Mrs Sujatha HR

Module 3

Corrosion

by chemical and/or
Corrosion is the gradual destruction of materials (usually a metal)
electrochemical reaction with their environment

Effects or disadvantages of corrosion

are lost due
"The valuable properties of metal like ductility, malleability, conductivity
to corrosion.

"Corrosion is responsible for the wastage of metal in the form of its compounds.
Failure of machinery, chemical plants etc., so life span is reduced.

Examples of corrosion,

Rusting of steel utensils and iron.

Rusting on copper utensils.

Rusting on iron towers.

The Changing Colour of the Statue of Liberty

Corrosion of the Eiffel Tower

Discoloration of the Taj Mahal

Marine Corrosion

CLASSIFICATION & THEORIES OF CORROSION

Based on the environment, corrosion is classified into

() Dryor ChemicalCorrosion (ii) Wet or Electrochemical Corrosion

DRY or CHEMICAL CORROSION: This type of corrosion is due to the direct chemical
attack of metalsurfaces by the atmospheric gases such as oxygen, halogen, hydrogen
sulphide, sulphur dioxide, nitrogen or anhydrous inorganic liquid, etc. Example: (i) Silver
materials undergo chemical corrosion by Atmospheric H2S gas. (i) Iron metal undergo
chemical corrosion by HCl gas

Wet or Electrochemical Corrosion: This type of corrosion is due to the electro chemical
attack of metal surfaces by the atmospheric air and moisture.
 Example: Rusting of Iron, corrosion of metals like Zn, Mn,Cu etc.
ELECTROCHEMICAL THEORY

Electrochemical theory of Wet corrosion: taking Fc as example.

Electrochemical corrosion involves,

i)The formation of anodic and cathodic areas (galvanic cells) in contact with cach other on
the same metal surface due to the presence of two metals in conducting medium, impurities
and stress in metals.

Corrosion occurs at anodic areas only and formation of corrosion product takes place
somewhere between anodic and cathodic areas.
This involves flow of electron-current between the anodic and cathodic arcas.

1)Atanodic area oxidation reaction takes place (liberation of free electron).

M (metal) ’ Mn* +ne

M* (metal ion) ’ Dissolves in solution ’ forms compounds such as oxide

At anode: Fe ’ Fe2* + 2e
2)At cathodic area, reduction reaction takes place (gain of electrons), usually cathode
reactions do not affect the cathode.

Cathodic reaction consumes electrons with either by (a) evolution of hydrogen or (b)
absorption of oxygen, depending on the nature of the corrosive environment. Possible ways
are,

i) Hydrogen Evolution Type:

The electrons flow through the metal, from anode to cathode, where H' ions of acidic
solution are eliminated as hydrogen gas.
2 H* +2 e’ H2‘
ii) Rusting of iron in neutral medium &in the absence of atmospheric oxygen involves
liberation of H) and OH
2H,0 + 2 e- ’ H2t+ 20H
ii)Oxygen Absorption Type:
In the presence of atmospheric oxygen.
½O2+ H,0 + 2 e ’ 20H
3) Formation of Hydroxide:
The Fe* ions and OH ions diffuse and combine to form ferrous bydroxide precipitate.
 Fe? + 2OH ’ Fe (OH)2
4) Formation of rust:

a) If sufficient oxygen is present, ferrous hydroxide is casily oxidized to ferric oxide.

4Fe (OH)2 +02 + 2H;0 ’2[ Fez0; H;0)]

Yellow rust
(b) If the supply of oxygen is limited, the corrosion product is black anhydrous magnetite,
Fe:O4
3Fe (OH): +0; Fe;O4.3 H;0
Black rust

wate
H,0
Rust
fe,0,H,0 cathodic
site
anodic
site

fels Fe

Types of Corrosion:
(1)Differential metal corrosion (Galvanic corrosion)
(2) Differential Aeration corrosio
1. Differential metal Corrosion/Galvanic corrosion/Bimetallic corrosion.
When two dissimilar metals are in contact with each other a potential difference is set
up resulting in a galvanic current which leads to galvanic corrosion. The two metals with
different reduction potentials have the tendencies to undergo oxidation. The one with lower
electrode potential or the more active metal acts as anode and the one with higher electrode
potential acts as cathode. The anodic metal undergoes corrosion and the cathodic metal is
generally un attacked. A metal placed above in an electrochemical series is said to be anodic
to the metal placed below it. Thus, iron is anodic to Cu, Ni & Sn. On the other hand, iron is
cathodic to Zn and Mg. The rate of galvanic corrosion depends on the potential difference
between the metals.

Eg: Iron corrodes severely in presence of copper (pot difference +0.7v),than in the
presence of tin (pot diff +0.3v).

Electrolyte
Anode reaction: solution
Cathodie reaction:
MM+2e 0,t2H,0t4e40H

Low-potential High-potential
metal metal

Reactions:

At the anode), Fe’ Fe* +ne

At the cathode (more 0 concentration),
H;0 + h02 + 2e-’20H
Fet+20H’ Fe (OH) 2
2Fe (OH) z+1/202+H,0’ [Fe203. 3H20] (rust)
E. g (1) Steel pipes joined to copper plumbing, undergo galvanic corrosion, since Steel acts as
the anode.
E°Fe*/Fe = -0.44 V
E°Cu²/Cu = +0.34 V
(2) Steel screws or rivets used on copper sheet, or screws and washers of unlike metals.
(3) Steel propeller shaft in bronze bearing
In all the above cases steel corrodes due to differential metal corrosion.
Simple cellshowing the principle of differential metal corrosion.

Preventing galvanic corrosion

There are several ways of reducing and preventing this form of corrosion.

Electrically insulate the two metals from each other

 Ensure there is no contact with an electrolyte. This can be done by using
water-repellent
compounds such as greascs, or by coating the metals with an impermcable protective
layer, such as a suitable paint, varnish, or plastic
Choosing metals that have similar clectro potentials., because the smaller the potential
difference smaller is the galvanic current.
Electroplating or other plating are also helpful.
" Cathodic protection can also be applicd
2. Differential Aeration Corrosion

Differential acration corrosion occurs when a metal surfacc is cxposcd to differencc in

concentrations of air or oxygen. The part of the metal exposed to higher oxygen
concentration acts as a cathodic region and the part of the metal exposed to lower oxygen
concentration acts as anodic region.
Corrosion of metal arising as a result of the formation of an oxygen concentration ccll
due to uneven supply of air on the metal surface is known as differential aeration corrosion.

Ametal strip partially immersed in an aerated solution of Nacl undergoes corrosion.

The portion of the metal strip outside the solution has higher concentration of oxygen at its
surface than immersed portion and acts as cathode, whereas the immersed portion acts as
anode. The corrosion product will be formed in between the anodic and cathodic areas and
not on the active electrode surface. Generally, well aerated region becomes the cathode and
remains unaffected and the less aerated region becomes the anode and is corroded.
Metal strip More acrated part

Less acrated part

Anode corrosion
product
Differential acration corrosion

At the anode (less O2 concentration), Fe- Fe + ne

At the cathode (more O; concentration), H20+ ½ O: +2e- ’ 20H
Fez++OH’ Fe (0H):
2Fe (OH)2+1/202+H;0’ [Fe;O3. 3H;0) (rust)
E.g.: - 1. Part of the nail inside the wall, being exposed to lower oxygen concentration than
the exposed part, under goes corrosion.
 2. Paper pins inside the paper gets corroded, and the exposed part is free
from corrosion.
3. Metal under dirt, dust, scale or water
undergoes corrosion

(b) Pitting Corrosion:

OH lon

Cahode

Pitting corrosion is a localized and accelerated form of corrosion, resulting in the

formation of pits or pin holes, around which the metal is relatively un-attacked. Pitting
corrosion results due to deposition of extraneous matter like dust particles, oil droplets etc., or
due to breakdown of protective film or due to non-uniformities in the metal structure itself.
The portion covered by the dust will not be well aerated compared to the exposed
surface. The covered portion acts as anode with respect to the surface exposed. Once a pit is
formed the rate of corrosion increases. This is because of the formation of small anodic area.
The cathode induces the small anodic area to corrode faster by accepting clectrons from the
anodic area resulting in the enlargement of the pit. Pits grow downwards towards the
direction of gravity. Pitting corrosion is one of the dangerous and destructive form since
failure occurs with extreme suddenness.

E.g.: (1l)Less aerated part of the machinery

(2) Less aerated parts of barbed wire
(3) Cracks in metals which are not well aerate.
Pitting corrosion can be prevented through:
1. Proper selection of materials with known resistance to the service environment.
2. Control pH, chloride concentration and temperature.
3. Cathodic protection and/or Anodic Protection.
Corrosion prevention methods

1. Applied coatings.
a. Metal coatings
b. organic coatings
2. Surface conversion coatings
a. Anodizing.
 b. Chromating
c. Phosphating
3. Cathodic protection.
a
Sacrificial anode protection.
b. Impressed current cathodic protection.
4. Anodic protection

5. Corrosion inhibitors

6. Design and selection of materials

Corrosion Control:
Corrosion of a metal is a natural spontaneous process and there are
many types of corroSion.
The mechanisms of corrosion are so different and
conditions under which corrosion takes
place are so varied that no single method can be used to control all
possible corrosion cases.
In general, the corrosion control methods depend on the
factors such as nature and structure
of corrosion. CorrOsion can be controlled by preventing the formation of galvanic cells.
Various methods include,
1)Protective coating
Application of protective coating is one of the important methods of corrosion
control. The protective coating protects the metal from corrosion by acting as a barrier
between the metal and the corrosion environment.
(a) Metal coating:
Deposition of a protective metal over the surface of a base metal (the metal to be protected) is
called metallic coating. The base metal is isolated from the corrosive environment thus
preventing the metal from corrosion. Metal coatings are applied by electrodeposition, flame
spraying, hot dipping, diffusion coating &vapour deposition.

Substrate

Solution.

Anodic Coating: Anodic coatings are produced by coating a base metal with more active
metals which are anodic to the base metal.
 E.g.: Iron is coated with anodic and active metals like
Zn, Mg, and Al.
One advantage of anodic coating is that,
even if the coating is rupturcd, the base mctal
does not undergo corrosion. The exposed
surface of the metal is cathodic with respect to the
coating metal. Therefore, anodic coating is also known as
sacrificial coating.
Galvanisation is a process of coating a base metal surface with Zinc metal.
Galvanisation is carried out by hot dipping method.

Surface Preparation

Cooling and
Drying Zinc Inspection
Flux bath
Rinsing solution
Plckling
Degreasing Rinsing

The galvanization process involves the following steps.

(1) The metal surface is washed with organic solvents to
remove organic matter on the
surface
(2) Rust and other deposits are removed by washing with dilute
sulphuric acid.
(3) Finally, the article is well washed with water and air-dried.
(4) The article is then dipped in a bath of molten zinc, maintained at 425 - 430°C and
covered with a flux of ammonium chloride to prevent the oxidation of molten Zinc.
(5) The excess Zinc on the surface is removed by passing through a pair of hot rollers,
which
wipes out excess of Zinc coating and produces a thin coating.
Uses:

Galvanization is used to protect roofing sheets, water pipes, barbed wire, buckets etc.
Galvanised articles are not used for preparing and storing foodstuffs, since Zinc dissolves in
dilute acids producing toxic Zinc compounds.

2)Inorganic Coating:
Inorganic coatings are generally chemical conversion coatings. A surface layer of the
metal is converted into a compound, by chemical or electrochemical reactions, which forms a
barrier between the underlying metal surface and the corrosion environment.
 Anodized coating or Anodising:
Anodized coating is generally produced on nonferrous metals like Al, Zn, Mg and their
alloys by anodic oxidation process.
In anodization of aluminium, by passing direct current
through the electrolytic cell containing
clean, polished aluminium as anode, immersed in an acid bath like
chromic acid & sulphuric
acid. Inert elcctrodes like lead are generally used as cathode. The
anodic oxide film formed
on Al in bath as aluminium oxide, which is porous and
provides goodadherence for paints.
The strength and corrosion resistance of the anodised film can be
increased by sealing.
The pores are finally sealed by dipping in hot water to produce
Al;03.H:0, which acts as a
non-porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H;0 ’ Al,0; + 6H+ +6e
Cathode reaction: 6H+ + 6e-’ 3H2
Anodizing of aluminium produces a hard, compact, and strongly adherent oxide film that
significantly improves corrosion resistance. The appcarance and characteristics of the oxide
film can be a function of the type of anodizing treatment. The
appearance can also be
impacted by a wide range of dyes.

Aandos thode

Electro

A’o,

Advantages:
1. Anodised aluminium products have a protective layer; they have harder and
durability
than normal aluminium.
2. The anodized surface show good adhesion to paint and gives a
coloured appearance.
3. The thick outer coating produced, along with the proper sealing, increases the
corrosion
resistivity of the surface as it prevents further oxidation.
Common applications for anodized finishes:
Structures and architectural categories of all types.
Appliances.
Commercial and residential building products.
" Food preparation equipment.
Furniture.

Sporting goods and boats.

Motor vehicle components.

Jewellery and art work.

3. 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.
Electrons from the external source for cathodic protections can be provided by two
methods.
()Using sacrificial anode method
(i) Impressed current method

(i) Sacrificial anode method:

The protected metal structure is converted into a cathode by connecting it to a more
active metal. This active metal acts as an auxiliary anode Zn, Mg and Al are the common
auxiliary anodes and are more reactive undergo corrosion, protecting the metal structure.
Since the anodic metals are sacrificed to protect the metal structure; the method is known as
sacrificial anode method. Exhausted sacrificial anodes are replaced by new ones as and when
required.
poer source s needed
.Lead wre

Ooject
Sacrlcial
anode
protected
ProteCtve urert

A magnesium block connected to a buried oil storage tank

Mg bars are fixed to the sides of ocean-going ships to act as sacrificial anodes.
Mg blocks are connected to buried pipe lines.
 Cathodic protection by sacrificial anode method
Advantages:
(1) The method is simple
(2) Low installation cost
(3) Minimum maintenance cost
(4) Does notrequire power supply
Disadvantage: Replacement of consumed anodes.
Corrosion Penetration Rate (CPR)
The corrosion penetration rate (CPR) is defined in
three ways:
The speed at which any metal in a specific
environment deteriorates due to a chemical
reaction in the metal when it is exposed to a
corrosive environment or The amount of
corrosion loss per year in thickness orThe speed at which corrosion spreads to the inner
portions of a material.

The speed or rate of deterioration depends on the

environmental conditions and the type
and condition of the metal under study.
Corrosion penetration rate may also be known as
Corrosion rate,

Several pieces of data must be collected to calculate the corrosion

penetration rate for any
given metal:

The weight lost (the decrease in weight of the

metal during the period of reference).
The density of the metal.
The total surface area initially present.
The time taken for the metal to corrode.

The CPR is calculated as follows:

CPR =(kx W) /(DxAx T)
where k=a constant

W= total weight lost

T= time taken for the loss of metal

A = the surface area of the exposed metal

6
 D= the metal density in g/cm
The corrosion penetration rate is best expressed in
terms of thickness or weight loss where
the surface of the metal corrodes
uniformly across an area.
The units used are in terms of penetration of pits on a
metal.
Mils per year is commonly used corrosion rate
expression as it measures corrosion rate in terms
of depth of penetration of pit.

Electrode Systems:
Reference electrode:

Definition: Reference electrode is an electrode whose electrode potential is arbitrarily fixed

or known and is reliable. or It is the electrode of standard
potential with which the potential
of other electrodes can be
compared.
Two types of reference electrodes are,
1. Primary reference electrode, Example: Hydrogen gas electrode

2. Secondary reference electrode, Example: Calomel electrode, silver-silver electrode and

glass electrode.

Calomel electrode:

Construction and working:

It is a metal-insoluble salt clectrode, where metal in contact with its insoluble salt and the
solution contains the anion of the salt.

Electrode representation: Hg(s)/Hg:Clh (paste)/Ct

H HC
H

Stancard Catomel El4cde

 Mercury is placed at the bottom of the glass tube above which a paste of
mercury and
Mercurous chloride are present. It is filled on the top with the saturated solution of KCI.
A
platinum wire sealed into a glass tube is dipped into mercury and used to provide the
external
electrical contact. Depending on the nature of the other electrode it can either acts as anode or
cathode.

If the electrode behaves as anode, the electrode reaction is:

2Hg (l) -’>Hg?*+2e

Hg:* +2CI-’ Hg:Clz(s)
NCR 2Hg (|) +2CI> HgClz(s) +2e
If the electrode behaves as cathode, the electrode
reaction is:

Hg,?+2e-’ 2Hg (I)

Hg:Clh(s) -’ Hg:* +2CI
NCR Hg:Clh(s)+2e---’2Hg (l) +2CI
The electrode potential may be represented by the Nernst equation as at 298K

E- E°-0.0591 logCI at 298K

The electrode potential decreases with increase in the concentration of chloride ions.

The potential values depend on the concentration of the solution used in the construction of
the electrode:

For saturated KC1, E°= 0.241V (called Saturated calomel electrode-sCE)

Advantages:
1)It is simple to construct.

2)Cell potential is reproducible and stable for a period long

3) Cell potential does not vary with temperature.

Disadvantages:
It cannot be used above S0°c, because Hg:Cl; breaks down yielding unstable readings and it
is toxic.
Uses:1)It is used as a secondary reference electrode in the measurement of single electrode
potential

2) It is the most commonly used reference electrode in allpotentiometric determination.

E.g.: Estimation of FAS by Potentiometric method, Determination of pKa of weak acid.
lon Selective Electrode:

Definition:

Electrodes which can selectively detect and quantitatively measure a particular

chemical species in a system are referred to as ion selective electrode. Ion-selective
electrodes have the ability to respond to a specific ion in a mixture of ions in solutions
ignoring all other ions and develops a potential. The potential developed is a function of the
concentration of that particular ion. The electrode generally consists of a membrane which is
capable of exchanging the specific ions with the solution with which it is in contact.
Therefore, these electrodes are also referred to as membrane electrodes.
Glass Electrode:

Principle:
When two solutions of different hydrogen ion concentrations, i.e., different pH values
are separated by a thin glass membrane, there develops a potential difference between the two
surfaces of the glass membrane. The potential developed is proportional to the difference in
the pH values of the two solutions. If the pH of the one solution is kept constant, the potential

becomes proportional only to the pH of the other solution. This is the basis of the glass
electrode.

Construction:

-Vacuun tube

Platinum wire

GHass.
clectrode

KO Nd
solutn
He

0 1M HCI Ig +HgCl; Calonel clectre

 -0.0591 log C2 =L, is a constant because internal solution is a standard
solution. Since, the boundary potential E, depends only upon the hydrogen ion
activities of the solutions. Since the concentration of the inner solution is constant, C2
is constant. The above equation simplifies to,

Es= L+0.0591 log C1

Cj is thc hydrogen activity (concentration)of external solution.

E_= L+0.0591 log [H"]

Es= L-0.0591 pH wkt, pH=-log [H"]
The total potential of the glass electrode Eg has three components

(i) The boundary potential

(ii) The potential of the internal Ag/AgCl reference electrode and

(ii) A small asymmetry potential

Therefore,

EG- Es+ERertEAssy
difference in response of the inner
EAsy is the asymmetric potential which arises due to the
activity. ERefr is the potential of
and outer surface of the glass bulb to changes in H ion
internal reference clectrode. Substituting for Eb we get,
EG- L-0.0591 pH +ERertEAy
is simplified to,
Since, L, ERef, and EAssy are constants, the equation
EG- EG°-0.0591 pH Where, Ec'= L+ ERertEAssy is a constant.

EG is the glass electrode potential.

Advantages:
range 0-9, with special type of glass
1. This electrode can be used to determine PH in the
even up to 12 can be calculated.

2. It can be used even in the case of strong oxidising agents.

3. The equilibrium is reached quickly.

 The glass clectrode consists of a glass
bulb made up of a special type of ylass with
high clectrical conductivity. The
Na0, 6% CaO, and 72% SiO2. The glass
composition of the ylass nembranc is approzimatcly 22%
bulb is filled with a solution of known pH (0.1M
HCI)and is inserted with an Ag-AgCl
electrodc, which is the internal reference clectrode and
also serves for the external clectrical
contact. The clcctrode is dipped in a 5olution whose pH
is to be determined
(containing H' ions).
The glass clectrode system can be
represented as follows:
glass membrane/0. IMHCV Ag/AgCl(s)/
When dipped in a solution of unknown pH, it can be
represented as,
Analyte solution / glass membrane /0.IMHCI IAgCIV Ag
Working:
The glass surface acts as an
electrochemical membrane and is non conducting.
The mechanism steps are as follows.
1)The glass surface gets hydrated both on outside and inside surfaces.
2) H ions get absorbed on the hydrated layer.

3)The glass membrane exchanges ions with the solution

H(solution) + NaGI (glass)-’ Na»(solution) + H GI(glass)

The exchange of ions by the inner and outer membrane gives rise to a boundary potential.
This boundary potential consists of two potential E, and E, which are associated with the
outer and inner membrane respectively.
Eb=Ex- E,

Therefore, from thermodynamic consideration it has been shown that E, and E; are related to
the hydrogen ion activities, Ci and C; in the outer and inner solution respectively.
By Nernst equation,
Es=E° +0.0591 Log Ci- [E° +0.0591 log C:)
Es= 0.0591Log Ci -0.0591 log C:
 4. It is simple to
operate, hence extensively used in various
laboratories.
Limitations
1. The glass membrane though it is very thin, it offers high
resistance. Thereforc, ordinary
potentiometers cannot be used; hence it is necessary to use electronic
potentiometers.
2. This electrode cannot be used to determine the pH above 12
because it will become
sensitive to Naand includes alkaline
erTors.
Determination of pH using Glass Electrode:
The given glass electrode is dipped in the
unknown solution containing hydrogen ions,
constitutes a half cell. It is coupled with reference electrode (ex:
saturated calomel electrode)
through a salt bridge, where calomel electrode forms an
outer reference electrode.
The above cell may be
represented as:
Hg/ Hg-Clz (paste) /Sat. KCI/ analyte solution l glass
membrane /0.1M HCL/AgCV Ag
In the above cell, the glass
electrode behaves as cathode and calomel clectrode as
anode.
The cell potential may be determined
using electronic potentiometer.
The EG is obtained by repeating the
experiment the using solution of known pH.
The pH value of the experimental solution can be
calculated by substituting the values
of Ecell, Ecalomel and EG in the following relation:

0.0591pH = Ec'- EscE - Ecell

pH = (EG'-EsCE Ecelly 0.0591

pH = (EG'- EsCE- Ecell/ 0.0591 Where K= EG'- EsCE, EscE =0.241V

K is known as GIass electrode assembly
constant.
Analytical Techniques

Analytical technique is the instrumental methods of analysis. It is the

modern methods of
analysis used for the estimation of constituents of a sample of a substance in
chemical
analysis.
 Analytical techniques involve a measurement of physical property of a substance to
determine its chemical composition using a suitable a device, which converts the property of
the substunce under investigation into a readily measurable form. The
measured quantity is
related to quantity or quality of the sample.
Analytical techniques may be classificed into two types,
1) Electro analytical or clectrical methods.
2) Spectro analytical or optical methods.

Electro analytical methods are the techniques that involves the analysis of the sample
containcd in clcctrochemical ccll, by measuring the potential or current.
Different electroanalytical methods are,
1) Potentiometry
2) Conductometry

POTENTIOMETRY:
Potentiometry is an electroanalytical technique which the concentration of ionic solution
can be determined by measuring emfbetween the two electrodes dipped in the solution.

PRINCIPLE:
The potential difference between the two electrodes is the basis of the potentiometry. The
addition of a titrant leads to a change in the ionic concentration, causing changes in the
potential difference.
Which is given by Nernst equation,
E- E° +0.0591 log (M"*)

n
i.e., the potential of an electrode depends on concentration of ion to which it is
reversible.

INSTRUMENTATION:

Potentiometer consists of a reference electrode whose potential is constant, an indicator

electrode, and a potential measuring device. The indicator electrode responds to the changes
in concentration of analyte.

A simple arrangement of potentiometric titration is as shown.

 Burette

Patertiometer
Indicator
Saturatad elactrode
calumel
electrode

Analyte
solutlon

Magnetic stirter

A reference electrode and an indicator electrode are dipped in a known volume of

analyte is taken in the beaker and its potential is determined. The titrant is added in
increments and emf is measured each time. At equivalence point, emf increases rapidly. A
few readings are taken beyond the end point. Thus, the changes in potential at
different
volumes of titrant arc recorded using potentiometer. It is determined by plotting change in
potentials against the volume of titrant by employing derivative methods i.e., AE/ AV against
volume V.
ADVANTAGES:
Potentiometric titrations can be carried out in coloured solutions where indicators
cannot be used.

By potentiometry, it is possible to determine the end point in titrations of very weak

acids or very weak bases.
Applications:
The Potentiometric titrations find applications in acid base, redox and precipitation
reactions.
1) Estimation of FAS potentiometrically using standard K2Cr:0; solution.
2) Determination of pKa of weak acid using pH meter.

Applications:
1) Estimation of FAS potentiometrically using standard K2Cr;0, solution
Redox titrations can be carried out potentiometrically. In potentiometric titration of Mohr's
salt solution with potassium dichromate solution, the standard calomel electrode is used as
 reference clectrode and platinum electrode is used as indicator electrode. When, acidified
Fe'solution is titratcd slowly against K;Cr:0; from the burcette, the following reaction takes
place.
6Fe+Cr, o 6Fe*+2C'*

Before the cquivalence point, the potential is determined by the Fe? /Fe redox system. After
the cquivalence point the potential is determined by the Cr20, /C system. At the
equivalence point, the potential is average potential of both the systems. Thus, there is an
abrupt incrcase in potential of the solution near the end point.
Procedure:
Pipette out 10cm offerrous ammonium sulphate (FAS) solution into a 100 ml beaker.
Add one test tube full of dilute sulphuric acid. Immerse, the platinum calomel electrode

assembly in to the solution. Mcasure the potential by adding K,Cr0; solution from the burette
in increments of 0.5 cm². Stir the mixture for few seconds, and measure the potential of the
solution after each addition.

Plot a graph of AE / AV against volume of K;Cr:O, as shown in the figure. Find the equivalence
point from the graph. Knowing the equivalence point, calculate the normality of the FAS
solution and determine the amount of FAS per litre of the solution
Report: Mass of FAS present in one dm of solution =

mVem-3

K;Cr:0, in cm'

Note: for observations and calculations refer lab manual.

CONDUCTOMERTIC TITRATION:
The electrical conductance (C) of a solution is a measure of the ability of a solution to
conduct electricity. It is expressed in Ohm -,mho's or Siemen (S) in SI units.
 According to Ohm's law, current (I) flowing in a conductor is directly proportional to
cmf (E) and inversely proportional to resistance (R).
|=R
Therefore, the reciprocal of resistance is conductance. The
resistance of a homogencous
material of uniformcross section with an arca of 'a'sqg.cm and
length " cm is given by,
R= PI /A
Proportionality constant P is the spccific resistance.
The reciprocal of specific resistance is spccific conductance.
Specific conductance:( K)
Specific conductance is the conductance ofa solution present
betwcen 2 parallcl
clectrodes of arca lcm² which are kept lcm apart.
K= 1/R* Va Va =cell constant
When I =1, a=lcm², K =C
The unit of K in SI units is Sm!
The specific conductance of an electrolytic solution at any
temperature depends on
ions present and hence varies with ionic concentration. On
dilution, specific conductance
decreases as no of ions per ml also decrease.
Principle:
Electrolytic conductivity is a measure of the ability of a solution to carry electric current.
Electrolyte solutions conduct current by the migrations of ions under the influence of an
electric field. To measure the conductance of a solution, conductivity cell is placed.

INSTRUMENTATION:
A simple arrangement of consists of conductivity cell or conductance cell dipped in the
analyte solution taken in a beaker.

Conductivity cell consists of 2 platinum clectrodes, clectroplated with platinum black and a
conductance measuring device. The 2 electrodes have unit area of cross section and are
placed unit distance apart. The system responds readily to changes in concentration of
analyte.
 NaOH + HCI NaCl + H,0

HCI

conductvity
meter

end point

-NaOH volume of HCI added

The titrant is added from a burette and the solution is stirred. The conductance is measured
after the addition of the titrant in the increments of 0.5ml or one ml.

Applications:
Used to determine the solubility of sparingly soluble salts.
Determination of degree of dissociation.
Conductometric titrations.
Conductometric titrations:

In this method, the variation of electrical conductance of a solution during the course of a
titration is followed.

The principle of conductometric titrations is that ions ofa particular conductance are replaced
by ions of different conductance. Therefore, there is a sudden change in conductance of the
solution at the equivalence point. The conductance of a solution depends on the number and
mobility of ions. The equivalence point is determined graphically by plotting conductance
against titre values.

ADVANTAGES:

1. Mixture of acids can be titrated accurately.

2. When visual or potentiometric methods fail due to solubility or hydrolysis, in such
cases conductometric methods are suitable.
3. Accurate results are obtained in dilute as wellas more concentrated solutions.
4. The method can be employed for coloured solutions.
5. Very weak acids which cannot be titrated potentiometrically, can be titrated by
conductometric method.
APPLICATIONS:
1. Titration of weak acid with a strong base: e.g.: CH;COOH Vs. NaOH
The conductance of weak acid is initially low, due to poor dissociation. When a strong base is
added, the salt is formed, gets ionized and conductance increases slowly. On complete
neutralization, further addition of base increases no of OH ions, and conductance increases
sharply. The plot of conductance versus volume of strong base is as follows.

Volume of NaoH(m).

Limitations:
Can be employed only when there is appreciable change in conductance during titration.
Redox titrations cannot be carried out.

Note: for observations and calculations refer lab manual(only acetic acid).
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