-Tul-Kubra
 Introduction

 Amperometry refers to the measurement of current under a constant applied

voltage and under these conditions it is the concentration of analyte which
determine the magnitude of current.
 In Amperometric titrations, the potential applied between the indicator
electrode (dropping mercury electrode) and the appropriate depolarizing
reference electrode (saturated calomel electrode) is kept constant and current
through the electrolytic cell is then measured on the addition of each increment
of titrating solution. It is a form of quantitative analysis.
 Principle
 According to Ilkovic equation
Id = Constant nCm2/3 t1/6 D1/2
 Where,
Id= diffusion current due to electroreducible ions
C=conc. Expressed in mol/litre.
n= no of electrons involved in reduction of one molecule.
D=diffusion coefficient of ions (cm^2/sec).
m= weight of mercury flowing through capillary.(mg/sec)
t= drop time in seconds.
 Conditions for performing Amperometric Titration

 The potential applied should correspond to the limiting current

 Either the titrate or titrant or both should be electro reducible .

 Titration apparatus

 It consists of a titration cell a micro burette, an indicator electrode and a

reference electrode.
 The titration cell is a Pyrex 100 ml H shaped cell , fitted with a micro burette ,
graduated in 0.01 ml a dropping electrode and one inlet for passing nitrogen and
one for its exit .
 The indicator electrode may be a dropping mercury electrode or a rotating metal
microelectrode or a stationary electrode with a magnetic stirrer .
 The reference electrode is a saturated electrode, fitted in the right arm of the cell
 Titration apparatus
 A complete assembly for Amperometric titration is shown in this picture
 procedure
 Amperometric titrations are usually carried out as follows :
 Assemble the apparatus as shown in picture
 Connect the dropping mercury electrode as cathode and saturated calomel
electrode as anode.
 Place a known volume of the solution in the titrating cell, bubble the Nitrogen gas
through the solution for about 10-15 minutes . Fill up the micro or semi micro
burette with the reagent solution of known concentration .
 Adjust the voltage at the desired value and note the initial diffusion current . Add
a known volume of the reagent , bubble the nitrogen gas for about 2 minutes to
eliminate the traces of oxygen from the reagent. Note the burette reading and
corresponding current reading .
 procedure
 Repeat the process until sufficient readings have been obtained .
 Correction in the observed current due to change in volume of the solution
during the titration in necessary , especially when the concentration of the
reagent is not very high relative to the concentration of the solution .
 The correction is applied using the formula
i (corr) = i(obs) (V+v)/V
 where ' is the initial volume of the test solution and v is the volume of titrating
reagent added . The corrected current is plotted as ordinates against the volume
of the reagent added as abscissae and a straight line is drawn through the two
branches of the curve . The point of intersection is the end point .
 Advantages of Amperometric titration
 Rapid, simple apparatus
 Dilute solution can be analysed.
 The reaction carried out can be reversible or irreversible.
 Can be carried out at dilution (10-4M) at which many visual or potentiometric
titrations no longer yield accurate results.
 The method is relative therefore, fewer distributing factors are prevalent.
 These titration can be carried out rapidly because the end point is found
graphically.
 disadvantages of Amperometric titration
 Due to the effect of co - precipitation and post - precipitation the Amperometric
titrations sometimes give inaccurate results

 Due to the presence of foreign substances , the relative change of current

during the titration is very little in Amperometric titrations
 Applications of Amperometric titrations
 Wider range of applications than polarography because even electro-inactive
substances can be determined using electro active titrant.

 Determination of water using karl fischer reagent{ bioampereometry}.

 Quantification of ions or mixture of ions.

 Amperometric titration are quantitative in nature they are used to determine the
end point of such titration.