MODULE-III

CORROSION AND ELECTRODE SYSTEM

CORROSION
Introduction
Corrosion is defined as the destruction and consequent loss of metals through chemical or
electrochemical attack by the environment.
Ill effects of corrosion

 Contamination of product
 Damage of metallic equipments.
 Inability to use metallic materials
 Lose of valuable materials such as blockage of pipes, mechanical damage of underground
water pipes
 Accidents due to mechanical loss of metallic bridges, cars, aircrafts etc.

Global losses of corrosion

 Efficiency loss.
 Equipment shut down due to corrosion failure and cost of replacing the corroded
equipment
 Sudden failure of equipment due to corrosion can cause an explosion, fire, release of a
toxic product, and/or construction collapse which challenges the safety measures.

 An escaping product from corroded equipment or corrosion product itself can cause
pollution hence may result serious health problems.

Electrochemical Theory of Corrosion:

Principle: According to electrochemical theory, corrosion of the metal take place due to the
formation of anodic and cathodic regions on the same metal surface in the presence of a
conducting medium. At the anodic region oxidation reaction takes place and the metal gets
corroded into ions liberating the electrons. Consequently, metals undergo corrosion at the anodic
region. At the cathodic region reduction reaction takes place. Metal ions in the cathodic region
are unaffected by the cathodic reaction.

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 The electrons liberated at the anodic region migrate towards the cathodic region
constituting corrosion current. The metal ions liberated at the anode and some anions formed at
the cathode region diffuse towards each other through the conducting medium and form a
corrosion product somewhere between the anode and the cathode. Corrosion of metal continues
as long as both the anodic and cathodic reactions take place simultaneously.
Corrosion reactions:
At the anodic region:
At anodic region, iron is liberating Fe2+ ions and electrons,
Fe →Fe2+ +2e-
At the cathodic region:
The chemical species present in the surrounding of cathode under goes reduction by accepting
electrons coming through metal from the anodic region. Depending on the surrounding medium,
there are four possible reduction reactions at the cathodic region,
1) Hydrogen liberation takes place in the absence of oxygen.
(a) In acidic medium and in the absence of oxygen the cathodic reaction is
2H++2e-→H2↑
(b) In neutral or alkaline medium and in the absence of oxygen, hydroxide ions are
formed with simultaneous liberation of hydrogen
2H2O+2e- →2OH─+ H2
2) Absorption of oxygen takes place in the presence of oxygen.
(a) In acidic medium and in the presence of oxygen
2H+ +1/2O2 +2e- →H2O
(b) In neutral or alkaline medium and in the presence of oxygen hydroxide ions are
formed by the following reaction.
H2O+1/2O2 +2e- →2OH─
Corrosion of iron produces Fe2+ and OH─ ions at the anode and cathode sites respectively.
These ions diffuse towards each other to produce insoluble Fe (OH)2.
Fe2++2OH─→ Fe (OH) 2
. In an oxidizing environment it is oxidized to ferric oxide and the yellow rust is hydrated
ferric oxide.
4 Fe (OH) 2+ O2+2H2O →2 [Fe2O3. 3H2O] (rust)

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 In the presence of limited oxygen ferrous oxide is converted into magnetic oxide of iron
(Fe3O4) and is known as black rust.
3 Fe (OH) 2+1/2 O2→ [Fe3O4. 3H2O] (black rust)

Types of Corrosion:
(1) Differential metal corrosion (Galvanic corrosion)
(2) Differential Aeration corrosion
1. Differential metal Corrosion
Definition: When two dissimilar metals are in contact with each other a potential difference is
set up resulting in a galvanic current.
Principle: The two metals differ in their 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 unattacked.
At the anode), Fe→ Fe2+ + ne-
At the cathode H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

Process: When two metals having different electrode potentials are in contact with each other in
the presence of an electrolyte, one metal acts as a cathode whereas the other acts as an anode.
This leads to an electrochemical reaction as a result of which, the anode is dissolved into the
electrolyte. Galvanic corrosion can only occur when there exists an electric conducting path

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connecting the metals and when an electrolyte which can offer a channel for the migration of
ions is present.

Differential Metal Corrosion

Examples:
(1) Steel pipes joined to Copper plumbing, undergo galvanic corrosion, since Steel acts as the
anode.
E0Fe+2/Fe = - 0.44 V E0Cu+2/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.

2. Differential Aeration Corrosion

Differential aeration corrosion occurs when a metal surface is exposed to differential air
concentrations of Oxygen concentrations. 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 cell
due to uneven supply of air on the metal surface is known as differential aeration corrosion.
At the anode (less O2 concentration), Fe → Fe2+ + ne-
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O → [Fe2O3. 3H2O] (rust)

Eg.:- 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.

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 3. Metal under dirt, dust, scale or water undergoes corrosion.
Water line Corrosion:
Principle: Water line corrosion is a case of differential aeration corrosion. The water line
corrosion takes place due to the formation of differential oxygen concentration cells. The part of
the metal below the water line is exposed only to dissolved oxygen (acts as anode) while the part
above the water is exposed to higher oxygen concentration (acts as cathode) of the atmosphere.
A distinct brown line is formed below the water line due to deposition of rust.
At the anode (less O2 concentration), Fe → Fen+ + ne
At the cathode (more O2 concentration), H2O + ½ O2 + 2e- → 2OH-
Fe2++2OH─→ Fe (OH) 2
2Fe (OH) 2+1/2O2+H2O →[Fe2O3. 3H2O] (rust)

Water - line Oxygen

Cathode

Corroded part (anode)

Examples:
(1) Ships that are left in the water for extended periods of time can be at risk of waterline
corrosion.
(2) Steel water tanks in which water is stored for a long period.

Corrosion Control
(a) Galvanisation
Galvanisation is a process of coating a base metal surface with Zinc metal. It is an anodic
coating which is produced by coating a base metal with more active metals which are anodic to
the base metal. Eg.: Iron is coated with anodic and active metals like Zn, Mg, and Al.
Galvanisation is carried out by hot dipping method.

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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.
One advantage of gavanisation is that, even if the coating is ruptured, the base metal does not
undergo corrosion. The exposed surface of the metal is cathodic with respect to zinc. Therefore,
galvanisation is also known as sacrificial coating.
(b) Anodization
Anodization is generally produced on nonferrous metals like Al, Zn, Mg and their alloys
by anodic oxidation process. It is a type of inorganic coating where 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
In anodization of aluminium, clean, polished aluminium is taken as anode and immersed
in an electrolytic cell containing chromic acid. Inert electrodes like lead is generally used as
cathode. The anodic oxide film formed on Al in bath as aluminium oxide, which is porous. The
pores are finally sealed by dipping in hot water to produce Al2O3 .H2O, which acts as a non-
porous protective layer preventing corrosion.
Anode reaction: 2Al + 3H2O → Al2O3 + 6H+ +6e-
Cathode reaction: 6H+ + 6e- → 3H2

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(c) Sacrificial anode method:
In this method, the protected metal structure is converted into a cathode by connecting it
to a more active metal. This active metal acts as an auxillary anode Zn, Mg and Al are the
common auxillary 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.
Eg.;1. A magnesium block connected to a burried oil storage tank
1. Mg bars are fixed to the sides of ocean going ships to act as sacrificial anodes.
2. Mg blocks are connected to buried pipe lines.

Anodic Reaction : Mg → Mg2+ + 2e

Cathodic Reaction : ½ O2 + H2O + 2e →2OH-

Mg
Under
ground Mg Mg
steel Pipe line
tank

(a) (b) (c)

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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;

CPR =

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.
Numerical Problem on CPR:
1. A thick steel sheet of area 400 cm2 is exposed to air near the ocean. After one-year period it
was found to experience a weight loss 375 g due to corrosion. If the density of the brass is
7.9 g/cm2 calculate the corrosion penetrating rate in mpy and mmpy (given K= 534 in mpy
and 87.6 in mmpy).
To calculate CPR in mmpy:

Given CPR in mmpy

K 534 87.6

W (wt loss) 375 g 375 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

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 A 400 cm 2 400 cm 2
t 1 year 1 x 365 x 24 hrs

CPR =

CPR =1.186 mmpy

To calculate CPR in mpy :

Given CPR in mpy

K 534

W (wt loss) 375 g 375 x 1000 mg

Ρ 7.9 g/ cm3 7.9 g/ cm3

A 400 cm2 400 X 0.155 inch2

T 1 year 1 x 365 x 24 hrs

(1 cm2 = 0.155 inch2)

CPR =

CPR = 46.67 mpy

2) Calculate the CPR in both mpy and mmpy for a thick steel sheet of area 100 inch2 which
experiences a weight loss of 485g after one year. (Density of steel=7.9g/cm3).

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 To calculate CPR in mmpy :

Given CPR in mmpy

K 534 87.6

W (wt loss) 485 g 485 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

A 100 inch 2 100 X 6.45 cm 2

t 1 year 1 x 365 x 24 hrs

1inch2=6.45cm2

= 87.6 X 485 X 1000

7.9 x 100 x 6.45 x 365 x 24
=
= 0.9518 mmpy

To calculate CPR in mpy :

Given CPR in mpy

K 534 534

W (wt loss) 485 g 485 x 1000 mg

ρ 7.9 g/ cm3 7.9 g/ cm3

A 100 inch 2 100 inch 2

t 1 year 1 x 365 x 24 hrs

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 534 X 485 X 1000
7.9 x 100 x 365 x 24
= 37.424 mpy

ELECTRODE SYSTEM
Introduction

An Electrode can be defined as the point where current either enters or leaves the electrolyte or
circuit. When the current leaves the Electrode it is known as the cathode while when the current
enters the Electrode it is known as an anode.
Electrodes are the main component of electrochemical cells. An Electrode must be a good
conductor of electricity.

Types of electrodes:

1. Metal-metal ion electrode:

An electrode of this type consists of a metal dipped in a solution containing its own ions
eg:Zn/Zn2+, Cu/Cu2+
2. Metal-metal salt ion electrode: (Metal-insoluble salt electrode):
These electrodes consist of a metal in contact with a sparingly soluble salt of the same
metal dipped in a solution containing anoin of the salt.
Eg: Calomel Electrode (Hg/Hg2Cl2/Cl-)
Silver-silver chloride electrode (Ag/AgCl/Cl-)
Lead-lead sulphate electrode (Pb/PbSO4/SO42-)
3. Gas electrode:
Gas electrodes consist of a gas bubbling about an inert metal wire or foil, immersed in a
solution containing ions to which the gas is reversible.
Eg: H2 electrode (Pt/H2/H+)
Chlorine electrode (Pt/Cl2/Cl-)
4. Amalgum electrode:
Amalgum electrode is similar to metal-metal ion electrode except for the fact that in an
amalgam electrode, metal-amalgum is in contact with a solution containing its own metal
ions.
Eg: Lead amalgam electrode (Pb-Hg/Pb2+)
5. Oxidation- Reduction electrode:

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 An oxidation-Reduction electrode is the one in which the electrode potential arises from
the presence of oxidized and reduced forms of the same substance in solution. The
potential arises from the tendency of one form to change onto the other more stable form.
The potential developed is picked up by inert electrode like platinum.
Eg: Pt/Fe2+,Fe3+
6. Ion selective electrode: (Membrane electrode):
hichititcan
IN an ion selective electrode, a membrane is in contact with a solution, with which can
exchange ions.
Eg: Glass electrode: (exchanges H+ ions with the solution)
Ion Selective Electrode

Definition: Ion-selective electrode is one, which selectively responds 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:

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When two solutions of different hydrogen ion concentrations, ie 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:
The glass electrode consists of a glass bulb made up of a special type of glass with high electrical
conductivity. The composition of the glass membrane is approximately 22% Na2O, 6% CaO, and
72% SiO2. The glass bulb is filled with a solution of known pH (0.1M HCl) and is inserted with
an Ag-AgCl electrode, which is the internal reference electrode and also serves for the external
electrical contact. The electrode is dipped in a solution whose pH is to be determined (containing
H+ ions).
The glass electrode system can be represented as follows:
Ag/AgCl(s)/0.1MHCl/glass
When dipped in a solution of unknown pH, it can be represented as,

The glass membrane exchanges ions with the solution

H+(solution) + Na+Gl (glass) Na+(solution) + H+Gl(glass)

The exchange of ions by the inner and outer membrane gives rise to a boundary potential. This
boundary potential consists of two potential E1 and E2, which are associated with the outer and
inner membrane respectively.

Therefore,
From thermodynamic consideration it has been shown that E1 and E2 are related to the hydrogen
ion activities at each face, by Nernst like equation,

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Where j1 and j2 are constants and a1 and a2 are activities of H+ in the outer and inner solution
respectively, a11 and a21 are the activities of H+ ions at the external and internal surface of the
glass membrane.
Since the glass at the inner solution and outer membrane are identical, j1 = j2 and also a11 = a21

Then (n = 1 for H+ ions)

Thus the boundary potential Eb depends only upon the hydrogen ion activities of the solutions.
Since the concentration of the inner solution is constant, a2 is constant. The above equation

simplifies to,

Where L1 = −0.0591, loga2 = −0.0591logC2

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
(iii) A small asymmetry potential

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Where is a combination of three constant terms.

Asymmetric potential arises due to the difference in response 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 known H+ activity (pH).

Applications

 Glass electrodes have been utilized in a wide range of applications including pure
research, control of industrial processes.
 Analysis of foods and cosmetics.
 measurement of environmental indicators, and microelectrode measurements such as cell
membrane electrical potential.

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:

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Hg  Hg2Cl2 (paste) Sat. KCl  experimental solution  glass membrane 0.1M HCl AgCl Ag
 In the above cell, the glass electrode behaves as cathode and calomel electrode as anode.
 The cell potential may be determined using electronic potentiometer.
 The EG0 is obtained by repeating the experiment using the solution of known pH.
 The pH value of the experimental solution can be calculated by substituting the values of
Ecell, Ecalomel and EG0 in the following relation:

0.0591pH = E0G – ESCE - Ecell

Reference electrode:

The absolute value of single electrode potential cannot be measured since the metal and its
ions are in equilibrium. We can only measure the potential difference between two electrodes.
This can be done by choosing a reference electrode whose electrode potential is arbitrarily fixed
or known. This reference electrode can be combined with other electrodes to form a galvanic
cell. From the measured cell potential we can calculate the electrode potential of any particular
electrode, with reference to the reference electrode.
Definition: Reference electrode is an electrode whose electrode potential is arbitrarily fixed or
known and is reliable.
This can be used to measure the electrode potentials of other electrodes by constructing a
galvanic cell using the electrode tend the reference electrode.
Two types of reference electrodes:
1. Primary reference electrode, Example: Hydrogen gas electrode
2. Secondary reference electrode, Example: Calomel electrode and silver-silver electrode
Limitations of Primary Reference Electrode (Standard hydrogen electrode):
1.The equilibrium between the two processes is not reached quickly.
2.It is difficult to control the pressure of hydrogen gas at 1 atm.

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 3.The electrode cannot be easily setup.
4. The electrode gets poisoned by impurities

Secondary Reference Electrodes:

For the sake simplicity and to overcome the above difficulties, there was a need for the
development of secondary reference electrodes. The potentials of these electrodes are known on
the hydrogen scale and are used in place of hydrogen electrode. These electrodes can be easily
set up.

Calomel electrode:

Construction and working:

It is a metal-insoluble salt electrode, where metal in contact with its insoluble salt and the
solution contains the anion of the salt.
Electrode representation: Hg(s)Hg2Cl2 (paste);Cl-
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 KCl. 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)  Hg2+2 +2e-
Hg2+2 +2Cl- Hg2Cl2(s)

2Hg (l) +2Cl- Hg2Cl2(s)+2e-

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

Hg2+2 +2e-2Hg (l)
Hg2Cl2(s)Hg2+2+2Cl-

Hg2Cl2(s) +2e- 2Hg(l)+2Cl-

The electrode potential may be represented by the Nernst equation as

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 at 298K

E = E 0  0.0591 logCl   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
For saturated KCl E=0.2422V (called Saturated calomel electrode)
Uses: It is used as a secondary reference electrode in the measurement of single electrode
potential. It is the most commonly used reference electrode in all potentiometric determination.
Applications
 Calomel electrode is used in cyclic voltammetry to study the electrochemical properties
of an analyte in solution or of a molecule that is adsorbed onto the electrode.
 General aqueous electrochemistry.
 For pH measurement in all practical and research fields.
Concentration cells:
Definition: Concentration cells are those in which both the anode and the cathode are made up
of the same element (metal or nonmetal) in contact with the solutions of the same electrolyte, but
of different concentrations.
Eg: A cell in which the electrodes are made up of zinc metal dipped in ZnSO 4 solutions of
different concentrations C1 and C2. The cell is represented as:
Zn / Zn2+ (C1) // Zn2+ (C2) / Zn

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At the anode zinc gets converted into Zn2+ ions and goes into the solution liberating two
electrons.

At the anode: Zn(s) → Zn2+ (C1) + 2e-

At the cathode Zn2+ ions are deposited as zinc metal.

At the cathode: Zn2+ (C2) + 2e- → Zn(s)

There is no net cell reaction. At one electrode zinc atoms go into the solution and at the equal
number of zinc atoms are deposited. The emf of the cell is given by,

Ecell = Ecathode - Eanode

logC 2cathode  E 0  logC1anode

2.303RT 2.303RT
Ecell  E 0 
nF nF

2.303 RT 2.303 RT
E cell  log(C 2 )  log(C 1 )
nF nF

2.303 RT C  0.0591  C 2 
E cell  log 2  (or) E cell  log  ; at 298 K
nF  C1  n  C1 

It is evident from the above expression that Ecell can be positive only if C2>C1.
Thus in a concentration cell, the electrode with lower electrolyte concentration acts as the anode
and the one with higher electrolyte concentration acts as the cathode. The concentration of ions
increases at the anode and decreases at the cathode when cell is in operation. The emf of the cell
is dependent on the ratio of electrolyte concentrations at two electrodes. Higher the ratio (C2/C1),
higher is the emf. Therefore, the cell can operate only as long as the concentration terms are
different. When the current is drawn from the cell, C1 increases and C2 decreases and as a result
the emf of the cell goes on decreasing and becomes zero when the two becomes equal.

Numerical Problems

1) The cell potential of Cu concentration cell Cu I Cu 2+(0.0093 M) II CuSO4 (X) I Cu is 0.086 V

at 25o C. Write cell reactions and calculate the value of X.

Equation to be used is E = 0.0591 𝑛 log

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0.086 = 0.0591 x 2 x log

x =0.0093M

2) The cell potential of Cd concentration cell Cd I Cd2+(XM) II CdSO4(0.025 M) I Cd is 0.035

V at 28o C. Calculate the value of X.

Equation to be used is E= 0.0591𝑛 log 𝐶2/𝐶1

0.035= 0.05912 log 0.025/𝑥

x =0.0016M

Analytical Techniques
Analytical techniques are the techniques involved in the study of separation, identification and
quantification of chemical components of materials. Qualitative analysis and quantitative
analysis are the analytical techniques used to determine the identity of chemical species and
amount or concentration of species present in the sample respectively.

Instrumental methods use simple or advanced instrument to measure physical quantities of

analyte by relating concentration with light absorption, fluorescence, conductivity or potential.
Some of the important instrumental methods of analysis are discussed below.

1. Conductometric titrations
Principle:
According to Ohm’s law, current (i) flowing in a conductor is directly proportional to emf (E)
and inversely proportional to resistance (R).

E
Therefore, i =
R

The reciprocal of resistance is conductance. It is expressed in ohm-1,mho

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Or Siemen. The resistance of a homogeneous material of uniform cross section with an area of
‘a’sq.cm and length ‘l’ cm is given by,

x l is specific resistance

R =
a

The reciprocal of specific resistance is specific conductance

Specific conductance:
Specific conductance is the conductance of a solution present between 2 parallel electrodes of
area 1cm2 which are kept 1cm apart.

1 l l
K= X a = cell constant
R a

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.
Equivalent conductance is defined as the conductance of a solution containing one gram
equivalent weight of the electrolyte. It is denoted as γ. Molar conductance is defined as the
conductance of a solution containing one mole of an electrolyte. It is denoted as μ.
Instrumentation:
It consists of two platinum electrodes of unit area of cross-section placed unit distance apart. The
electrodes are dipped in electrolyte solution taken in a beaker. It is connected to a conductance
measuring device. The titrant is added from the burette and the solution is stirred. The
conductance is measured after the addition of the titrant at intervals of 0.5ml.

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 To, conductometer

Stirrer

1cm2 Platinum electrode

1cm

Application
Titration of Weak acid v/s Strong base (Ex: CH3COOH Vs NaOH)
The conductance of the acid will be initially less since

conductance(mhocm-1)
acetic aided acid is a weak electrolyte. When NaOH is
added to the acid, the salt formed is highly ionized
because of this conductance increases.
CH3COOH + NaOH  CH3COONa + H2O equivalence point
After the neutralization point, further addition of base
volume of strong base
(NaOH) increases the fast moving OH- ions. Hence the
conductance increases sharply. 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.
2. Potentiometry
Principle:
Redox titrations can be carried out potentiometrically using platinum calomel electrode
combination in a manner similar to acid-base neutralizations. For the reaction,
Reduced form  Oxidised form + n e-
The potential is given by;
o 0.0591 Oxidizedform 
E  E 
n
log
Re ducedform
o 0.0591 
Fe3 
E  E 
n
log

Fe2 
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Where Eo is the standard potential of the system. The potential of the system is controlled by the
ratio of concentration of the oxidized and reduced form of the species present. As the reactions
proceed the ratio increases and reaches to a highest value at the end point.
Instrumentation:
To, potentiometer
Potentiometer consists of a reference
electrode (Saturated Calomel Electrode), Indicator electrode

an indicator electrode, and a potential Reference electrode

measuring device. The indicator Stirrer

electrode responds to the changes in

concentration of analyte. An emf is
measured at each time when titrant is added in the increments of 0.5 ml to a known volume of
analyte taken in the beaker. At equivalence point, emf increases rapidly and a few readings are
taken beyond the end point.
Application of potentiometry in the estimation of iron
Mohr’s salt is treated with 2 test of dil H2SO4. The calomel and platinum electrodes are dipped
and connected to a potentiometer.and the initial potential is measured. The burette is filled with
standard potassium dichromate solution. Added 0.5 ml of potassium dichromate solution to the
beaker, stirred well and the potential is measured. Potential is continuously measured by adding
0.5 ml increments of dichromate solution at a time. Initially the emf increases slowly and at the
equivalence point there will be a sudden jump in the emf. At least 5-6 readings are recorded
after equivalence point.
The end point is determined by plotting ∆E/∆V versus volume of potassium dichromate. The
volume of potassium dichromate corresponding to the peak of the curve indicates the end point.
From this the concentration and finally the amount of FAS, in turn amount of iron per litre is
determined.
Observations and Calculation:
Volume of Mohr’s salt pipetted out VFAS = 25 ml
Normality of K2Cr2O7, NK2Cr2O7 = 0.5 N

Vol. of
K2Cr2O7 in Emf (mv) ∆E ∆V ∆E/∆V
ml
0.0
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 0.5 0.5
1.0 0.5
1.5 0.5
2.0 0.5
2.5 0.5
3.0 0.5
3.5 0.5
4.0 0.5
4.5 0.5
5.0 0.5
5.5 0.5
6.0 0.5
6.5 0.5
7.0 0.5
7.5 0.5
8.0 0.5
8.5 0.5
9.0 0.5
9.5 0.5
10.0 0.5

E
V

Volume of K2Cr2O7 required for the reaction = ……………… (V eq) ml (determined from
graph)
Normality of FAS solution, NFAS = NK2Cr2O7 x VK2Cr2O7
-----------------------------------

VFAS

=--------------------------N

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Amount of FAS (iron) per litre = NFAS x Eq. wt. of FAS
= x 392

= -------------------- g

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