MODULE 3: CORROSION AND ELECTRODE SYSTEM

Syllabus
Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of
corrosion-differential metal and differential aeration. Corrosion control - galvanization,
anodization and sacrificial anode method. Corrosion Penetration Rate (CPR) - Introduction
and numerical problem.
Electrode System: Introduction, types of electrodes. Ion selective electrode – definition,
construction, working and applications of glass electrode. Determination of pH using glass
electrode. Reference electrode - Introduction, calomel electrode – construction, working
and applications of calomel electrode. Concentration cell– Definition, construction and
Numerical problems.
Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its
application in the estimation of weak acid. Potentiometry; its application in the estimation
of iron.

Single Electrode Potential (EMn+/M):

It can be defined as “the potential developed at the interface between the metal and solution, when it
is in contact with a solution of its own ions”
OR
“Single electrode potential is a measure of tendency of a given half-cell reaction to occur as reduction,
when it is in equilibrium with the other half cell”
Standard Electrode Potential (EoMn+/M):
“Standard electrode potential is the electrode potential when the electrode is in contact with a solution
of unit concentration, at 298K or if the electrode involves a gas then the gas at 1 atmosphere pressure”.

Emf of cell: “Emf is the potential difference between the two electrodes of a galvanic cell, which
causes the flow of current from one electrode to other”
OR
“The voltage under the influence of which the electric current flows in the cell is called the
electromotive force of the cell or the emf of the cell”

Ecell= Ecathode-Eanode
Ecell = Ecathode - Eanode
For standard conditions: E°cell = E°cathode - E°anode
Note: Among the given two SRP values, more value is cathode and less value isanode in the galvanic cell.
Example: The E° values of Zn and Cu are -0.76 V and +0.34 V respectively.
 Zn is anode and Cu is cathode.
Derivation of Nernst equation for single electrode potential
Single electrode potential (E), Change in free energy (G) and the concentration (Mn+) are related
by Nernst equation. According to thermodynamics, the decrease in free energy (– ∆G) represents
the maximum amount of work that can be obtained from a chemical reaction or In a reversible
reaction, the electrical energy is produced at the expense of free energy decrease.
–∆G= Wmax
The work performed by an electrochemical cell depends on the no. of coulombs of electricity that
flow and the energy available per coulomb.
Work = No. of coulombs x Energy available/ coulomb
The number of coulombs of current is the product of number of moles of electrons that are involved
in the cell reaction and the Faraday’s constant.
No. of coulombs= n x F
Energy available per coulomb is the cell potential “E”, since volt is equal to energy per coulomb.
The cell potential is maximum, when the work derived from the cell is maximum. Thus, (Wmax = Wele);
Wmax = Wele = n x F x E.
Wmax = (No. of moles of electrons) x (Faraday’s constant) x (No. of volts or Energy)
Therefore G = - n F E ------------------------- (1)
Under Standard condition equation (1) may be written as
o o ---------------------
G = - n F E (2)
Consider the following reversible electrode reaction,
Mn+ + ne- ⇄ M
For the above reaction the equilibrium constant Kc can be written as
[M]
Kc =
[Mn+]
Equilibrium constant Kc is related to change in free energy by the Vant Hoff equation,
G = Go + RT 𝑙n KC ------------- (3)
o
Substitute the values of G, G & Kc in equation (3) we get,
o
- n F E = - n F E + RT ln [M] -------------------- (4)
[Mn+]
Divide the above equation throughout by – n F, we get
RT [M]
E = EO - ln − − − − − − − (5)
nF [Mn+]
Under standard conditions M=1. Hence the above equation becomes
RT
E = EO + ln[Mn+] − − − − − − − (6)
nF
Converting natural logarithm to the base 10 in equation (6), we get
2.303RT
E = EO + log 10 [Mn+ ] --------------- (7)
nF
Substituting values of R =8.3143 J K-1 mol-1 & F =96500 C mol-1 at 298K above equation, we get,
0.0591
E = EO + log [Mn+ ] ------------------ (8)
n 10
 3

Where; E = Electrode potential, E0 = standard electrode potential, n = no. of electrons

[Mn+] = Concentration of metal ions, R = Universal gas constant , T = Temperature (In Kelvin).

It may be seen from Eq. 7 & 8 that the electrode potential increases with increase in the
concentration of Mn+ and increase in temperature.

Note: The Nernst equation is not only applicable for single electrode but it isalso applicable for a cell
made out of two electrodes.

Types of Electrodes
Some important types of single electrodes are as follows:
1) Metal – metal ion electrode: where a metal is in contact with its ionic solution,
E.g.: Cu2+/Cu, Zn2+/Zn, Ag+/Ag.
2) Gas electrode: where a gas is in contact with an inert metal dipped in an ionic solution of the
gas molecules, E.g.: hydrogen electrode.
3) Metal-metal salt ion electrode: where a metal is in contact with a solution containing the
anion of the salt.
E.g.: Calomel electrode, Ag/AgCl electrode.
4) Amalgam electrode – where a metal dissolved in Hg is in contact with the metal salt solution.
E.g.: Pb-Hg/ Pb2+, Zn-Hg / Zn2+.
5) Redox electrode: where an inert metal dips into a solution containing ions of two different
oxidation states. E.g.: Pt/Fe2+, Fe3+.
6) Ion – selective electrode/ Membrane electrode - where a membrane is in contact with an
ionic solution with which it can exchange ions. Or electrodes which have the ability to respond
to specific ions.
E.g.: Glass electrode (which responds to hydrogen ions), Solid state electrode and liquid
membrane electrode.

Reference Electrodes:
Reference electrodes are electrodes whose potential are known and are used for the
determination of potentials of other electrodes. These electrodes must satisfy the following conditions.
1) Their potential values should be known, stable, reliable and reproducible.
2) Their potential gradient with the temperature shall be the least at the temp. of measurement

Reference electrodes are of two types:

1. Primary Reference electrodes – Standard Hydrogen Electrode (Pt/H2(1 atm.)/H+(1M))

2. Secondary Reference electrodes - Calomel electrode and Ag – AgCl electrode.

 4

Calomel electrode: It is a metal-metal salt ion electrode & Secondary reference electrode.

Calomel electrode consisting of a glass container at the bottom of which mercury is placed
above which a layer of mercury and mercurous chloride (called calomel) is placed with 3/4 th of
bottle is filled with saturated KCl solution. The platinum wire is used for electrical connections.
Salt bridge is used to couple with other half cell. Electrode potential of the cell depends on the
concentration of KCl used.

The calomel electrode can be represented as.

Hg (l) / Hg2Cl2 (S) / Saturated KCl.
The calomel electrode acts as both anode and cathode depending upon the other electrode used.
When it acts as anode the electrode reactions is,
2Hg + 2Cl- Hg2Cl2 + 2e-
When it acts as cathode the electrode reaction is
Hg2Cl2 + 2e- 2Hg + 2Cl-

NCR: Hg2Cl2 + 2e- 2Hg + 2Cl-

Applying Nernst equation, Electrode Potential, E = Eo – 2.303 RT log 10[Cl-]2

nF
E= Eo – 2.303 RT log10 [Cl-]2 where n=2
2F
E= Eo – 0.0591 log10 [Cl-] at 298 K
The electrode potential is decided by the concentration of chloride ions and the electrode is
reversible with chloride ions. At 298 K, the electrode potentials are as follows:
0.1N KCl = 0.334 V,
1N KCl = 0.281 V &
Saturated KCl = 0.2422 V
 5

Advantages:
 It is easy to construct and maintain.
 Its potential can remain constant and it can easily be reproduced.
 It can be used in the presence of oxidizing agents.
Applications:
 It is used as reference electrode in all potentiometric titrations.
 It is used as reference electrode with glass electrode in pH determination.
 It is used as a secondary reference electrode in the measurement of single electrode potential.

Ion selective electrodes: These are the electrodes, which responds to specific ions only and
develops a potential against that ions (is proportional to concentration of the ions), while ignoring
the other ions present in the solution.
Ex: Glass electrode.
Glass Electrode
Glass electrode is a pH sensitive electrode widely used
for pH determinations. It is consisting of a long glass tube at the
bottom of which a thin and delicate glass bulb, which made up
of special type of glass (22 % Na2O, 6% of Cao, 72% of SiO2)
with low melting point and high electrical conductance is used.
The glass bulb is filled with a solution of constant pH (0.1 M
HCl), and is inserted with a Ag – AgCl electrode, which is the
internal reference electrode and also serves for the external
electrical contact. The electrode is dipped in a solution
containing H+ ions.

Electrode Potential of Glass Electrode (EG)

The glass electrode can be represented as Ag/AgCl(s) /0.1M (HCl) / Glass.

When dipped in a solution it can be represented as

Glass Membrane
External analyte 0.1 M Ag/AgCl
Solution [H+] = C2 HCl Electrode
C1 = 0.1 (Internal reference)

E2 E1 Eref

Eb = E2 – E1
 6

The glass membrane exchanges ions with the solution:

-
H+ (Solution) + Na+Gl- (Membrane) Na+ (Solution) + H+Gl (Membrane)

The exchange of ions by the inner and outer membrane gives rise to a boundary potential.
This boundary potential consists of two potentials E1 and E2, which are associated with the outer
and inner membranes respectively.
Then Eb = E2 – E1
= 0.0591 log (C2 /C1) (n = 1 for H+ ion)
Thus, the boundary potential Eb depends only upon the hydrogen ion activities of the
solutions. Since the concentration of the inner solution is constant, C1 is constant. The above
equation simplifies to
Eb = 0.0591 log C2 - 0.0591 log C1
= L + 0.0591 log C2 Where, L = - 0.0591 log C1

The potential of the glass electrode EG has three components:

1. The boundary potential (Eb)
2. The potential of the internal Ag / AgCl reference electrode (E ref) and
3. A small asymmetry potential (E asy).

EG = Eb + E ref + E asy
= L + 0.0591 log C2+ E ref + E asy
= E0G + 0.0591 log C2
= E0G + 0.0591 log [ H+] Where C2 = [ H+]
EG = E0G – 0.0591 pH Where pH = - log [ H+]

Where E0G is a combination of three constant terms,

E0G = L + E ref + E asy
Asymmetric potential arises due to the difference in responses of the inner and outer surface of the
glass bulb to changes in H+ ion activity. This may originate as a result of differing conditions of
strain in the two glass surfaces (due to difference in curvature). This asymmetric potential varies
with time and therefore, glass electrode must be standardized frequently by placing a solution of
know H+ activity (pH).
Advantages:
 Glass electrodes are portable and easy to operate
 Can be used in oxidizing and reducing environments.
 It can be used for coloured, turbid and colloidal solutions.
 Accurate results are obtained between pH range 1 – 9. However, by using special glass
electrodes, pH 1 – 14 can be measured.
 Electrode does not get poisoned.
Disadvantages:
Because of the high resistance of glass, simple potentiometers cannot be used. It requires
sensitive electronic potentiometers for EMF measurement.
 7

Determination of pH using Glass Electrode:

Principle: When a thin glass membrane is placed between two solutions of different pH values, a
potential difference arises across the membrane. The potential difference varies as the pH of these
solutions varies. In practice, pH of one of these solutions is kept constant and therefore the
electrode potential depends on pH of the other solution ie., experimental solution.
Procedure: To determine pH of unknown solution the glass electrode is combined with secondary
reference electrode such as calomel electrode and the glass - calomel electrode assembly is dipped
in the solution whose pH is to be determined. The two electrodesare connected to potentiometer or
pH meter.

The combined electrodes can be represented as.

Hg(l) / Hg2 Cl2 (S) / Saturated KCl //solution of unknown pH /glass/0.1M HCl/Ag/AgCl(s)

The emf of the cell is given by E cell = E cathode – E anode

E cell =E glass - E calomel
E cell = EG – E cal
Ecell = E0G – 0.0591 pH - E cal
pH = (E0G - E cal - E cell) / 0.0591
E0G value is evaluated by dipping the glass electrode in a solution of known pH and measuring the
emf of the cell formed when combined with a calomel electrode.
 8

CONCENTRATION CELLS: (Electrolyte Concentration Cells)

These are the galvanic cells consisting of same metal electrodes dipped in same metal ionic solution
in both the half cells but are different in the concentration of the metal ions.
Ex: Consider the following concentration cell constructed by dipping two copper electrodes in
CuSO4 solutions of C2 molar and C1 molar where C2>C1.

The two half-cells are internally connected by a salt bridge and externally connected by
ametallic wire through voltmeter or ammeter.

The electrode, which is dipped in less ionic concentrations solutions (C1) act as anode and
undergoes oxidation. The electrode, which isdipped in more ionic concentration (C 2) act as cathode
and undergoes reduction.
The cell can be represented as,
Cu/Cu2+ (C1)||Cu2+ (C2)/Cu

By convention, left hand electrode is the anode and right hand electrode is cathode.
At anode : Cu (S) Cu2+ (C1) + 2e-
At cathode : Cu2+ (C2) + 2e- Cu (S)
NCR: Cu2+ (C2) Cu2+ (C1)

EMF of Concentration cell:

We know that electrode potential depends upon the concentration of the electrolyte. By convention,
the potential of the cell is

Ecell = Ecathode – Eanode

Ecell = [ Eo + 0.0591 log (C2) ] – [Eo + 0.0591 log (C1)]

n n

Note: Where, (C2) > (C1), cell potential will be positive.

(C2) < (C1), cell potential will be Negative.
(C2) = (C1), cell potential will be Zero.

[Note: Follow regular class notes for numerical problems on Concentration Cells]
 MODULE -3
CORROSION CHEMISTRY
Syllabus: 22CHES12/22
Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of
corrosion-differential metal and differential aeration. Corrosion control - galvanization,
anodization and sacrificial anode method. Corrosion Penetration Rate (CPR) - Introduction
and numerical problem.

Corrosion is defined as the “destruction or deterioration of a metal or its alloy and consequent
loss of metal, caused due to direct chemical action or electrochemical reactions with its environment”.
Several metals undergo corrosion when exposed to air, water or other substances. The primary factors which
initiate corrosion of metals are atmospheric air and water.
A typical example of corrosion is rusting of iron.
 Corrosion of metals can be regarded as the reversal of its extraction.
 Rusting weakens bridges, buildings; ship’s hulls iron railings, car bodies, equipment/machine tools,
pipeline, airplane, water treatment plants etc.,
 A recent study by National Association of Corrosion Engineering (NACE) international estimates
global cost of corrosion is at US$ 2.5 trillion. The study found that implementing corrosion
prevention best practices could result in global savings of between 15 to 35 % of the damage or
between US$ 375 to 875 billion. Therefore corrosion or rust prevention is a major economic
expenditure.

Corrosion may occur either in a dry environment or in an aqueous medium. The former is called dry
corrosion and the latter is wet corrosion.

Dry Corrosion: Dry corrosion occurs in the absence of moisture or conducting electrolyte medium,
due to direct attack of metals by dry gases mainly through chemical reactions. Ex: the attack of dry gases
such as O2, Halogen, H2S, SO2, NOX etc., on a metal to form an oxide layer over the surface. However, such
a process is not common.

Wet Corrosion: Wet corrosion involves reactions in aqueous medium. The conducting surface of
the metal undergoes an electrochemical reaction with the moisture & oxygen present in the atmosphere. Ex:
Rusting of Iron. Wet corrosion can be better explained on the basis of electrochemical theory.

Electrochemical theory of corrosion:-

According to electrochemical theory, when a metal such as iron is exposed to environment, the
following electrochemical changes occur gradually.
a) Formation of Galvanic cells: A large number of minute galvanic cells are formed which acts as anodic
and cathodic areas.
b) Anodic reaction: At anode the metal undergoes oxidation and electrons are liberated which migrates towards
cathodic region
c) Cathodic reactions: The electrons flow from anodic to cathodic area. Oxygen of the atmosphere
undergoes reduction at cathodic area in the presence of moisture forming hydroxyl ions at the cathode
Anodic reactions: At anode the metal undergoes oxidation-liberating electrons
M Mn+ + ne-
Metal Metal ions
Ex: when iron is exposed to the environment it undergoes oxidation as
Fe Fe2+ + 2e-
Cathodic reactions:-
The electrons released at anode migrate to the cathodic area and reduces oxygen to hydroxyl ions.
The different cathodic reactions are,
a) If the solution/medium is deaerated and acidic, hydrogen ions are reduced to hydrogen gas.

2H+ + 2e - H2
b) If the solution/medium is deaerated and almost neutral (alkaline), H2O is reduced to H2 and OH-

-
2 H2O + 2e- 2OH + H2
c) If the solution/medium is aerated and almost neutral, oxygen is reduced in the presence of water
to hydroxyl ions as follows.

O2 + 2 H2O + 4e- 4OH-

d) Formation of corrosion product:

The metal ions formed at the anode combine with the hydroxyl ions to form the metal hydroxide
and finally the insoluble hydrated ferric oxide known as Rust.
2Fe2+ + 4OH - 2Fe (OH) 2
2Fe (OH) 2+ O2 + (n-2) H 2O (Fe 2O 3. nH2O) Rust

Types of corrosion: Corrosion can be classified into 3 types

1. Differential metal corrosion (Galvanic corrosion)
It occurs When two dissimilar metals are in .contact with each other, the metal with
lower electrode potential becomes anodic and undergoes corrosion, whereas, the metal
with higher potential becomes cathodic and remains unaffected. The rate of corrosion depends
mainly on the difference in potential between two metals. Higher the difference, faster is the rate
of corrosion.
Example:- a) Standard electrode potential of Fe (-0.44 V) is less than that of Cu (0.34 V).
Therefore, when iron is in contact with copper, iron becomes anodic and undergoes
corrosion, whereas copper becomes cathodic and remains unaffected

b) Standard electrode. potential of Zn (-0.76 V) is less than that of Fe (-0.44 V). Therefore,
when iron is in contact with zinc, Zn becomes anodic and undergoes corrosion. Fe becomes
cathodic and remains unaffected.
 2. Differential aeration corrosion-
This type of corrosion occurs when a metal is exposed to different concentrations of oxygen. The
part of metal which is more exposed to air act as cathode and remains unaffected. The other part of the
metal, which is less exposed to air act as anode and undergoes corrosion. Typical examples of differential
aeration corrosion are the water line corrosion and pitting corrosion.
i) Water line corrosion:
Water line corrosion is commonly observed in steel water storage tanks and in ships floating in
seawater for long periods of time. The anodic area moves gradually upwards and the entire tank corrodes
with an intense corrosion at the water line.

The metal just below the water line is more anodic (less oxygenated). The meniscus (creep) which is
immediately above the water line is more oxygenated, acts as cathode and is unaffected. The size of the
creep determines the rate of corrosion. Larger the creep, the more cathodic the waterline area and more is the
rate of corrosion just below the water line.

At anode Fe Fe2+ + 2e-

At cathode O2 + 2H2O + 4e- 4OH-

ii) Pitting corrosion:

Pitting corrosion occurs when small particles like dust, mud etc get deposited on metals surface. The portion
of metal covered by the dust or other particles is less aerated and acts as anode. The other portion of the
metal exposed to more oxygen of the environment act as cathodic region. Corrosion takes place at the
portion below dust and a small pit is formed. Once a pit is formed, the corrosion progresses rapidly. This is
because of the formation of small anodic area (pit) compared to a large cathodic area (surface). The latter
induces the small anodic area to corrode faster by accepting electrons from the anodic area.

At anode Fe Fe2+ + 2e-

At cathode O2 + 2H2O + 4e- 4OH-
Corrosion control:-
INORGANIC COATINGS: Surface Conversion Coating
Inorganic coatings are surface conversion coatings or chemical conversion coatings. In this method
outer surface of the base metal is converted into protective coating through chemical reactions.
Example: Anodizing ,Phosphating.
ANODIZING: Anodizing is a process of artificially forming protective passive oxide film on the surface of
metals such as Al, Mg, Ti, Zr, Ta, Cr, etc by electrochemical oxidation.

ANODIZING OF ALUMINIUM:
In anodizing of aluminum, the article (aluminium) is cleaned,
degreased, polished and taken as anode in an electrolytic cell.
It is immersed in an electrolyte consisting of 5-10%
chromic acid. Steel or copper is taken as cathode.
Temperature of the bath is maintained at 35°C. A current
density of 100 Acm-2 or more (or applied potential 0-40 V) is
applied which oxidizes outer layer of Al to Al2O3 that gets
deposited over the metal. The passivity of aluminium is due
to the formation of a thin and compact layer of
aluminium oxide over the metal. This phenomenon is
known as anodizing or anodic oxidation or anodic passivity.

Uses: Anodized articles are used as an attractive, highly durable and corrosion resistant material in ceilings,
floor, escalators, lobbies, staircase, curtain walls, tiffin carriers, soapboxes, household utensils, window
frames, exterior for roofs, walls, buildings and in many home appliances. Anodized aluminium is also used
in computer hardware, exhibit displays, scientific instruments and in a range of home appliances and
consumer products.

METAL COATINGS:-

Deposition of protective metal over the surface of base metal is known as metallic coatings.
It is divided into anodic metal coatings and cathodic metal coatings.

a) Anodic metal coatings:

Anodic metal coatings are coatings which are anodic to the base metals. Examples are
aluminium, magnesium, zinc, and cadmium coatings on iron. These metals are above iron in the galvanic
series and undergo corrosion thereby protecting iron. A characteristic feature of anodic coatings is that the
base metal on which the coating is done will not get corroded even if the coating peals off. This is due to the
formation of large anodic and small cathodic areas.
Example: Galvanizing.
 Galvanizing (Zinc coating on iron):

The process of coating a layer of zinc on iron by hot dipping is called as galvanizing. It
involves the following steps,

1) Iron sheet is passed through organic solvent to remove oil or grease present on it.
2) Then it is washed with dil.H2S04 (pickling) to remove any rust (oxide layer) present on the surface '
3) Then it is treated with a mixture of aqueous solution of zinc chloride (ZnC12) and ammonium
chloride (NH4Cl) which acts as flux and then dried.
4) The treated sheet is dried and dipped in molten zinc at 430-470 ºC.
5) Excess zinc present on iron sheet is removed by rolling, wiping or passing blast of air.

Uses: Galvanization is used for roofing sheets, buckets, bolts, nuts, nails, pipes etc.

Galvanizing and tinning by hot dipping is more economical than electroplating. Hot dipping is
limited to the coating of low melting point metals like Zn, Sn and Al over iron.

CATHODIC PROTECTION:-

Cathodic protection is a method in which the base metal to be protected from corrosion is made to
act as cathodic by attaching more active anodic metal to it. The active anodic metal undergoes corrosion and
base metal is protected from corrosion.
The following methods are used to protect metal from corrosion.
Example: a) Sacrificial anodic protection method b) Impressed voltage method

a) Sacrificial anodic protection method-

In this method, metallic material to be protected is
connected to a more active metal (anodic metal).
Anodic metals like Zn or Mg can be employed to
protect iron articles. When an anodic metal is in
contact with iron specimen; a galvanic cell is set up,
where anodic metal becomes anodic area and whole
iron article becomes cathodic area. Anodic metal
undergoes oxidation and provides electrons to the
specimen. Hence the entire specimen becomes
cathodic and thus protected from corrosion. In the
process, anodic metal undergoes corrosion and
sacrifices itself to protect the specimen; therefore it
is called as sacrificial anode. Sacrificial anodes have
to be replaced in due course of time.
b) Impressed voltage method:
In this method, the electrons are supplied from a
source of direct current (dc). Metal structure to be
protected is connected to negative terminal of a dc
source. The positive terminal of dc source is connected
to inert anode like graphite to complete the circuit.
Potential greater than potential of anodic reaction is
applied in the reverse direction to prevent anodic
reaction. Thus, whole metal becomes cathodic and hence
protected from corrosion.
 Corrosion testing by weight loss method

Corrosion Penetration Rate (CPR)

The Corrosion penetration rate is the speed at which any metal or alloy deteriorates in a specific
corrosive environment through chemical or electrochemical reactions. It is also defined as the
amount of weight loss per year in the thickness of metal or alloy due to corrosion. The Corrosion
penetration rate also referred as corrosion rate.
Corrosion penetration rate depends on following factors;
1. Nature of metal.
2. Nature of corrosive environment/medium.
3. Nature corrosion product.
4. Speed at which corrosion spreads in the inner portion of metal.
The Corrosion penetration rate is calculated using the following formula;

Where,
W is weight loss after exposure time.
T is exposure time in corrosive medium.
D is the density of metal or alloy.
A is surface area of exposed specimen.
K is constant.
The CPR is conveniently expressed in terms of either mils (0.001 inch) per year (mpy) or
millimeters per year (mmpy). K=534 to give CPR in mpy when surface area of test specimen is in
inch2 and K=87.6 for CPR in mmpy when surface area of test specimen is in cm 2
Where, 1 mil =0.001 inch
CPR in mpy CPR mmpy
K 534 87.6
W (wt loss) mg mg
(D)ρ g/ cm3 g/ cm3
A inch2 cm2
t hrs hrs

****Follow regular class notes for Numerical Problems on CPR

MODULE-3:
Analytical Techniques: Introduction, principle and instrumentation of Conductometry; its
application in the estimation of weak acid. Potentiometry; its application in the estimation
of iron.

ANALYTICAL TECHNIQUES:
Analytical chemistry deals with the qualitative and quantitative characterization of a material or
materials. The chemical analysis deals with method of identification, quantification and
determination of molecular structure of a substance. In chemical analysis, the first step involves
identification of a compound or compounds in a mixture. This is called qualitative analysis. The
next step is to determine the amount of the element or substance present in the sample. This is
called quantitative analysis.

The quantitative analysis can be classified into two types, depending upon the method of analysis.

i. Chemical methods of analysis (classical)

ii. Instrumental methods of analysis (modern)

Chemical methods of analysis involve gravimetric and volumetric analysis. Gravimetric

analysis is the quantitative estimation by weight. The volumetric or titrimetric analysis involves
the determination of the volume of a solution of known concentration, which is required to react
quantitatively with a measured volume of a solution of the substance to be determined. The main
limitations of these methods are time consuming procedures, lack of versatility and lack of
accuracy when small quantities of substances are involved.

In instrumental methods of analysis, a physical property of a substance is measured to

determine its chemical composition. For example, colorimetry, potentiometry, conductometry,
AAS and flame photometry. The advantages of instrumental methods are that these methods are
much faster than the chemical methods, applicable at lower concentrations, find wide
applications in industries and the analytical process can be automated.

The main limitations of these methods are that these instruments are expensive, an initial or
continuous calibration is required, the concentration range is limited and a specialized training is
needed for the operation of certain sophisticated instruments.

Instrumental methods of analysis can be classified into two types:

1. Electroanalytical methods: involve the measurement of current, voltage or resistance in

relation to the concentration of a certain species in solution. Examples: potentiometry,
conductometry, voltammetry etc.,
2. Optical methods: are based on, how the sample acts towards the electromagnetic
radiation.
CONDUCTOMETRY:
Conductance is ease with which current flows through the solution. It is reciprocal of resistance.
C=1/R = Ω-1 or mho or Siemens.

Theory or Principle: The Conductance of the solution is explained by considering ohm’s law.
According to ohm’s law the current flowing through the conductor is directly proportional to
voltage and inversely proportional to the resistance.
I= or E = I R
The resistance of the any conductor is directly proportional to the length of inversely
proportional to the area of cross section of the conductor
Therefore R = S (l/a) where S is specific resistance
Therefore C = 1/R = 1/S (a/l), K (a/l), K = specific conductance
The conductance of the solution is depends on mobility of the ion and number of the ion.
Types of conductance: There are three type’s namely specific conductance, equivalence
conductance, and molar conductance.
Specific conductance (K) is conductance of the solution which are placed between two
electrodes of area 1cm2 and at 1cm apart
K = 1/R (l/a) K = Siemen m-1
Equivalence conductance (λ) is the conductance of the solution when 1g equivalent weight of
solution is placed between two electrodes of area 1cm2 at 1cm apart.
Molar conductance (µ) is the conductance of the solution when 1g molecular weight of solute is
placed between two electrodes of area 1cm2 at 1cm apart.

Conductance measurements are used to determine the equivalence point in acid-base titrations.
There is a sudden change in conductance of the solution after the equivalence point.

Instrumentation: It consists of two platinum electrodes each of unit area of cross section placed
unit distance apart. The electrodes are dipped in the electrolyte solution taken in a beaker. It is
connected to a conductance measuring device. The titrant is added from a burette and the
solution is stirred. The conductance is measured after the addition of titrant at intervals of 0.5
mL.
Applications of Conductometry: Explain the nature of conductometric graph for the following
titrations

Weak acid v/s Strong base

Ex: CH3COOH vs NaOH
Consider the titration of acetic acid against NaOH.
The conductance of the acid will be initially low since acetic
acid is a weak electrolyte. When NaOH 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 increases in the number of mobile OH - ions. Hence
the conductance increases sharply.
CH3COOH+ NaOH CH3COONa + H2O
A plot of conductance against the volume of base added is shown in the figure. The point of
intersection of two curves gives the neutralization point.

Calculation:

Normality of NaOH = 1.0 N

Volume of weak acid (CH3COOH) taken = 50 cm3

Volume of NaOH required to neutralize CH3COOH (V1) = _ _ cm3

Normality of CH3COOH = NNaOH × (V1) = N (a)

Volume of weak acid

Weight of CH3COOH/dm3 = NCH3COOH x Eq. Wt. of CH3COOH = b×60.05 = g/dm3

Result:

Volume of NaOH required to neutralize CH3COOH (V1) = _ _ cm3

Weight of CH3COOH/dm3= g/dm3

Strong acid v/s strong base

Ex: HCl v/s NaOH
If the strong acid like HCl is titrated against a strong base such
as NaOH, the conductance first decreases due to replacement
of fast moving H+ ions by slow moving Na+ ions
HCl + NaOH NaCl + H2O
After the neutralization point, conductivity rapidly rises with further addition of NaOH because
of continuous addition of fast moving OH- ions. A plot of conductance against the volume of
base added is shown in the figure. The point of intersection of two curves gives the neutralization
point.
Mixture of strong acid and weak acid v/s strong base

HCl, CH3COOH v/s NaOH

the strong acid like HCl is titrated against a strong base
such as NaOH, the conductance first decreases due to
replacement of fast moving H+ ions by slow moving Na+
ions
HCl + NaOH NaCl + H2O

The weak acid do not get neutralized initially

because of the well known common ion effect.
In the presence of excess of H+ ions, the ionization
of the weak acid is suppressed and hence, weak acid
like CH3COOH ionizes gradually after the first end point and the available H + ions are
neutralized giving the second end point. Because of common ion effect dissolution of acetic acid
is suppressed. Hence it does not provide H + ions which required for neutralization.

CH3COOH+ NaOH CH3COONa + H2O

After the neutralization point of HCl, CH3COOH, conductivity rapidly rises with further addition
of NaOH because of continuous addition of fast moving OH - ions. A plot of conductance against
the volume of base added is shown in the figure. The point of intersection of two curves gives
the neutralization point.

Advantages of conductometric titrations:

 Mixture of acid can be titrated
 Indicators are not used
 Very weak acids can be titrated
 Can be used with colored solution
 Suitable for turbid solution also.

POTENTIOMETRY:
Principle: Potentiometry is an electroanalytical technique in which the amount of a substance in
solution is determined, either directly or indirectly, from measurement of the EMF between two
electrodes that are dipped into the solution. When a metal M is immersed in a solution containing
its own ions, Mn+, the electrode potential is given by Nernst equation,
E  E0 
2.303RT
 
.log M n
nF
E can measured by combining the electrode with a reference electrode and measuring the emf of
the cell. The concentration can be calculated, provided E 0 of the electrode is known.

Redox titrations can be carried out potentiometrically using platinum and calomel electrode
combination in a manner similar to acid-base neutralizations. For the reaction
Re duced form  Oxidised form  n electrons

The potential is given by Nernst equation

0.0591
E  Eo  log [Oxidised form]
n [Re duced form]

0.0591 [Fe3]
E  Eo  log
n [Fe2]

Where E0 is the standard potential of the system. The potential of the system is thus controlled
by the ratio of concentration of the oxidized to that of the reduced species present. As the
reactions proceed the ratio increases and hence the potential also increases more rapidly in the
vicinity of the end point of titration. A plot of change in potential against volume is characterized
by a sudden change of potential at the equivalent point. At the end point potential is determined
by a large increase in potential at the end point

Instrumentation: A potentiometer consists of an indicator electrode (e.g.: Platinum), A standard

reference electrode (E.g.: Calomel electrode), & potentiometer to read the values directly as
change in potential. The, electrode whose potential is dependent upon the concentration of the
ion to be determined is termed as the indicator electrode. It responds to change in concentration
of the analyte species present in the solution, in which it is in contact with.

Procedure: Pipette out 25.0 cm3 of ferrous ammonium sulphate solution into a beaker. Add a
test tube of dilute sulphuric acid. Immerse the platinum-calomel electrode assembly into the
beaker containing the solution. Connect the electrodes to the potentiometer. Note down the emf
of the cell before the addition of K2Cr2O7. Now add 0.5 ml of K2Cr2O7 from the semi micro
burette. Allow the solution to mix well and measure the potential. Continue the procedure till a
sudden rise in emf of the cell is observed. Take about 5-6 more readings.
Vol.of K2Cr2O7 Emf E ∆V ∆E ∆E / ∆V

(V) ml (mv) (V2-V1) ml (E2-E1) (mv/ml)

E
Determine the end point by plotting V against the

volume as shown in the figure.

( N V )K Cr O
N FAS  2 2 7

VFAS

Amount of FAS per liter  NFAS Eq. Wt.of FAS (392)

 .................. g (say ' a ' )

392 g of FAS contains 55.85 g Fe

55.85  a
a g of FAS contains
392

 .................. g

Result: Normality of the given FAS solution = N

Weight of FAS / ltr = g/ltr.
Weight of Fe present in one liter = g/ltr.

Applications:
1. Coloured solution can also be titrated.
2. Acid-base titration can also be done in this method.
3. In this method Oxidation-reduction titrations can also be carried out.
4. Precipitation reactions can also be carried out potentiometrically.
5. Potentiometric titrations does not depend on the color change
6. Several analytes present in the same solution can be estimated by a single titrating
solution
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