MODULE 3

CORROSION AND ELECTRODE SYSTEM

ELECTRODE SYSTEM

with the inter conversion of

Electrochemistry is a branch of science, which deals
energy and electrical energy that takes place through oxidation reduction
chemical
electrochemical cells. In oxidation, a species
reactions. Redox reactions form the basis of
increase in the oxidation number.
loses one or more electrons resulting in an

M M* +ne oxidation

resulting in a decrease in oxidation

In reduction, the species gains one or more electrons
number.

Mt +ne M --- reduction

Electrochemical cell: The basic device used for electrical measurements due to chemical

reactions taking place in solutions is called an electrochemical cell for it is a device which
converts chemical energy into electrical energy or electrical energy into chemical energy].

There are two types of electrochemical cells. Namely,

1. Galvanic cell or Voltaic cell

2. Electrolytic cell
Galvanic cell or Voltaic cell: An electrochemical cell that produces electricity as a result
of the spontaneous chemicalreaction occurring inside it is called a galvanic cellor voltaic
cell. [It is a device used to transform chemical energy of a spontaneous reaction into
electrical energy.]

In a galvanic cell, the electrode at which oxidation occurs is called a negative

electrode or anode, while the electrode at which reduction occurs is called a positive
electrode or cathode.

Elcctrolytic cell: An electrochemical cell in which a non - spontaneous chemical

reaction is driven by an external source of electrical energy is called an electrolytic cell.
 Electrode: An electrode consists of an element (metal or non metal) in contact with a
solution containing its own ions and is regarded as a half cell. During the operation of a
cell, oxidation occurs at one electrode and reduction at the other. A potential called the

electrode potential arises at the electrode in contact with its ionic solution. The difference
between the potentials of the two half-cells constitutes the electromotiveforce (emf) or the
cell potential.

Single electrode potential (E): The potential that is developed due to the tendency of an
element (metal or non-metal) to lose or gain electrons when it is in contact with the solution
containing its own ions is called single electrode potential or half-cell potential (E).
Standard electrode potential (E"): The potential that is developed when an element
(metal/non metal) is in equilibriumn with a solution containing its own ions of unit
concentration (1M) at 298 K is called standard electrode potential.

If the electrode system involves gaseous substances, they must be passed at a partial
pressure of 1atmosphere.
EMF of a cell (Ecel): The energy supplied or work done by a cell to drive unit electric
charge around a cell is called electromotive force of a cell. [or the
potential difference
between the two electrodes of a cell which causes the flow of current from one
electrode to
the other is called emf of a cell]. It is also called as cell
potential or cell voltage. It is
expressed in volts. Mathematically,
Ecel) = Ecathode - Eanode Or Eçell= Eright
electrode - Elet electrode

Types of electrodes
In electrochemical work, the cells used involve various types of
depending upon the purpose for which they are used.
electrodes
Some of the important types may be
grouped into the following types.
 i)Metal metal ion electrode:
contact
The electrodes of this kind consists of an element (metal or non metal) in
with a solution of itsown ions. The electrodes of this type are reversible with respect to ions
of the electrode material.

e.g., Zn in ZnSO, solution, Cu in CuSO, solution.

ii) Metal- metal insoluble salt electrode:

The electrodes of this kind consists of ametal and a sparingly soluble salt of a metal
in contact with a solution of a soluble salt of the same anion.

e.g., Calomel electrode [Hg(l)]Hg,Ch(s), KCl solution]

Silver- silver chloride electrode [Ag(s))AgCl(s), KCl solution]
The electrodes of this type are reversible with respect to a common anion i.e., the
chloride ion in the above electrodes.

Electrodes of second kind are of great value in electrochemistry, because they permit
the ready establishment of the electrode reversible with
respect to anions.
ii) Gas electrode:

Gas electrodes consist of a gas bubbling about an

inert metal foil or wire, immersed
in a solution containing ions to which the gas
is reversible. The metal provides
contact and facilitates the establishment of electrical
equilibrium between the gas and its ions.
e.g., Hydrogen electrode (PtH,/H)
Chlorine electrode (Pt/Cl,/CI)
iv) Amalgam electrode:

Amalgam electrode is similar to metal-metal ion

an amalgam electrode, electrode except for the fact that in
meal-amalgam is in contact with a solution containing its own
10ns. metal
e.g., Lead-amalgam electrode (Pb-Hg/Pb"), Sodium amalgam
electrode (Na-Hg/Na")
 v) Redox cloetrode:

A redox olectrode (oxidation0reduction clcctrodo) is the one in which the electrode

potential arises fhom the presence of oxidised and reduced forms of the same species in
solution. The potential arises fiom the tendency of one form to change into the other more
stable fornm. The potentialdeveloped is picked up by and inert electrode like platinum.

c.g, Pt/ Fe", Fe", P/ Sn,Snt

vi) lon sclective electrode (menmbrane electrode):

The electrodes that are able to respond to certain specific ions only and develop a
potential while ignoring the other ions in a solution are called ion selective electrodes. The
potential developed at the electrode is a function of the concentration of that ion in solution.
e.g., Glass electrode (exchanges Hions with the solution)
vii) Reference electrodes: The electrodes of standard potential (i.e., constant and
reproducible potential) with which the potentials of the other electrodes can be computed
are known as reference electrodes.

There are two types of reference electrodes, namely,

Primary reference electrodes - Standard Hydrogen Electrode (SHE)

Secondary referenceelectrodes - Calomel electrode, Silver-silver chloride electrode

Construction and working of Calomel clectrode: Calomel electrode is a secondary

reference electrode. It is constructed as follows.

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> Salt bidye
 Calomel electrode consists ofa long glass tube having two side tubes as depicted in
figure. Highly pure mercury is placed at the bottom of the tube and is covered by a
paste of
pure mercury, calomel (Hg,CI,) and potassium chloride solution. The electrical
connection
is made by means of a platinum wire sealed into
another small glass tube having litle
mercury at its bottom. The rest of the tube is filled with an appropriate
concentration of KCI
solution. The electrode is connected to other electrode to make the cell
complete by means
of a salt bridge.

Calomel electrode is represented as, Hg()Hg,Cl,(s), KCl solution

Calomel electrode can act as anode or cathode depending on the
nature of the other
electrode of the cel1. When calomel electrode acts as anode., the
electrode reaction is,
2 Hg(l) ’ 2Hg (ag) + 2 e
2 Hg (ag) + 2CT
Hg,Cl,(s)
2 Hg(l) + 2CT’
Hg,Cl,(s)+ 2e
When the calomel electrode acts as
cathode, the electrode reaction is,
Hg,Clh(s) ’ 2Hg(aq) + 2 CI (aq)
2 Hg (ag) + 2e 2 Hgl)
Hg,Clh(s) +2e ’2 Hg(l) +2 CT(a)
The electrode potential of calomel
electrode depends on the concentration of
KCl solution with which the tube is
filled.
chloride ion or
E = E-0.0591 log[CI]

Applications of calomel electrode:

1. Calomel electrode is used as a
secondary reference electrode to determine the
electrode potentials of the other electrodes.
2. It is the most
commonly used reference electrode in all
determinations. potentiometric
3. It is used in
corrosion studies.
 Lon selective electrodes:

The electrodes that are able to respond to certain specific

ions only and develop a
potential while ignoring the other ions in a solution are called ion selective
electrodes. The
potential developed at the electrode is a function of the concentration of that ion in
solution.
e.g., Glass electrode

Glass electrode: Glass electrode is an ion selective electrode which

responds to
hydrogen ions in a solution while ignoring the other ions. One of the most
advances in
recent years in connection with the determination of pH is the use
ofglass electrode.

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Tin wallbd gas bullb

ty-Agcl eleetate
The glass electrode consists of a long
glass tube having a small bulb at its bottom.
The bulb is made up of a special type of thin
walled glass of relatively low melting point
and high electrical conductivity. The
composition of glass is 22% Na,O, 6% CaO and 72%
SiO,. The bulb contains 0.1 M
hydrochloric acid. An Ag - AgCl electrode (internal
reference electrode) is placed in the solution and connected bya
platinum wire for electrical
contact. The glass electrode is represented as,

Ag (s) |AgCl (s) |0.IM HCI|glass

 When the glass electrode is dipped in the test solution, the Na" ions of the
glass membrane
are exchanged for H ions of the test solution.

Na G + H Na +HG
Glass electrode works satisfactorily in the pH range of 1to 9.
Applications of glass electrode:
1. Simple to operate glass electrode and therefore extensively used in
chemical,
industrial, agricultural and biological laboratories.
2. It is commonly used for pH
measurements.
3. It is used in pure research, control of industrial
processes, analysis of foods and
cosmetics.
4. It is used in the measurement of environmental indicators.
5. It is used in microelectrode measurements such as cell
membrane electrical potential
and soil acidity.

Determination of pH of a solution using glass electrode:

Principle: When a thin glass membrane is placed between two solutions of different pH
values, a potential difference exists across the membrane. The potential difference
varies as
the pH of the two solutions varies. In actual practice, the pH of one of
these solutions is
made to remain constant. Therefore, the electrode potential depends on the pH of the
other
solution.
VTP ’ Vauun Tube
VTP
Poteutiocty

aloel eechde

Exprimeutal
 The bulb of the glass electrode is placed in the experimental solution, i.., the
solution whose pH is to be determined. The glass electrode is coupled to a reference
electrode, say, calomelelectrode and emf of the resulting cell is determined using special
vacuum tube potentiometer.

Cell representation: Calomel electrode| Solution of unknown pH| Glass electrode

We have, Ecell = Ecathode- Eanode

Ecell = EG - EscE --- (1)

The potential of the glass electrode is given by,

EG = Eh t EAgiAgCI t Easy

= RT [lnC,- InCi] + EAg|AgCI + Easy

nF

C=concentration of Hion inside the glass

bulb, is a constant.
Therefore, -RT InC; =L, a constant
nF

.:. Eg = RT InC, +L+

EAgAgCi t Easy
nF

Eg = 0.0591 log [H]+ L+

EAg|AgCi + Easy
1

0.0591 pH + L+ EAgAgCI t Easy { pH=-log[H]}

EG = LË - 0.0591 pH

Where L=L+EAgIAeCI + Easy iS a

constant.
:. From equation (1), Ecell
LË 0.059l pH-EscE
. pH =
L-EscE-Egell
0.0591
The value of the
constant can be determined by
with a series of buffer
solutions. calculating the electrode potential
 Concentration cells: The galvaniccells consisting of both anode andcathode made up of
the same element (metalor non metal) in contact with the solutions of the same electrolyte
of different concentrations are referred to as concentration cells.

In a concentration cel, the electrode at which the metal ion concentration is low
compared to the other would become an anode while the other electrode at which the metal
ion concentration is high would act as cathode. The electrode potential depends on the
concentrations afeterent. od the 1Ons.
The concentration cell consisting of the electrodes of the same metal 'M dipped in
solutions of their own ions of concentrations C, and C, is represented as,

M(9) | M"(C)| M"C) |M(9) where C>C;

e.g., A concentration cell consisting of two copper electrodes dipped in
CuSO4 solutions of
different concentrations such as 0.1M and 1.0M is represented as,

Cu(s) | CuSO,(0.1M) | CuSO,(1.0M) |Cu (s)

Construction:

Anoda athode
A copper
concentration cell is formed when two copper rods in contact
and 1.0M copper sulphate with 0.1M
solutions respectively are connected externally by a
material, i.e., a metallic wire and internally by conducting
means of a salt bridge and thereby
an electric current. At
anode, copper metal passes into produce
release of electrons. At the cathode, the solution cupric ions with the
as
metal ions (Cu) present in the
deposited on the metal surface. These ions gain the solution get
and conducted to the electrons that are released at the anode
cathode through the external circuit and get
reduced to copper atoms.
 Half-cell reactions:

At anode: Cu(s) ’ Cu"(0.IM) + 2e

Atcathode: Cu(1.0M) + 2 e ’ Cu(s)

Net cell reaction:Cu"(1.0M) ’ Cu(0.IM)

EMF of a concentration cell:

The emf of aconcentration cell, M(9) |M"C) | M(C,) |M(S) is given by,
Ecell Ecathode -Eanode
-[E cathode t+ 0.0591 log C]-[Enode t 0.0591 log Ci]

Since the electrodes are made up of the same material, E cathode Fo

anode

.. Ecell =E cathode E"anode 0

.. Eell = [Ecathode -Ear

anodel +0.0591[logC, - logCi]
n

=0 +0.0591 logC,
n

Ecell = 0.0591 logC,

n

When, C2 >C, Ecell is positive.

C< Ci, Eoll iS negative.
Ch= C), Ecell 0S Zero.
 CORROSION CHEMISTRY
"The gradual destruction or deterioration of a metal or its alloy caused by direct
chenmical
action or electrochemical reaction with its environment is called metallic corrosion".
There are two types of corrosion. Namely,
1. Dry corrosion It takes place due to attack of dry acidic gases
like SO2, H,S, NO2, etc.
2. Wet corrosion - It is also known as
electrochemical corrosion. It takes place in the
presence of moisture or electrolyte at the surface.

Electrochemical theory of corrosion:

Air

Water film
or moisture
(neutral)
Anodic area
Fe -->Fe +2e Cathodic area
O; +2H0 + 4e --> 40H
Iron rod

Rusting of iron

According to electrochemical theory, corrosion of

metals takes place due to the
formation of a large number of minute galvanic cells on
the surface of the metal. These
cells arise due to the presence of
heterogeneities at the interface of the metal and corrosion
environment. The heterogeneities on the metal surface could
arise in several ways, such as
difference in concentration of air or oxygen on
metal surface. The part of the
contact with more air or Oxygen metal in
becomes cathode while the other part in
Oxygen concentration becomes an anode. contact with low
Thus two unlike parts exist on the
metal surface.
An aqueous solution
(derived from moisture) constitutes an
electrolyte.
At the anodic site, metal
undergoes oxidation releasing electrons.
M ’ M + ne
 e.g., Fe ’ Fe + 2e

At the cathodic site, the following reduction

reactions take place.
a) Liberation of hydrogen: It takes place in the absence of oxygen.
() In acidic medium, the H ions of the medium take up electrons and get
reduced to
hydrogen gas.
2 H(ag) + 2e ’ H(g)

(ii) In neutral or alkaline medium,

2 H,0(1) ’ 2H(ag) + 2 OH (aq)

2 H(aq) + 2e ’ H(g)
2H,0(|) + 2e ’ H(g) +2 OH (ag)
b) Absorption of oxygen: It takes place in the presence of oxygen.
(i)) In acidic medium,

O,(g) + 4 H(aq) + 4e ’ 2H,O()

(ii) In neutral or alkaline medium,

O(g) + 2H,0(1) + 4 e ’ 4 OH (ag)

The cell reaction is, M + n/2 O(g) + n H0 () ’
M"(a) + 2n OH(ag)
2 Fe+ O(g) +2 H0 () ’ 2
Fe"(aq) + 4 OH (aq)
The metal ions so formed at the anode
combine with hydroxyl ions to form the
corresponding metal hydroxide, a corrosion product. In an oxidizing
oxidized to metal oxide. environment, it is

M"(aq) +t n OH (aq) ’ M(OH),

Fe"(aq) + 2 OH (a) ’ Fe(0H)
2 Fe(OH), +O, + (n-2) H,0 ’
Fe,O,.nH,0
Rust
 In the presence of limited oxygen, ferrous hydroxide is converted in to magnetic
oxide. It is known as black rust.

3 Fe(OH), +½0, Fe,O4.3H,0

Black rust

Types of corrosion:

1. Differential metal corrosion or Galvanic corrosion:

Differential metal corrosion occurs when two dissimilar metals or galvanic couples
are in contact with each other in a corrosive conducting medium, i.e., in contact with an
electrolytic solution. The potential difference between the two metals is the cause or driving
force for corrosion. The rate of differential metal corrosion depends on the difference in
electrode potentials. Higher the difference, faster is the rate of corrosion. The more active
metal, i.e., having low standard reduction potential value, becomes anodic while the less
active metal having high standard reduction potential value becomes cathodic. Anodic
metal gets corroded and cathodic metal remains unaffected, i.e., electrons flow from anode
to cathode and come in contact with oxygen forming OH at cathode. The metal ion formed
combines with OH ions giving corrosion product.
Consider a galvanic cell consisting of iron and copper in contact with an aerated
solution of sodium chloride as shown in the figure.

Nacl
4>Aesat siuhn f
Cosscion pouduc
 A current flows between the two electrodes spontancously and electrons flow from iron to
copper indicating that iron is anode and copper is the cathode. Hence iron corrodes in
preference to copper. The reactions taking place are,
Fe -’ Fe +2e Anode

O:(g) + 2 H,0(1) +4e ’ 4OH (aq) Cathode

Fe*+2 OH ’ Fe(OH); 2Fe(OH), + O, +(n-2) H,0 ’ Fe,O3.nlH,0

2. Differential aeration corrosion:

Differential aeration corrosion occurs when a metal surface is exposed to differential

air or oxygen concentrations. The galvanic cell formation takes place due to
the difference
in the oxygen concentration on the metal surface. The
part of the metal exposed to higher
Oxygen concentration acts as cathodic region, while the other
part of the metal exposed to
lower concentration of oxygen acts as anodic region.
Consequently, the anodic region
undergoes corrosion and the cathodic region remains unaffected,
e.g., A metal rod half immersed in NaCl solution.

Iron rod Fe ’ Fe +2e

Cathodic region + O(g) + 2 H,0() + 4 e ’ 4 OH(aq)
Anodic region Fe +2OH ’ Fe(OH))
NaCl solution
Fe(OH)) +O, +n H,0

The part of the metal which is

Fe,0j.nH,O
inside the
exposed part. Therefore, the part of the metal solution less aerated compared to the
is
inside the solution becomes anodic and
exposed part becomes cathodic. The metal at the
the anodic region gets
corrosion product formed settles at the bottom. corroded and the
The pitting corrosion and water line
phenomenon of differential aeration. corrosion can be explained using the
 Waterline corrosion: Waterline corrosion is a case of differential aeration corrosion,
which is commonly observed when a portion of the metal is under water for a long time.
This type of corrosion takes place due to the formation of differential oxygen concentration
cells. The part of the metal below waterline is less aerated, and becomes anodic, while the
area above waterline is more oxygenated and acts as cathode. Therefore, intense corrosion
takes place just beneath the level of water as shown in the figure.

Cathodic region 0,t 2H,0t te 404

Anodic region FeFe

’ Steel tank 204’toH),.
’ Water

This type of corrosion is observed in steel tanks used to store water for a long time and
ships floating in sea water for a long time.

At anodic region: Fe ’ Fe +2 e
Atcathodic region: Og) + 2 H,0() + 4e ’ 40H (aq)

Fe + 20H ’ Fe(OH))

Fe(OH), +O, +n H,0 ’Fe,0,.nH,0(Rust)

CORROSION CONTROL

Some of the important methods commonly used in controlling corrosion of metals

are as follows.

IAnodizing: Anodizing is the process of forming a surface oxide film byelectrochemical

Oxidation of the metal.

e.g., Al,03 on Al, Cr,03 on Cr, MgO on Mg.

The oxide coating on the base metal prevents the metal exposure to environment and
corrosion is prevented.
 Anodizing of aluminium: Aluminium i.. the article to be anodized is subjected to
cleaning (pre-treatment) prior to anodizing. The pre-treatment includes degreasing followed
by electro polishing. Aluminium is connected to the positive terminal of an external source,
i.e., made as anode and steel or copper is made as cathode. The electrolyte consists of
5-10% chromic acid. The temperature of the electrolytic bath is maintained at 35°C. The
voltage is programmed to increase from zero to 50V (optimum 40V) so as to maintain an
anode current density of 10 - 20 mAcm2.
The electrode reactions occurring during anodizing process are,
At anode: 2 Al + 3 H,0 Al,O, + 6 H + 6e

Atcathode: 6H + 6 e ’ 3 H,

Overall reaction: 2 Al + 3 H,0 ’ Al,O, + 3H

The oxide coating is slightly porous. The pores are covered by
dipping the anodized
aluminium boiling water. Al0; gets hydrated to Al,O,.H,0, which occupies
in
more
volume and hence covers up pores.

Applications:

Sulphuric acid anodized film is used for automotive, weather-strip,

architectural
building panels, transformer windings, etc.
Chromic acid anodized film finds application in high
corrosion resistance, aircraft
assemblies, flow detection in metal casting or forgings.

II Corrosion control by cathodic

protection:
Cathodic protection is a method of protecting a metal or
alloy from corrosion by
converting it completely into cathodic and no part of it is
allowed to act as anode. The
primary cause for corrosion of a metal is the flow of
electrons from anodic region to
cathodic region. Consequently, anodic region undergoes
would remain unaffected. Therefore, corrosion can be
corrosion whereas cathodic region
sites and converting the entire metal cathodic.
prevented by eliminating the anodic

Cathodic protection can be achieved by two ways.

 1) By connecting the metal to the
negative terminal to a d.c. source Impressed voltage
method.

11) By connecting the metal to another metal which is

anodic Sacrificial anode method.
Sacrificial anode method:
In sacrificial anode method, the metal structure to be
protected is converted into
cathodic by connecting it to more active metal like zinc, magnesium or
aluminium. The
pieces of more active metal or its alloy are buried in the ground
near the metal structure to
be protected, with the help of a wire. The metal
structure, instead of losing its own
electrons directly to the corrosion process, merely relays electrons from the more
active
metal through the wire. The more active metal corrodes away to
give protection for the
metal structure. Since the protection is given at the cost of the life of
an active metal, the
method is referred to as sacrificial anode method. The active metal is
known as sacrificial
anode. The exhausted anodes are replaced by fresh ones from
time to time.

>Achve matal
(Zn|g)
Meral strutue tobe
This method is used to protect buried pipe lines, ship hulls and
industrial water tanks.
II Corrosion control by Metal coatings:

Corrosion of metals can be controlled by isolating them from the

corrosion
environment. This can be brought about by covering the metal (substrate or base metal)
with a layer of another meal. This process is referred to as metal
coating. There are two
types of metal coatings, namely, anodic metal coating and cathodic metal coating.
Anodic metal coating The metals used for anodic metal coating are anodic in
nature and
lie above the metal to be protected in the electrochemical series. For
example, iron iscoated
with anodic metals such as, zinc, magnesium and aluminium. One of
the important
characteristic features of anodic coating is that, even if the coating is ruptured, the base
 metaldoes not undergocorrosion. The exposed surface of the metal is cathodicwith respect
to the coating metal and hence the coating metal preferentially undergoes corrosion.
Galvanizing: Galvanizing is the process of coating the base metal surface with zinc metal.
Iron sheet Rollers
Drier Galvanised iron

Organic solvent Dil. H)S04 ZnCl, + NHCI Molten Zn (450°c) Excess Zn

Technique of galvanizing

Zinc coatings are generally obtained by hot-dipping of the base metal in molten zinc
bath. The following steps are involved in galvanizing.
i) The article to be galvanized is first washed with
organic solvents to remove
organic impurities such as oil and grease present on it.
ii) It is then pickled in dilute sulphuric acid to
remove rust and other inorganic
deposits.
ii) Then it is washed with water and dried.
iv) The metal is treated with a mixture of molten
ZnCl, and NH,CI flux to enable the
coating metal to adhere on base metal.
v) The article is then dipped in molten zinc at
about 450°C.
vi) The excess zinc deposit on the surface is
removed by drilling.
Applications: Galvanizing is used extremely to protect iron from
roofing sheets, fencing wire, water pipe, etc. corrosion in the form of
Galvanized steel is used in building
construction where high degree of corrosion resistance is
required.
 ANALYTICAL TECHNIQUES

Analytical technique is amethod used to determine a chemical or physical property

of a chemical substance, chemical element, or mixture. There is a wide variety of
techniques used for analysis, from simple weighing to advanced techniques using highly
specialized instrumentation.

Instrumental methods of analysis involve an instrument referred to as analytical

instrument. An analytical instrument converts a property of a substance under investigation
into an electrical signal that can be measured by a suitable device.
Instrumental methods of analysis is advantageous because, it is faster, requires only
Smallquantities of the sample. Easy when alarge number of samples have to be analysed
and it is accurate.

CONDUCTOMETRY

Principle: Measurement of conductance can be employed to determine the equivalence

point in acid-base titrations. When indicators are used, the end point is detected by a change
in the colour. In conductometric titrations, there is a sudden change in
conductance of the
solution after the equivalence point. Hence, the equivalence point is determined graphically
by plotting conductance against titre values. The principle underlying conductometric
titration is the replacement of ions of a particular conductance by ions of different
conductance during the titration.

This experiment is based on Ohm's law.

Instrumentation: A simple arrangement of conductometric titration is depicted in

figure.

Titont

Conductometer
+ Stirrer

+ Platinum electrode

-Solution to be analysed
 Conductoneter consistsof acondctivity cell baving (wo platinum clectrodes and a
conductivity measuring devico. "The (wocleclroden huve unit areaof eross sectionand are
placcd unit distanceapart. The asscnbly responds to the change in the concentration of the
analyte.

Aknown volune of he analyte is taken in abrenker and the Conductivity cell

containing platinun1 electrodes is immesed in the solution and connected to the
conductonmeter. The conductivity of the solution is mcasured. The base is added in an
inerement of 0.5 ml at a time and the conductivity i& mcasured after cach addition. A yraph
of conductivity against the volume of the base added plotted which consistsof two straight
lines intersecting at the cquivalence.

Application of conductometry in the estimation of weak acid:

Conductometric titrations can be employed to estimate the amount of weak acid
present in the given solution by titrating it with a strong base.
A known volume of the weak acid (CH,COOH) is tritrated with a strong base like
sodium hydroxide.
CH,C00H + NaOH ’ CH,CO0" + Na" + H,0

In case of this, the conductance will be initially low due to poor dissociation of the
weak acid. When a strong base is added to the acid, the salt formed is highly ionized and the
conductance increases. On complete neutralization of the acid, further addition of base leads
to an increase in the number of more mobile OH ions. Hence, conductance increases
sharply. Thus a plot of conductance against volume of the base added gives two straight
lines as shown in the figure. By knowing the volume of the base required to react with a
known volume of the weak acid, the amount of weak acid can be estimated.

Conductance
base Tgre
(Qm'
jo Teat wth the weat acd
Volume of strong base (ml)

We have
POTENTIOMETRY
Determination of concentration of ionic solution by measuring the emf is referred to
as potentiometry.

Principle: The potential of an electrode is given by Nernst equation,

E-E+0.0591 log[M]

Thus, the potential of an electrode depends on the concentration of the ion to

which it is
reversible. One of the most important practical applications of electrode potentials is in the
determination of end points of various types of titrations such as red-ox and neutralization.
In such a titration, the change in cell emf occurs most
rapidly in the neighborhood of the
end point. The equivalence point of the reaction will be
revealed by a sudden change in
potential in the plot of emf readings against the volume of the titrating solution. One
electrode of the cell must maintain a constant potential and the
other must serve as an
indicator the changes in the concentration. The emf of the cell
of
containing the initial
solution is determined and relatively large increments of the titrant
solution are added until
the equivalence point is reached. The emf is
determined after each addition. The approach
of end point is indicated by more rapid change of
emf. Beyond the equivalence point, there
willbe no significant change in potential. By plotting a
graph of change in potential against
volume of the titrant added, the equivalence point can be
determined.
Instrumentation:
Shge

AH B
Potentiometer
 Potentiometer consists of a reference electrode A', an indicator electrode 'B', a
mechanical stirrer C" and a potential measuring device. The indicator electrode responds
rapidly to the changes in the concentration of the analyte i.e., solution under study. The
solution to be estimated is taken in the beaker.

A known volume of the analyte is taken and its potential is measured. The titrant is
added in increments of 0.5 ml or 1.0 ml at a time and the emf is measured after each
addition. At the approach of equivalence point, the emf tends to increase rapidly. At this
point, small increments of titrant are added. Afew more readings are taken beyond the end
point.

Application of potentiometry in the estimation of iron:

Redox titrations are also carried out potentiometrically. The amount of iron gtFAS
present in the given solution can be estimated using acidified K,Cr,0, solution. Aknown
volume of FAS solution is taken in a beaker. Two test tubes of dilute sulphuric acid is
added. The indicator electrode such as platinum electrode and a reference electrode like
calomel electrodes are immersed in the solution and are connected to the potentiometer. The
potential is measuré. The standard K,CrO, solution is added in an increment of0.5cm' and
the emf is measured after each addition. The approach of the end point is indicated by a
rapid change in emf. Few more readings are taken after the cquivalence point. The ionic
reactions taking place are,

Fe ’ Fe* + e

Cr,0, + 14 H + 6e’ 2 Cr* + 7 H,0

Prior to the equivalence point, the potential is determined by the Fe Fe redox system and
the potential is given by,

E-E+0.0591 log[Fe"]

The potential of the indicator electrode depends upon the ratio of [Fe VFe. As the
titration proceeds, the concentration of Fe goes on increasing and that of Fe?* goes on
decreasing. As a result, the value of the ratio in the expression goes increasing and hence

2
the potential also increases. The increase in the value of
concentration ratio becomes very
large near the end point. This results in the large increase in electrode potential and
hence
the emf of the cell. Beyond the equivalence point, the potential is determined by Cr/Cr
system. This change over of the indicator electrode at the end point also contributes to the
large increase in potential at the end point. The equivalence point can be determined by
plotting a graph of AE/AV versus volume of K,Cr,0, solution. Knowing the equivalence
point, the amount of iron present in the given solution can be estimated.

AE
AV Ou m

Volume of K,Cr,0, solution (cm')

Ne