Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

MODULE-3

CORROSION AND ELECTRODE SYSTEMS

3.1 Introduction

A wide variety of metals/alloys are used for the construction of bridges, buildings, large

houses and industries. These are having natural tendency to get tarnished or deteriorated by the

environment to which they are exposed.

Corrosion is a process which involves the interaction with ambient oxygen can cause the

formation of oxide layers via diffusion controlled growth. These may passivate the material against

further oxidation.

Corrosion can be defined as “The destruction or deterioration of metals or alloys by

the surrounding environment through chemical or electrochemical changes”.

In wet environment, aqueous corrosion can occur due to electrochemical processes which depend

upon metal ion transport and reaction. The following factors are influence corrosion rate

1. Metallic and electrolytic ion concentrations.

2. Ambient Temperature and pressure.

3. Presence of other metals.

4. Bacteria or active cells.

3.2 Types of corrosion

Corrosion may occur either in dry environment or in a wet environment (aqueous medium).

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

(a) Dry corrosion: It involves the direct interaction of metals with dry gases like O2, SO2, Cl2,

NOx etc. mainly through chemical reactions.

E.g.: The attack of metals by O2 to form an oxide layer over the surface

(Mg + ½ O2 MgO)

(b) Wet corrosion: It involves electrochemical attack on metals in aqueous environment. This

type of corrosion occurs when the metal comes in contact with a conducting liquid or when

two dissimilar metals are dipped partly in a solution. E.g.: Rusting of iron.

NOTE: Wet corrosion can be explained on the basis of electrochemical theory

3.3 Electrochemical theory of corrosion

According to electrochemical theory, when a metal such as iron is exposed to corrosive

environment, following changes occur.

Schematic diagram of iron metal interact with corrosive environment

(a) Formation of galvanic cells: Anodic and cathodic areas are formed due to the formation of

minute galvanic cells.

(b) Anodic reaction: At the anodic area, Oxidation of metal takes place at the anodic region.

E.g.: Fe  Fe2+ + 2e-

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

(c) Cathodic reaction: The electrons travel through the metal from the anodic region to

cathodic region. There are three possible ways in which reduction can takes place.

1. If the medium is aerated and neutral, oxygen is reduced in presence of water to form OH -

ions.

O2 + 2H2O + ne- 4OH-

2. If the medium/solution is deaerated and almost neutral, water is reduced to H2 and OH-

2H2O + 2e- 2OH- + H2

3. If the medium is deaerated and acidic, the H+ ions are reduced to H2.

2H+ + 2e- H2

The metal ions which are formed at the anode that combines with the OH- ions to form the metal

hydride and finally the hydrated metal oxide (rust).

𝐅𝐞𝟐+ + 𝟐𝐎𝐇 − → 𝐅𝐞(𝐎𝐇)𝟐 ↓

𝟑
𝟐𝐅𝐞 (𝐎𝐇)𝟐 + 𝐎 + 𝐇𝟐 𝐎 → 𝐅𝐞𝟐 𝐎𝟑 . 𝟑𝐇𝟐 𝐎 (𝐑𝐮𝐬𝐭; 𝐛𝐫𝐨𝐰𝐧 𝐜𝐨𝐥𝐨𝐮𝐫)
𝟐 𝟐

3.4 Types of wet corrosion

a. Differential metal corrosion.

b. Differential aeration corrosion.

c. Stress corrosion. (not included in syllabus)

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

3.4.1 Differential metal corrosion

This type of corrosion occurs when two dissimilar metals are in contact with each other and

are exposed to a corrosive environment. The two metals differ in their electrode potentials. The

metal with lower electrode potential acts as anode and the other metal with higher electrode

potential acts as cathode.

The anodic metal undergoes oxidation and gets corroded. A reduction reaction occurs at

the cathodic metal. The cathodic metal does not undergo corrosion.

The reactions may be represented as follows

Cell reactions:

At anode : M Mn+ + ne- (Oxidation of metal M)

At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)

Higher the potential difference between the anodic and cathodic metals, higher is the rate of

corrosion.

E.g.: When iron is in contact with zinc, iron acts as cathode and zinc acts as anode because zinc

has lower electrode potential compared to iron. Therefore, zinc undergoes corrosion.

Zn metal Fe Metal

Anode Cathode
On the other hand, when iron is in contact with Cu, iron acts as anode because iron has lower

electrode potential compared to Cu. Hence iron undergoes corrosion.

Fe Anode Cu metal

Anode Cathode
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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Few examples are: Steel screws in copper sheet.

Steel screws with copper washer.

Bolt and nut made of different metals.

To generalize, when two metals are in contact with each other results in a formation of

galvanic cells and current produced. The metal acting as anode undergoes corrosion and the metal

acting as cathode is unaffected.

3.4.2 Differential aeration corrosion

It occurs when a metal surface is exposed to differential air concentration or oxygen

concentration. The part which is exposed to higher oxygen concentration acts as cathode and the

part that is exposed to lower O2 concentration acts as anode.

Consequently, the poorly oxygenated region undergoes corrosion. The reactions may be

represented as follows:

Cell reactions:

At anode : M Mn+ + ne- (Oxidation of metal M)

At cathode : O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)

Schematic diagram of iron metal rod partially immersed in water

Other few examples are

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

1) Part of the nail inside the wall undergoes corrosion.

2) When a dirt particle sits on a metal bar, the part under the dirt undergoes corrosion.

Typical examples of differential aeration corrosion are the water line corrosion and pitting
corrosion

3.4.3 Pitting corrosion

This is an example of differential aeration corrosion

Schematic diagram of iron metal interact with dust particles

These type of corrosion occurs when dust particles gets deposited on a metal surface. The

portion covered by the dust will be less aerated compared to the exposed surface. So the covered

portion becomes anodic with respect to the exposed surface. In the presence of electrolytes,

impurities and moisture corrosion starts beneath the dust resulting in a pit. Once the pit is formed,

the corrosion progress rapidly due to the formation of small anodic area and large cathodic area.

This is the localized form of corrosion.

3.5 Metal coatings: The process of deposition of protective metal over the surface of a base metal

is called metallic coating.

Metal coating are two types’ anodic metal coatings and cathodic metal coatings

Anodic metal coatings: These are the coatings which are anodic to the base metals. For example

Al, Mg, Zn and cadmium coatings on iron.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Galvanization is an example for anodic metal coating

Example: Galvanization: the process of coating a base metal surface (Fe) with zinc metal. This

process can be carried out through hot dipping method.

Schematic diagram of Galvanization through Hot dipping method

Galvanization involves following steps.

1. The metal surface is washed with organic solvents (CCl4, toluene) to remove organic
matter on the surface (Degreasing).

2. Rust and other deposits are removed by washing with dilute sulphuric acid.(Pickling
process).

3. Then article is washed with water and air-dried.

4. Finally article is then dipped in a bath of molten zinc. Temperature should be 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 that

wipe the excess zinc coating and produces a thin film coating.

Application: Galvanization of iron is carried out to produce roofing sheets, fencing wire, buckets,

bolts, nuts, pipes etc.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Note: 1. Even if the Zn coating falls off at some places, the base metal (Fe) does not get

corroded at those places. This is because the base metal acts as cathode. In corrosion

process, the cathodic metal always remains unaffected.

2. Galvanized articles are not used for preparing and storing food because zinc

dissolves in dilute acids producing toxic zinc compounds.

3.6 Surface conversion coating (Inorganic coatings)

These are generally chemical conversions 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.

3.6.1 Inorganic Coatings

In practice, there are two types of inorganic coating techniques (a) Anodizing (b)

Phosphating

Anodizing: Anodizing is process in which a protective passive oxide film is produced chemically

or electrochemically on certain metals (Al, Zn, Mg, Cr etc) in oxidizing acid bath.

Anodizing is a process of developing an oxide layer on the surface of metal by anodic

oxidation in an electrolytic cell. Metals such as Al, Ti, Mg, V and Zr are anodized in the presence

of electrolyte like chromic acid, sulphuric acid, oxalic acid or boric acid, by electrochemical

oxidation. This method is not applicable to ferrous and its alloys.

Anodization (Anodizing of aluminum)

Anodizing is applicable for non-ferrous metals such as Al, Mg Zn etc.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Schematic diagram of Anodizing of Al

1. The Al article to be anodized is first treated (washed) with organic solvents and polished to get

clean surface. It is used as anode.

2. Pb is generally used as cathode.

3. Both the electrodes are dipped in the 5-10 % chromic acid electrolytic solution (any acid

electrolyte /solution). The electrolysis is carried out by passing D.C voltage of 40 V at 35-40

˚C.

4. A thin oxide layer of aluminium (Al2O3) of 5-20 mm thickness is formed on the anode. This

oxide layer is slightly porous.

5. The strength of oxide layer formed is increased by dipping in boiling water. This treatment

changes the porous surface into a sealed surface by forming monohydrate of aluminium oxide

(Al2O3.H2O)

Reactions: At Anode 2Al + 3H2O Al2O3+ 6H+ + 6e-

At Cathode 6H+ + 6e- 3H2

Overall reaction 2Al + 3H2O Al2O3 + 3H2

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Applications

1. Anodized aluminium is used in manufacture of pressure cookers, aircrafts & window frames.

2. Anodized aluminium is used in office partitions.

3.7 Cathodic protection

It is a method of protecting a metal or alloy from corrosion by converting it completely into cathode

and no part of it allowed to act as anode. It can be achieved by

1. Sacrificial anode method.

2. Impressed current method. (not included in syllabus)

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 auxillary anode. Usually Zn, Mg

and Al are the common used as auxillary anodes. Moreover, these metals are active in nature which

acts as an anode and undergoes preferential corrosion by protecting the metal structure. Since the

anodic metals are sacrifices themselves for the protection of metal structure. Therefore this method

is called as Sacrificial anode method. Exhausted sacrificial anodes are replaced by new one, if it is

required.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Applications

1. It is used for protecting underground steel tanks with Mg blocks.

2. Mg bars are fixed to the sides of ocean-going ships to act as sacrificial anodes.

3. It is used for protecting buried iron pipe lines with Mg blocks.

3.8 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.

 The amount of corrosion loss per year in thickness.

 The speed at which corrosion spreads to the inner portions of a material.

Or

Note: 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.

Corrosion Penetration Rate (CPR) is mathematically expressed as

𝐊×𝐖
CPR= 𝛒 × 𝐀 × 𝐭

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

The CPR is conveniently expressed in terms of either mils per year (mpy) or millimeters per

year (mm/yr)

Where, 1 mil =0.001 inch

CPR in mpy CPR in mm/y

K 534 87.6
W (wt. loss) mg mg
ρ g/cc g/cc
A Inch2 Cm2
t Hrs Hrs

3.9 Problems on CPR

1. A sheet of carbon steel one meter wide by three meter long has lost 40 g to corrosion over the

past six months. Convert that mass loss to a penetration rate of the steel in mm units and mpy.

What would be the corrosion rate? (Carbon steel density = 7.8 g/cc)

To calculate the CPR in mm/yr

Given CPR in mm/yr
K 87.6
W 40 g 40 × 1000 mg
𝝆 7.8 g/cc 7.8 g/cc
A 1 m × 3 m = 3 m2 3 × 100 × 100 cm2
t 6 months 6 × 30 × 24 hrs

𝐊𝐖
𝐂𝐏𝐑 =
𝛒𝐀𝐭
87.6 × 40 × 1000 mg
CPR = g
7.8 cc × 3 × 100 × 100 cm2 × 6 × 30 × 24 hrs

= 3.44 × 10-3 mm/yr

CPR = 0.03466 mm/yr

To calculate CPR in mpy

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Given CPR in mpy

K 534
W 40 g 40 × 1000 mg
𝝆 7.8 g/cc 7.8 g/cc
A 1 m × 3 m = 3 m2 3 × 1550 inch2
t 6 months 6 × 30 × 24 hrs
1 sq. mt. = 1550 sq. inch
𝐊𝐖
𝐂𝐏𝐑 =
𝛒𝐀𝐭

534 × 40 × 1000 mg
CPR = g
7.8 cc × 3 × 1550 inch2 × 6 × 30 × 24 hrs

CPR = 0.1363 mpy

2. A piece of corroded steel plate was found in a submerged ocean vessel, it was estimated that

the original area was 10 inch2 that approximately 2.6 kg had corroded away during the

submersion. Assuming a corrosion penetration rate of 200 mpy for this alloy in sea water.

Estimate the time in years, density of steel is 7.9 g/cc.

Given CPR in mpy

K 534
W 2.6 kg 2.6 × 1000 × 1000 mg
𝝆 7.9 g/cc 7.9 g/cc
A 10 inch2 10 inch2
t x x hrs

𝐊𝐖
𝐂𝐏𝐑 =
𝛒𝐀𝐭
KW
t=
ρ × A × CPR
534 × 2.6 × 106 mg
t= g
7.9 × 10 inch2 × 200 mpy
cc
t = 87873.41 hrs
87873.41
𝑡= = 𝟏𝟎. 𝟎𝟑 𝒚𝒓𝒔
365 × 24

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

3.10 Electrode is a device consists of metal and its own ionic solution. Following are some

important types of single electrodes

3.10.1 Reference Electrodes

These are the electrodes, used to determine the potentials of unknown electrodes. They are of
two types;
1. Primary Reference Electrodes: These are the electrodes whose potentials are known
from the method of construction.
E.g.: Standard hydrogen electrode (SHE).

Limitations of primary reference electrode (SHE)

(a) Construction is difficult.
(b) Electrode becomes inactive in presence of impurities in H2 gas.
(c) It cannot be used in the presence of oxidizing agents.
(d) It cannot be used in solutions of redox systems.

To overcome all these difficulties, secondary reference electrodes are used to measure the
electrode potential of unknown electrodes

2. Secondary Reference Electrodes

These are the electrode whose potential is known or constant and stable does not vary with
temperature.
I. Calomel electrode
II. Silver-silver chloride electrode

3.10.2 Ion Selective Electrode

These are the electrodes, selects only specific ions ignoring other ions. In this electrode, a

glass membrane is in contact with a solution, with which it can exchange ions.

E.g.: Glass electrode (exchanges H+ ions with solutions), various metal ion selective electrodes

which exchange metal ions with the solution.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

3.10.3 Glass Electrode

Principle: If a thin walled glass bulb containing an acid is immersed in another solution

containing H+ ions as shown in fig. A potential was developed across the glass membrane.

This is called boundary potential denoted by Eb.

Boundary potential (Eb); It is a potential developed across the glass membrane when
concentration of the solution inside and outside the glass membrane are different.

Mathematically it is represented as, Eb = E2 – E1

Eb = RT ln C2 (1)
F C1
Where C1 and C2 are the concentration of H+ ions of acid solution inside and outside the glass
bulb respectively.
Eb = – RT ln C1 + RT ln C2 (2)
F F
The concentration C1 of the solution inside the glass bulb is constant. Hence the first term on
the right side of the equ. (2) is constant. Further substituting the the value of R and F at 298
K the above equation becomes
Eb = L+ 0.0591 log C2 (3)

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

L is a constant which depends on the pH of the solution taken in the bulb and the glass
electrode assembly.
Since C2 = [H+] of the solution and -log [H+] = pH, equation (3) is written as

Eb = L ― 0.0591 pH (4)

Equation (4) is used to determine the pH solutions.

Construction: The glass electrode consists of a long glass tube with a thin walled bulb at the

bottom as shown in fig. The composition of the glass used in glass electrode is SiO2, Na2O,

Al2O3 etc., and it allows only H+ ions. The bulb consists of 0.1 N HCl (Assume concentration

is C1) and Ag/AgCl electrode it serves as internal reference electrode as shown in fig. If the

glass electrode is dipped into any solution containing H+ ions then glass electrode develops

potential called as glass electrode potential. It is represented as EG.

Then, EG = Eb+ E Ag/AgCl ……………... (5)

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

If C1 = C2, equation (1), Eb = 0. Moreover, it has been observed that under this condition, a small
potential is developed. This is called asymmetric potential and denoted by Eassy.

Therefore equation (5) can be written as

EG = Eb+ E Ag/AgCl + E assy
EG = L – 0.0591 pH + E Ag/AgCl + E assy
EG = L1 – 0.0591 pH (6)
(where L1 = L + E Ag/AgCl + E assy)

Advantages of Glass electrode

1. It can be employed in presence of strong oxidizing /reducing substances and metal ions.
2. It does not get poisoned easily.
3. It can be used in unbuffered solution and can be adopted for measurements with very
small quantities of solution.

3.10.4 Determination of pH
To determine the pH of given solution, glass electrode is dipped in a solution whose

pH has to be determined. It is combined with a saturated calomel electrode through a salt

bridge. Cell assembly representation:

Hg / Hg2Cl2 / Cl- // Unknown solution / glass membrane / 0.1N HCl / AgCl / Ag

pH Meter

Glass
Calomel Electrode
Electrode

Solution of
Unknown pH

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

From the emf, the pH of the solution is calculated as below:

Ecell = E cathode – E anode
Ecell = Eglass – Ecal (SCE)
Ecell = L1 – 0.0591 pH – Ecal (SCE) (SCE = Saturated calomel
electrode)
pH = L1 – Ecal– Ecell
0.0591
pH = K – Ecell
0.0591
(Whereas L1 – Ecal = K)
In order to evaluate k, a solution of pH is used and the potential of the cell is measured. From the
above equation K can be easily calculated.

Applications of Ion-sensitive electrode

1. To determine ions like H+, K+, Li+, etc.
2. To determine hardness of water (Ca+2 and Mg+2 ions)
3. To determine concentration of F-, NO3-, CN- etc.
4. To determine concentration of a gas using gas-sensing electrodes.
5. To determine pH of a solution using H+ ion sensitive electrode.

3.11 Calomel electrode

It is a metal-metal insoluble salt electrode is also called as secondary reference electrode.

Construction: It consists of glass tube. The bottom of the glass tube is filled with pure mercury

(Hg) on which a calomel paste (Hg + Hg2Cl2) is placed. The remaining part of the glass tube

is filled with sat. or std. KCl Solution.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

It also contains side tube serves as salt bridge and a platinum wire is dipped into the mercury
so that it serves as electrical contact.

Calomel electrode can be represented as Hg | Hg2Cl2 | Cl-

When it acts as anode, the electrode reaction is

2Hg  Hg22+ + 2e-

Hg22+ + 2Cl-  Hg2Cl2

2Hg + 2Cl-  Hg2Cl2 + 2e-

When it acts as cathode, the electrode reaction is

Hg22+ + 2e-  2Hg

Hg2Cl2  Hg22+ + 2 Cl-

Hg2Cl2 + 2e-  2Hg + 2Cl-

The electrode potential of the calomel electrode is mainly depending on the concentration of KCl
used; Electrode potential is calculated using Nernst equation,

2.303RT log[Cl]2 2.303RT log[Cl]

E = E° - = E = E° -
2F F

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

At 298 K, Substituting the values of R, T and F the above equation becomes

E= E° - 0.0591 log [Cl-]

For,
Electrode Concentration (KCl) Ecalomel (V)

Decinormal 0.1N 0.334

Normal 1N 0.281

Saturated Saturated 0.2422

Advantages

1. It is simple to construct.

2. The cell potential is stable and reproducible does not vary with temperature.

Applications

1. It is used as secondary reference electrode in all potentiometric determinations.

2. Used in glass or combined electrode to determine the pH of the unknown solution.

Limitations

1. Calomel electrode cannot be used beyond a temperature of 60 ℃.

2. Hg employed in construction poses pollution problem.

3.12 Analytical techniques

Analytical techniques are the methods utilized for the determination of compounds

(qualitative analysis) and concentration of analytes (quantitative analysis) by using different

techniques. This technique aids to study the physical or chemical properties of chemical substances

and mixture.

A chemical sensor is an analytical device that converts chemical evidence such as

concentration, partial pressure, and activity into a measurable signal. It is composed of two parts;

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

(a) recognition part: - interacts with the target ions or molecules in the sample, (b) transducer part:

- converts the chemical interactions into a signal, which can be measured.

3.12.1 Potentiometric sensors

Introduction

Principle: “It is an electro-analytical technique in which the amount of a substance in

solution is determined from measurement of the emf between two electrodes that are dipped

into the solution”.

Theory

When a metal M is immersed in a solution containing its own ions Mn+, the electrode

potential is given by Nernst’s equation,

2.303RT
Ecell = E O + log[M n+ ]
nF

E can be measured by combining the indicator electrode with a reference electrode and measuring

the standard emf of the cell, Whereas E° is the standard potential of the system. Especially for

redox titrations could be carried out potentiometrically using platinum – calomel electrode

assembly. The potential is given by

0.0591 [Oxidized form]

Ecell = E O + log
n [Reduced form]

Instrumentation and procedure (Estimation of Iron)

A potentiometer connected with the electrode assembly involves the combination of the

platinum-calomel electrode immersed in the given sample (FAS) into a 100 cm3 beaker followed

by the addition of 2 test tubes of H2SO4. Measure the change in potential by adding potassium

dichromate from the burette with 0.5 cm3 increments. Stir the mixture after each addition, and

measure the change in potential with an increase in the volume of K2Cr2O7.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Plot a graph of ∆E / ∆V against the volume of K2Cr2O7 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 liter of the solution

Reactions: Fe+2 → Fe+3 + e−

Cr2 O2− + −
7 + 14 H + 6e → 2Cr
3+
+ 7H2 O

Advantages

1. This technique gives experimental results more reliable than that obtained from

titrations involving the use of indicators.

2. This method is useful with colored or turbid solution.

3. This method is suitable for titration of week acids and bases for which indicators are

not available.

Applications

1. This method is used to find the end point of redox and acid base titrations.

2. It is also used in titrations where suitable indicators are not available.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

3.12.2 Conductometric sensors

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, it is placed in a cell carrying a pair of platinum

electrodes, electroplated with platinum black. In conductometric titrations ions of a 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.

Weak acid with a strong base

Let us consider that acetic acid is titrated against NaOH. Initially the conductance is low

due to the low ionization of weak acid. However, increase in addition of NaOH to the acid to form

salt (CH3COONa). This salt formation tends to increase the conductance of the system, because

conducting power of ionized salt exceeds that of weak acid. This phenomenon gradually increases

until the equivalence point. Beyond this point, conductance rapidly increases due to the highly

conducting OH- ions. Consequently, the linear portion shown in the figure in the alkaline region

is steeper. The equivalence point is obtained by intersection of two lines i.e., one in acidic region

and other one in alkaline region.

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 Dr. M. Vinuth M.Sc., PGDHRM, Ph.D.

Reaction: NaoH + CH3 COOH → CH3 COONa + H2 O

Other applications

It can be used for the determination of: -

i. Solubility of sparingly soluble salts.

ii. Ionic product of water.

iii. Basicity of organic acids.

iv. Salinity of sea water (oceanographic work).

v. Chemical equilibrium in ionic reactions.

vi. Conductometric titration.

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