Potentiometry

By: Arif Sultan

 Contents

 Principle
 Instrumentation
 Potentiometer
 Electrodes
 Salt bridge
 Electrode potential
 Sample solution preparation
 Working
 Cell potential calculation
 Limitations
 Applications
 Refrences
Potentiometry

Principle:
The principle involved in the potentiometry is
when the pair of electrodes is placed in the
sample solution It shows the potential
difference by the addition of titrant or by the
change in the concentration of the ions using
the high impedance voltmeter.
 Instrumentation
Potentiometer is an instrument used to determine potential
difference between a reference electrode and an indicator
electrode. These electrodes form electrochemical cells that are
dipped in solution to be analyzed.

Potentiometer has following parts

•Base electrode or reference electrode with known
potential constant over time and independent of
composition of the solution containing the analyte in
which it is immersed
•Indicator or working electrode (whose response
depends upon the concentration of the analyte
•Voltmeter
•Galvanometer
•Analytical solution
•Salt bridge ( U-shaped tube filled with an electrolyte)
Electrodes
Reference electrode
1. Standard Hydrogen Electrode
2. Calomel electrode
3. Silver-silver chloride electrode
Indicator electrode
1. Metal Electrode
2. Hydrogen electrode
3. Quinhydrone electrode
4. Glass membrane electrode
 Salt Bridge

U-shaped tube filled with an electrolyte

•Glass tube bridge (gel + KI or Na2SO4 )
•Filter tube bridge (filter paper + KCl or NaCl)
Function:
•Allow electrical contact between two solutions.
•Prevent mixing of two solutions.
•Maintain electrical neutrality.
Theory:
The main theory involved in the potentiometry is, when
the known potential electrode immersed in the sample
solution, then the potential is given by Nernst Equation:

E=Eo+ (0.592\n) log c

E = Potential of the solution
Eo = standard electrode potential
n = valency of the ions
c = concentration of the sample soln.
0.592 = the value obtained from the RT\F
R = gas constant
T = temperature in Kelvin
F = Faraday’s constant
Working:
Potentiometer consists of two electrodes, whose
reduction potential differ, inserted in a sample solution. The
voltmeter is attached to measure the potential difference
between them. Ions are present in two different oxidation
states. Oxidation takes place at anode.e.g. anode is made
up of zinc metal, it looses two electrons and converts into
cation. Reduction takes place at cathode made up of
copper metal, it gains two electrons and converts into
copper metal. When redox reaction takes place than
potential is develop which is measured by galvanometer.
The electrode potential of the complete cell is given by
the following equation:

Ecell=Eindicator-Erefrence+Ejunction
 Sample Solution Preparation
Sample solution should be in the range of 0.5 to 1.0 mM to minimize
measurement errors. It is possible to wok at lower concentrations without
compromising too much the accuracy of the results but not lower than o.2mM
in any case.
To measure cell potential two half cells required and an analyte solution e.g.
AgCl. To measure cell potential sample solution is titrated against standard
NaOH solution. Glass electrode is used to calculate pH of the solution. KCl
bridge minimize high concentration of salt with nearly equal mobilities of
cation and anion.
Reagents and Apparatus: NaOH, Kcl (primary standard),250ml beaker,
stirring rod, pH meter, glass electrode etc.
Procedure:
Metals selected for both the electrode should be compared with the value
of standard hydrogen electrode.
Take unknown sample into a 400ml beaker and add 100ml distilled water.
Titrate analyte solution with standard NaoH solution. Add small
increments of titrant and record pH for corresponding volume of titrant.
Potentiometric method
Cell potential calculation:

The first step is to determine the cell reaction to calculate cell potential. In order
For the cell to be galvanic, Eo cell must be greater than 0.
For cadmium metal, the oxidation reaction:
Cd Cd2+ + 2e Eo = +0.403V

Pb2+ + 2e Pb Eo = -0.126

by putting the values in Nernst equation, we get

Ecell = 0.277V – 0.013V x -2.303
Ecell = 0.277V + 0.023V
Ecell = 0.300 V

The cell potential for two reaction at 25 degree celcius , [Cd2+ ] = 0.020M
and [Pb2+ ] = 0.200M and cell potential is 0.300 V.
 Applications of Potentiometry

Analysis of Pollutants in water

Drug analysis in Pharmaceutical industry
Food industry for analysis of quality
Biochemical and biological Assay or analysis
To check the quality or cosmetics
Analytical tool in Texitle, paper, paints, explosive energy and more.
Agriculture :(Cl,K,Ca,I,CN in soils, plant material, fertilizers and foodstuffs.)
Detergent manufacture:Ca,Ba,F for studying effects on water quality
Food Processing:
Salt content of meat,fish,dairy products, fruit juices, brewing solutions.
Ca in dairy products and beer.
K in fruit juices and wine making.
 Limitations

•Difficult and expensive to maintain.

•Can’t be used in solution containing strong oxidizing agents.
•Mostly saturated solution of KCl is used that is temperature dependent.
•Silver electrode sometimes show reactivity.
•Metallic indicator electrodes are not very selective and respond not
only to their own cations but also more easily to reduced cations.
•Many metal electrodes can be used only in neutral or basic solutions
because they dissolve in the presence of acids.
 References

1. Analytical chemistry instrumental technique

By Mahinder Singh
2. Pharmaceutical Drug analysis
By Ashotoushkard
3. Fundamentals of analytical chemistry
By Skooj