NAME:Susmita Garai

Roll:89
Year:1st Year
Sem:1st Sem
Subject: pharmaceutical
analysis
Paper Code:
Topic: Report on Potentiometry
POTENTIOMETRY:
Introduction
Potentiometry is one of the methods of
electroanalytical chemistry. It is usually employed
to find the concentration of a solute in solution.
Definition : This is the method in which the
potential between two electrodes is measured
using a high impedance voltmeter.
Use of a high impedance voltmeter in important,
because it ensures that current flow is negligible.
Since there is no net current, there are no net
electrochemical reactions, hence the system is in
equilibrium.
Nernst equation:
The potential(E) of a metal electrode at 250C
immersed into a solution of its own ions is given
by
E= E0 + [0.0592/n] logC
Where, E0 = standard potential of the metal
n = valency of ions
C = concentration of ions
Hydrogen Electrode
• Electro chemical cell:
• Construction
The standard hydrogen electrode consists of a
platinum electrode coated with platinum black.
The electrode is dipped in an acidic solution and
pure hydrogen gas is bubbled through it.
H+ + e- →1/2H2
The concentration of both the reduced and
oxidised forms of hydrogen is maintained at unity.
This implies that the pressure of hydrogen gas is
one bar and the concentration of hydrogen ion in
the solution is one molar.
• Working principle:
Standard Hydrogen Electrode can work both as an
anode and as a cathode.
When a standard hydrogen electrode undergoes
oxidation in a cell, it acts as an anode. During this
process, hydrogen gets changed into H+
ions which go into the solution.
H2→2H++2e-
When a standard hydrogen electrode undergoes a
reduction in a cell, it acts as a cathode. During this
process, H+
ions from the solution change into hydrogen gas.
2H++2e-→H2
Thus, the electrode is reversible concerning H+
ions.
The electrode potential of the standard hydrogen
electrode is zero at 298K.

If we use a hydrogen electrode as reference to

determine the electrode potential another
electrode of half cell connected to hydrogen
electrode then unknown potential will be equal to
electromotive force of the cell.
Demerit
It can not be used for long time .
Calomel electrode
• Construction
(1) The calomel electrode consists of a glass vessel
having side arm B, for adding mercury and other
constituents and arm C, for dipping it in any
desired solution. A platinum wire A is used for an
electrical contact. Over this platinum wire are
placed pure mercury.
a paste of Hg and Hg2Cl2(mercurous chloride, i.e.,
the calomel and saturated KCl solution so as to fill
the vessel and the arm C as shown in figure.
(2) The potential developed on this electrode
epends upon the concentration of chloride ions.
(2) Representation of the calomel electrode
• Working principle:-
to provide an external electrical contact, a
platinum wire enclosed within a glass tube and
immersed in a layer of mercury is employed. The
side tube makes electrical contact with a salt
bridge. Depending on the nature of the other
electrodes in the cell, the calomel electrode can
function as an anode or a cathode.
Merit:-
The SCE has the advantage that the concentration
of Cl-, and, therefore, the potential of the
electrode, remains constant even if the KCl
solution partially evaporates.
Demerits:-
A significant disadvantage of the SCE is that the
solubility of KCl is sensitive to changes
in temperatrature
Silver-silver chloride electrode:-
significant disadvantage of the SCE is that the
solubility of KCl is sensitive to a change in
temperature. At higher temperatures the
solubility of KCl increases and the electrode's
potential decreases. For example, the potential of
the SCE is +0.2444 V at 25oC and +0.2376 V
significant disadvantage of the SCE is that the
solubility of KCl is sensitive to a change in
temperature. At higher temperatures the
solubility of KCl increases and the electrode's
potential decreases.
• Construction:-
Silver chloride is slightly soluble in strong
potassium chloride solutions, so it is sometimes
recommended that the potassium chloride be
saturated with silver chloride to avoid stripping
the silver chloride off the silver wire.(reference)

Typical laboratory electrodes use a silver wire that

is coated with a thin layer of silver chloride either
by electroplating or by dipping the wire in molten
silver chloride. Industrial electrodes are fabricated
using the same principle using other geometries
such as planar electrodes. When the electrode is
placed in a saturated potassium chloride solution
it develops a potential of 199 mV vs. SHE.
Merit: Silver is suitable for environmental
application and it is also less effected by higher
temperature so this electrode is stable.
Demerit: Ag/AgCl has a short life time due to the
small amount of it. The potential between these
electrode is very sensitive to the testing solution.

INDICATOR ELECTRODE
AN electrode which is useful for measuring
potential or pH of a solution is known as indicator
electrode. • It is used for indicating the potential
caused by some chemical species as compare to
the reference electrode. • There are two types of
Indicator electrodes: 1. Metallic indicator
electrode 2. Ion selective electrode.
➢METALLIC INDICATOR ELECTRODE:
These electrodes develop electric potential in
response to redox reaction on the metal surface.
Example: Platinum or gold are used as metal
indicator electrodes. These are mainly classified
into four types of electrodes used in the
potentiometry.
1. First kind electrode: It is a simple metal
electrode immersed in a solution containing its
 own ion.These kind of electrodes are reversible
with respect to its metal ion i.e., direct
equilibrium with solution.
2. Second kind of Electron : This type of electrode
can be used for direct determination of the
activity of the metal ion.
3. Third kind electrode: It is a metal electrode
assembly with the equilibrium potential being
a function of the concentration of a cation,
other than the cation of the electrode metal, in
the solution.
• Advantage:For the usage of stainless metal
these elctrodes are strong and have durable
welds that can withstand a lot of pressure
and stress.
• Disadvantage: The electrode response is slow
.It is very unstable electrode for not having
well denned electron.
➢ION SELCTIVE ELECTRODE :
It is also known as membrane electrodes. It is a
membrane that converts the activity of a
specific ion dissolved in a solution into an
electrode. e.g., Glass membrane is a most
common example of ISE. 1. Glass membrane
 electrode: It is a type of ion-selective electrode
made of a doped glass membrane that is
sensitive to a specific ion. The most common
application of ion-selective glass electrodes is
for the measurement of pH .
Advantages:
• It is relatively inexpensive and easy to operate
• It has wide concentration measurement range
• Is is particularly udefull in biological or
medical application.
Disadvantages:
• Precision is low.
• Only measures the activity of free ions.
• Organic solutes can foul electrodes.
➢GLASS ELECTRODE: glass electrode is a
type of ion-selective electrode made of a
doped glass membrane that is sensitive
to a specific ion. The most common
application of ion-selective glass
electrodes is for the measurement of pH.
The pH electrode is an example of a glass
electrode that is sensitive to hydrogen
 ions. Glass electrodes play an important
part in the instrumentation for chemical
analysis and physicochemical studies. The
voltage of the glass electrode, relative to
some reference value, is sensitive to
changes in the activity of a certain type
of ions.
• Advantage:
These electrodes are easy and convenient
to use for cleaning and calibrating with a
standard buffer solutions.
• Disadvantage:
These electrodes depend on various
factors like pH.By this electrode accurate
potential can not be determined.

APPLICATION OF POTENTIOMETRY:
• It is used in clinical chemistry for the
analysis of metals. It is used for the
analysis of cyanide, ammonia etc., in
water or wastewater.
• It is used in agriculture for the detection
of different elements in soils, fertilizers
 etc. It is used in detergent manufacturing,
food processing etc.
• They are useful sensors because analytes
in complex matrices are selective for ion-
selective electrodes in clinical chemistry.
• AgricultureNO3, NH4, I, Ca, K, and CN
Potentiometric titrationsTo calculate the
equivalence point, a potentiometric acid-
base titration is used. Chemical reactions
such as precipitation, acids, bases, redox
processes, complexations, and also
including the other chemical reactions
may be titrated in both aqueous and non-
aqueous solvents.
• Potentiometric titrationsTo calculate the
equivalence point, a potentiometric acid-
base titration is used. Chemical reactions
such as precipitation, acids, bases, redox
processes, complexations, and also
including the other chemical reactions
may be titrated in both aqueous and non-
aqueous solvents.
Principle of the Potentiometric Titrations:
When the pair of electrodes are placed in the
sample solution or analyte, it shows the potential
difference between two electrodes by theaddition
of the titrant or by the change in the
concentration of ions.
Apparatus for Potentiometry titration:
(1) pH meter; (2) reference electrode; (3)
indicator electrode (chalcopyrite or galena
electrode); (4) magnetic stirrer; (5) burette.
Requirements: potentiometric titrations, a cell is
used with a reference electrode, salt bridge,
analyte and an indicator electrode. Generally,
the electrolyte solution is used as an analyte.
Hydrogen electrodes, silver chloride electrodes
and calomel electrodes are generally used as
reference electrodes.
Method of detecting End point:
Potentiometric measurement: The potential
changes abruptly at the endpoint due to the
formation of a complex or the neutralization of
an acid or base.
Conductivity measurement: The conductivity of
the solution changes abruptly at the endpoint
due to the formation of ions.
The pH measurement: the pH of the solution
changes abruptly at the endpoint. Therefore,
measuring the pH of the solution with a pH
meter can be an effective way to determine the
endpoint.
Visual observation: The simplest way to
determine the endpoint is by visually observing
the solution.
Advantage:
• Require less amount of time for completion
of process.
• This does not require any indicator
• End result of the reaction is easily visible.