BCHES202 Module-1

MODULE 1
Electrode System, Corrosion and Analytical Techniques
Electrode System: Introduction, types of electrodes. Reference electrode - Introduction, calomel
electrode – construction, working and applications of calomel electrode. Ion selective electrode –
definition, construction, working and applications of glass electrode. Determination of pH using glass
electrode.
Corrosion Chemistry: Introduction, electrochemical theory of corrosion, types of corrosion-
differential metal and differential aeration. Corrosion control - galvanization, anodization. Corrosion
Penetration Rate (CPR) - Introduction and numerical problem.
Analytical Techniques: Introduction, principle, and instrumentation of Conductometry; its application
in the estimation of weak acid. Potentiometry; its application in the estimation of iron.
Self-learning: Principle and Instrumentation of IR spectroscopy.

Electrode System

Electrode or half cell: When a metal rod is dipped in a solution containing its own ions, equilibrium is
established at the interface between metal atom and its solution (ions). This arrangement is called single
electrode or half-cell.
Anode: M / Mn+
Cathode: Mn+ / M
Cell Potential
The cell potential is the way in which we can measure how much voltage exists between the two half
cells of a battery.
Ecell = Ecathode - EAnode and Eocell = Eocathode - EoAnode

Electrochemical series: The arrangement of elements in the increasing order of their standard
reduction potential is referred as electrochemical series.
Nernst’s Equation
In case of metal – metal ion electrode, as M is solid metal, [M] = 1,

Where, E = Electrode potential

Eo = Standard Electrode potential
n = no of electrons involved in reaction
F = Faraday constant = 96500 C
Changing ln to log, we get Nernst equation at any temperature.

This Expression is known as Nernst equation.

Substituting the values of R = 8.314 J/K/mol, T=298 K and F = 96500 C, We get

1|Page
 BCHES202 Module-1

This is the reduced form of Nernst equation for single electrode potential at 298 K or 25o C

Types of electrodes
In electrochemistry, we encounter various types of electrodes depending upon the purpose for which
they are used.
1. Metal-metal ion electrode
Metal-metal ion electrode consists of pure metal (M)in contact with a solution of its own ions (Mn+).
Example Zn/Zn2+ and Cu/Cu2+.

2. Metal- insoluble salt electrode.

A metal is in contact with a sparingly soluble salt of the same metal dipped in a solution containing
anion of the salt.
i) Calomel electrode (Consists of Hg covered by sparingly soluble mercurous chloride, which is
in contact with potassium chloride solution-Hg / Hg2Cl2 / Cl-).
ii) Silver- Silver chloride electrode (Ag / AgCl /Cl-).

3. Metal amalgam electrode

It is like a metal-metal ion electrode, except that in amalgam electrode, metal amalgam is in contact
with a solution containing its own ions.
Example: Pb-Hg/Pb2+ (lead amalgam electrode)
4. Gas electrode.
It consists of an inert metal (e.g., Pt) dipped in a solution through which gas is bubbled continuously.
As a result, the solution contains ions of the gas. Example: Hydrogen electrode, in which hydrogen
gas is bubbled continuously over platinum electrode.

5. Redox electrode.
It consists of an inert metal (e.g., Pt) dipped in a solution containing ions in two oxidation states of
the substrate. Example- Pt/ Fe2+, Fe3+.

Electrode System
Reference electrodes
The electrode with a known potential used to determine the potential of other electrode is called as
reference electrodes. Reference electrodes are classified as primary reference electrode and secondary
reference electrode.
Primary reference electrode
Standard hydrogen electrode (SHE) is considered as primary reference electrode as the electrode
potentials of other electrodes are assigned with respect to it and its electrode potential at all temperature
is taken as zero.
Secondary reference electrode
An electrode whose potential is measured with respect to SHE and then can be used as reference
electrode for measuring potentials of other electrodes is referred to as Secondary reference electrode.
Two such electrodes which are in common use are,
2|Page
 BCHES202 Module-1

1. Calomel Electrode
2. Silver-Silver chloride electrode.

Calomel electrode (CE)

The calomel electrode consists of a glass tube in which liquid mercury is placed at the bottom. It
is covered by a paste of Hg and Hg2Cl2 (mercurous chloride) called calomel which is further in contact
with a saturated or normal or decinormal potassium chloride solution. A platinum wire sealed in a glass
tube is dipped into mercury and used to provide external electrical contact.
The calomel electrode is represented as, Pt, Hg (l) | Hg2Cl2(s)| KCl

Depending upon the nature of the other electrode of the cell, the calomel electrode can act as anode or
cathode.
When it acts as anode the electrode reaction is

When it acts as cathode, the electrode reaction is,

Nernst equation for calomel electrode is,

The electrode potential depends on the concentration of the chloride ions. At 298K, the electrode
potentials are as follows,
Name Decinormal CE Normal CE Saturated CE
Concentration of KCl 0.1 N 1.0 N Saturated
Potential of CE in V 0.333 0.281 0.242

Uses
• It is used for the measurement of single electrode potential.
• It is used as reference electrode in all potential determination.

3|Page
BCHES202 Module-1

Advantages of calomel electrode

1. It is simple to construct.
2. The cell potential is reproducible and constant over a long period.
3. The cell potential does not vary with temperature.
4. Not poisoned by impurities.

Ion selective electrode

Ion selective electrode is the one which selectively responds to a specific ion in a mixture and
the potential developed at the electrode is a function of the concentration of that ion in the solution.
This electrode consists of a membrane which can exchange the specific ions with the solution with
which it is in contact. Therefore, these electrodes are also referred to as membrane electrode.
Glass electrode: The glass pH electrode is a long glass tube with glass membrane at the bottom. Glass
membrane made up of corning glass with composition 72% SiO2, 22% Na2O, 6% CaO. Its thickness
varies from 0.03 – 0.1 mm.

The glass bulb is filled with solution of constant pH (0.1 M HCl), and is inserted with Ag-AgCl
electrode, which is internal reference electrode and serves for the external contact. The electrode is
dipped in a solution containing H+ ions.
The glass electrode is represented as, Ag (s) | AgCl (s) | HCl (0.1M) | Glass membrane
Working
Glass pH electrode, when dipped in a solution the membrane undergoes an ion exchange reaction.
The membrane undergoes an ion exchange reaction. The Na+ ions on the glass are exchanged for H+
ions.

H+ (soln) + Na+Gl- (membrane) Na+ (soln) + H+Gl- (membrane)

The exchange of ions by the inner and outer membrane gives to a boundary potential (E b). This
boundary potential depends upon concentration of H+ ion in two solution (C1 and C2, where C1= 0.1 M).

4|Page
BCHES202 Module-1

Therefore, Eb = E2 – E1
Eb = 0.0591 log C2/C1 (n=1 for H+ ions)
Eb = 0.0591 log C2 - 0.0591 log C1
Since the concentration of the inner solution is constant (C1=0.1 M). The above equation
becomes, Eb = K + 0.0591 log C2 (where L is constant, C1=0.1 M, & K = - 0.0591 log C1)
Eb = K – 0.0591 pH (pH= -log [H+])
The potential of the glass electrode has three components.
1. The boundary potential
2. The potential of internal Ag-AgCl reference electrode
3. Small asymmetry potential

EG = Eb + EAg/AgCl + Easy
EG = K - 0.0591 pH + EAg/AgCl + Easy
EG = L - 0.0591 pH (Where L = K + EAg/AgCl + Easy)
EG = L - 0.0591 pH

Determination of pH using glass electrode

To determine the pH of a given solution the glass electrode is dipped in a solution whose pH needs to
be determined. It is combined with a saturated calomel electrode which is a reference electrode.
The cell is represented as
Hg (l) | Hg2Cl2 (s) | KCl | Solution of unknown pH | Glass membrane | HCl (0.1 M) | AgCl(s) | Ag(s)

5|Page
BCHES202 Module-1

The emf of the so formed cell is determined potentiometrically.

Ecell = EG – ECE
Ecell = L - 0.0591 pH –ECE
0.0591 pH = L– ECE - Ecell

L - ECE- Ecell
pH =
0.0591

Advantages of glass electrode

1. It is potable and compact.
2. Even in very diluted solutions, it gives accurate results.
3. The electrode can be used in the presence of oxidizing & reducing substances & metal ions.
4. It is not poisoned easily.
5. It is simple to operate. It can be used in portable instruments and therefore extensively used in
chemical, industrial, agricultural, and biological laboratories.
Limitations of glass electrode
1. The electrode can be used up to a pH of 13. But becomes sensitive to Na + ions above pH of 9
resulting in an alkaline error. (Because relationship between pH and glass electrode potential
will be slightly altered beyond a pH 9)
2. It does not function properly in pure alcohol and some organic solvents.
3. Because of the high resistance of glass, simple potentiometers cannot be used. It requires
sensitive electronic potentiometers for emf measurement.

Corrosion Chemistry
Corrosion is defined as “the destruction or deterioration of metals or alloys by the
surrounding environment through chemical or electrochemical changes.
The familiar examples of corrosion are,

i. Rusting of iron – A reddish brown scale formation on iron and steel objects. It is due
to theformation of hydrated ferric oxide.
ii. Green scales formed on copper vessels. It is due to the formation of basic cupric
carbonate[CuCO3 + Cu(OH)2].
6|Page
BCHES202 Module-1

The metals undergo corrosion due to the oxidation by losing electron and the resulting product is
called rust, which mainly contains oxides, sulphates, carbonates, and bicarbonates of the metals.
Due to corrosion, metals lose their valuable properties such as conductivity, strength, shining,
malleability, ductility etc.

Cause for corrosion: Each metal tries to get original state such as ore form (oxides, sulphates,
carbonates, and bicarbonates of the metals) which are more stable and lower energetic. Therefore,
corrosion is the reverse process of metallurgy.

Classification of corrosion

Chemical corrosion (Dry corrosion)

Chemical corrosion occurs due to the direct chemical reaction between the metal and the gases
present inthe corrosion environment. This type of corrosion is generally observed in the absence
of moisture. Therefore, it is also known as dry corrosion.

Example: Oxidation of metals or alloys on exposure to oxygen in air.

Electrochemical corrosion (Wet corrosion)

Electrochemical corrosion involves reactions in aqueous medium and moist air. The conducting
surfaceof the metal undergoes an electrochemical reaction with the moisture and oxygen present
in the atmosphere. This process can be explained based on electrochemical theory of corrosion.

Electrochemical theory of corrosion

Electrochemical theory of corrosion explains the corrosion based on galvanic cell formation.
According to this theory, corrosion of metal takes place due to the formation of anodic and cathodic
region on the same metal surface or when two different metals are in contact with each other in the
presence of a conducting medium. At anodic region metal undergo oxidation by losing its valence
electron and gets corroded. While in the cathodic region reduction reaction takes place. Thus,
cathodic regionis unaffected by the cathodic reaction.
The electrons liberated at the anodic region migrate to the cathodic region constituting corrosion
current.The metal ions liberated at the anode and the anions formed at the cathode diffuse towards
each other through the conducting medium and forms corrosion product.

When a part of the metal is dipped in an aqueous solution, the part which is exposed to lower
concentration of air (or oxygen) acts as anode, while the part which is exposed to higher
concentration ofair (or oxygen) acts as cathode. (Because oxygen as greater tendency to absorb
electrons)

7|Page
BCHES202 Module-1

Corrosion reaction
At anode region metal undergo oxidation liberating electron.

M Mn+ + ne-

Fe Fe2+ + 2e-

Cathodic reaction depends on the nature of the corrosion environment.

a) If the surrounding environment is aerated and almost neutral, oxygen and water are
reduced toOH- ions.
1
O2 + H 2 O + 2e − → 2OH −
2
b) If the surrounding environment is de-aerated and almost neutral the cathodic reaction
involves theliberation of hydrogen gas and hydroxyl ions.
2H2O + 2e- 2OH- + H2

c) If the surrounding environment is deaerated and acidic the cathodic reaction involves the
evolution of hydrogen gas.
2H+ + 2e- H2

Corrosion of iron produces Fe2+ ions and OH- ions at the anodic and cathodic region respectively.
Theseions diffuse towards each other forming insoluble product Fe(OH)2 (ferrous hydroxide)

2Fe2+ + 4OH¯ 2Fe(OH)2

In an oxidizing environment ferrous hydroxide is oxidized to ferric oxide.

4Fe(OH)2 + O2 + 2H2O 2[Fe2O3·3H2O] Rust

In the presence of limited oxygen, ferrous hydroxide is converted into magnetic oxide of iron
(Fe3O4)and is known as black rust.

Note: 1

(i) The cathodic and anodic process occurs at the same rate.
(ii) The formation of galvanic cells on the metal surface is due to the following reasons.
(a) Contact with other metal
(b) Difference in the concentration of air or oxygen.
(c) Stress and strain on the material.
(d) Precipitation at the grain boundaries.

Note: 2

An arrangement of metals in the order of their corrosion resistance in the given environment is
referredto as galvanic series.

8|Page
BCHES202 Module-1

Types of Corrosion

Differential metal Corrosion or Galvanic Corrosion:

When two dissimilar metals are in contact with each other in a corrosion conducting
medium, the metal with lower electrode potential becomes anodic and undergoes corrosion,
whereas the metal with higher electrode potential becomes cathodic and remains unaffected. This
kind of corrosion is called differential metal corrosion. The rate of corrosion depends on the
difference in electrode potential. The higher the difference, the faster the rate of corrosion.

Example: When Zinc is in contact with Copper, Zinc metal being placed higher up in the
electrochemical series acts as anodic and gets corroded, whereas Copper metal which is placed
below Zn in electrochemical series is protected from corrosion.

This type of corrosion can be observed in the following.

(i) Steel pipe connected to copper plumbing.

(ii) Lead antimony solder around copper wires

Differential aeration corrosion

Differential aeration corrosion occurs when one part of the metal is exposed to lower concentration
of air when compared to other parts. When a metal is exposed to different concentrations of air
(O2), part of the metal exposed to lower concentration of O2 will have lower potential becomes
anodic and undergoes corrosion. Other parts of the metal which are exposed to higher
concentration of O2 become cathodic and remain unaffected. Thus, a differential aeration of metal
causes a flow of currentcalled differential current.
Example: When an iron rod is partially immersed in water, the part exposed to atmosphere
is more oxygenated and forms cathode and the part immersed in water which is less oxygenated
forms anode.

There are two types of differential aeration corrosion.

i. Pitting corrosion
ii.Water line
corrosion
i. Pitting corrosion
Pitting corrosion results when a small particle of dust particle or oil drop or moisture (water
drop) getsdeposited on the surface of the metal. The portion covered is less aerated compared to
the large, exposedarea and thus acts as an anode with respect to the surface exposed. Corrosion
takes place below the depositresulting in the formation of pit. Once a pit is formed corrosion rate

9|Page
BCHES202 Module-1

accelerated due to further decrease in concentration of O2 within the pit.

ii. Water line corrosion

Water line corrosion can be observed in steel tanks partially filled with water. The area above
the water line, which is more oxygenated acts as cathode and is unaffected by corrosion, whereas
corrosion takes place along a line just beneath the level of water meniscus because it is exposed to
lower oxygen concentration. More intense corrosion is observed just below the water line, hence
it is called water line corrosion.

More
oxygen, Rust
(Cathode)

Less Oxygen
(Anode)

Water
Examples for differential aeration corrosion:
i. Part of the nail inside the wall being exposed to lower oxygen concentration than the
exposed partundergoes corrosion.
ii. Window rods inside the frame suffer corrosion but not the exposed parts.
iii. Metal surface under dirt, dust, scale, or water undergoes corrosion.
iv. Paper pins inside the paper get corroded and the exposed part is free from corrosion.
v. Partially buried pipeline in soil or water undergoes corrosion below the soil or water.
Whereas the exposed part is free from corrosion.

Corrosion Control

Corrosion of metal is a natural spontaneous process, by which a metal is converted into a

more stable compound state. Therefore, corrosion control is more realistic than corrosion
prevention. The corrosion types are so numerous, the mechanism of corrosion is so different and
conditions under whichcorrosion takes place are so varied that no single method can be used to
control all possible corrosion cases. Some of the important methods used in controlling corrosion
of metals are,

1. Protective Coating
The Protective coating protects the metal from corrosion by acting as a barrier between the
metaland the corrosive environment. The principal types of coating applied on the metal surface
are,

Metal Coating: The process of covering the base metal with a layer of another metal is known
as metal coating. By this method the base metal can be protected. Metal coating can be anodic
metal coating or cathodic metal coating.

10 | P a g e
BCHES202 Module-1

Anodic Coating: Anodic coatings are produced by coating a base metal with more active metals
whichare anodic to the base metal such as Zn, Al, Mg, etc.,

The important characteristics of anodic coating are that, even if the coating is ruptured, the base
metal does not undergo corrosion. The exposed surface of the base metal is cathodic w.r.t. the
coating metal and the coating metal preferentially undergoes corrosion. The protection is ensured
if the anodic coating metal is still present on the surface. Therefore, anodic metal coating is also
known as sacrificial coating.

Example: Galvanizing is a familiar anodic coating and is extensively used to protect iron and steel
objects.

Galvanization: It is a process of Coating a base metal with zinc metal. It is carried out by hot
dipping method.

Hot dipping method: It involves the dipping of base metal in molten anodic metal (Zn). The
coating metal should melt at a relatively low temperature and the base metal must withstand this
temperaturewithout undergoing any changes in its properties. The galvanization process involves
the following steps.

(a) The metal surface is washed with organic solvent to remove oil or grease present on the
surface.
(b) Rust and other deposits are removed by washing with dilute H2SO4.
(c) The clean and dry sheet is passed through aqueous solution of zinc chloride and
ammoniumchloride flux and dried. The flux helps the molten metal to adhere (adsorb) on the
metal surface.
(d) The article is then dipped in a bath of molten Zinc maintained at 425-430oC.
(e) The excess Zn on the surface is removed by passing through a pair of hot rollers which
wipes outexcess coating and produces a thin coating.

Galvanization is used extensively to protect iron from corrosion in the form of roofing sheets,
fencing wire, buckets, bolts, nuts, nails, screws, pipes, tubes etc. Galvanized steels are used in
construction wherea high degree of corrosion resistance is required. Galvanized articles are not
used for preparing and storingfood stuffs since zinc dissolves in dilute acids producing toxic Zinc
compound.

11 | P a g e
 BCHES202 Module-1

2. Surface conversion Coating

Inorganic coatings are generally chemical conversion coatings. A surface layer of metal is
converted into a compound, by chemical or electrochemical reactions, which forms barrier
between the underlying metal surface and the corrosion environment. The chemical conversion
coatings are different from other types of coatings in the sense that they are an integral part of
the metal itself. These types of coatings are formed on the metal surface by electrolytic method.
In addition to the corrosion resistance, also provide increased electrical insulation and enhanced
adherence for paints and other similar organic coatings.

Anodization

Anodization is the process of oxidation of the outer layer of metal to its metal oxide by electrolysis.
Oxide layer formed over the metal itself acts as protective layer. A protective oxide film generally
produced on nonferrous metals like Al, Mg, Cr, Zn, Ni, and their alloys by anodic oxidation process,
in which the base metal is made as anode in electrolytic bath of suitable composition (Chromic acid,
H2SO4, H3PO4, H2CrO4) and by-passing direct current. Lead is generally used as cathode.

The anodic oxide film formed on Al in the electrolyte bath tends to be porous and provides good
adherence for paints and dyes. The strength and corrosion resistance of the anodized film can be
increasedby the so-called sealing, which involves heating in boiling water or steam or metal salt
solution. The treatment changes porous alumina at the surface of coating into its mono hydrate
(Al2O3.H2O), which occupies more volume, thereby pores are sealed.
Anode : Aluminium article
Cathode : Steel or Copper
Temperature : 35OC
Electrolyte : 10% sulfuric acid or 5-10% chromic acid or oxalic acid
Current density: 10-20 mA/cm2

Anodized articles are used as exterior for roofs, walls and window frames, soap boxes and Tiffin
carriers etc.

12 | P a g e
BCHES202 Module-1

Corrosion Penetration Rate (CPR)

The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific
environment deteriorates due to a chemical reaction in the metal when it is exposed to a corrosive
environment” or the amount of corrosion loss per unit time in thickness or the speed at which corrosion
spreads to the inner portions of a material. Corrosion rate depends on the metal and the environmental
condition.

Weight loss method

It is a commonly used method for the measurement of uniform corrosion. It involves the exposure of
a
weighed piece of test metal or alloy to a specific environment for a precise time. This is accompanied
by thorough cleaning to remove the corrosion products and then determining the weight of the lost
metal as a result of corrosion.
The corrosion rate is best described in terms of the thickness or weight loss where the surface of
themetal disintegrates uniformly across the area that has been exposed.

The Corrosion Penetration Rate (CPR) is calculated by using the following mathematical relation,

𝐤𝐱𝐖
𝑪𝑷𝑹 =
𝐃𝐱𝐀𝐱𝐓
where k = a constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³

The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface of
the metal corrodes uniformly across an area.

This method involves the exposure of a weighed piece of test metal or alloy to a specific environment
for a specific time. This is followed by a thorough cleaning to remove the corrosion products and then
determining the weight of the metal after corrosion.

The rate may vary if the rate expressed by the formula above is used to compare corrosion rates for a
period longer than one year with rates calculated over short periods. This is because the short time
periods are prone to fluctuating environmental changes from season to season and from day to day.

Unit of CPR is mils per year if W is in mg, A in Inch2, D in g/cm3, t in hrs and k value will be 534. (1mil =
0.001 inch)

Unit of CPR is mm per year if W is in mg, A in cm2, D in g/cm3, t in hrs and k value will be 87.6. (1inch =
2.54 cm)

If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the applications.

13 | P a g e
BCHES202 Module-1

Sample problem on CPR

1. A steel of area 100 in2 is exposed to air near the seashore. After 1 year it was found that the steel
sheet has lost 485g due to corrosion. What is the value of CPR in mils/year and in mm/year? Can such
steel sheet be applicable for the construction purpose where the steel sheet is exposed?

Given - Area (A) =100 inch2, total weight lost (W) =485g = 485 x103 mg, T = 1 year =1 x 365 x 24hrs, D
= 7.9g/cm3 and k=534.
kxW
𝐶𝑃𝑅 =
DxAxT

534 x 485000
𝐶𝑃𝑅 =
7.9 x 100 x 365 x 24

CPR = 37.42 mils/year

Area =100 inch2 = 100 x 2.54×2.54 cm2 (1 inch = 2.54 cm) and k =87.6
kxW
𝐶𝑃𝑅 =
DxAxT
87.6 x 485000
𝐶𝑃𝑅 =
7.9 x 100 x 2.54 x 2.54 x 365 x 24
CPR = 0.9516mm/year
Since CPR is not less than 20m/year or 0.5 mm/year, it is not applicable for construction purposes.

ANALYTICAL TECHNIQUES
Analytical chemistry deals with the quantitative and qualitative characterization of materials. The
identification of elements/ radicals/ ions/ compounds is called qualitative analysis. The determination
of exact quantity of the constituents present in the substance is called quantitative analysis. A chemical
analysis which involves instruments is called instrumental analysis.
Advantages
1. It is faster.
2. We get accurate and reproducible results.
3. Low concentration sample solution can be analyzed.
4. Easy to handle large number of samples.
5. Widely applicable in industries.
Disadvantages
1. Instruments are expensive.
2. Calibration is necessary before analysis.
3. Concentration range is limited.
4. Training is needed to handle the instruments.

14 | P a g e
BCHES202 Module-1

Conductometry
Conductometry is an instrumental analysis in which the amount of a substance in solution can be
determined by measuring conductance of the solution. Conductance is the ability of an electrolyte to
conduct electric current (reciprocal of resistance).
Theory: Conductometric estimation is based on the measure of specific conductance (conductivity).
Specific conductivity is the conductance of the solution of one unit volume (two electrodes placed 1 cm
apart and length of each electrode is 1 cm). Conductivity of the electrolyte solution obeys Ohm’s law
and at constant temperature it depends on charge, mobility, concentration, and size of the ions. Ohm’s
law states that the current ‘I’ flowing through a conductor is directly proportional to the applied
potential ‘E’ and inversely proportional to the resistance ‘R’ of the conductor.
E = IR
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. Two electrodes are connected to a
conductometer and the conductivity of the solution is recorded. The titrant is added from the burette
in an increment of 0.5 cm3. The conductivity is measured after each addition. Then a graph of
conductivity against the volume of titrant is plotted. The point of intersection of the curve gives the
end point.
Estimation of weak acid (CH3COOH v/s NaOH)
Principle
NaOH + CH3COOH → CH3COONa + H2O
A graph of conductance against the volume of NaOH is as shown in the figure. On addition of NaOH, the
conductance increases because the partially dissociated weakly conducting weak acid is converted into
fully dissociated conducting salt (sodium acetate). Addition of base beyond the neutralization point
leads to increase in the more mobile OH- ions and conductance increases.
Procedure
Immerse a conductivity cell into the given weak acid sample solution in the beaker and connect it to
the conductometer. Measure the conductivity of the solution. Add standard solution of NaOH from
the burette in increment of 0.5 cm3. After each addition stir the solution and note the conductivity.
15 | P a g e
BCHES202 Module-1

Continue the titration till a sharp increase in conductivity is obtained and 5 to 6 reading thereafter.
Plot conductivity against volume of NaOH and note down the equivalence point.

Calculation
Normality of NaOH = ‘A’ N
Equivalence point (from graph) = Ve cm3
Volume of acid taken = ‘V’ cm3

Weight of CH3COOH per dm3 = N CH3COOH x Eq.wt of CH3COOH

= B x 60
= -------------
= ------------g/dm3
Potentiometry
Potentiometry is an instrumental analysis in which the amount of a substance in a solution is
determined by measuring the EMF between two electrodes dipped in the solution.
The potential of an electrode is given by Nernst equation.

Thus, the potential of an electrode depends upon the concentration of the ions.
Electrode potential is measured by combining the indicator electrode with reference electrode.
During titration, concentration of ions changes, hence, potential of the electrode changes. The
electrode, whose potential depends on the concentration of the ions to be determined, is called as
indicator electrode. The electrode with known potential is called reference electrode.

16 | P a g e
BCHES202 Module-1

Instrumentation
The potentiometer consists of a reference electrode, an indicator electrode and a potential measuring
device (Potentiometer). A simple arrangement is as shown in the figure.

A known volume of analyte is taken in a beaker and its potential is determined. The titrant is added
from the burette in increment of 0.5 cm3 and emf is measured for each addition. At the approach of
the equivalent point the emf tends to increase rapidly. A few readings are taken beyond the end point.
Thus, the change in potential at different volume of titrant are recorded. To locate the end point of the
titration emf value are plotted against the volume of titrant or ∆E/∆V values are plotted against the
volume of titrant.
Applications
1. To locate the end point of the titration.
2. To determine the concentration of the solution by finding emf.
3. To determine pH of the solution using glass electrode.
Potentiometric titration is applicable in oxidation-reduction titration to estimate the concentration of
analyte.
In redox titration the indicator electrode is an inert metal such as platinum and the reference
electrode is generally a saturated calomel electrode.
The potential of the electrode depends on the concentration of the substance being oxidized or
reduced.

Estimation of iron
Immerse indicator electrode (platinum electrode) and a reference electrode (calomel electrode) into
the given sample in the beaker and connect it to the potentiometer. Add one test tube of 2N sulfuric
acid. Measure the emf of the solution. Add standard solution of K2Cr2O7 from the burette in increment
of 0.5 cm3. After each addition stir the solution and note the emf. Continue the titration till a sharp
increase in emf is obtained and 5 to 6 reading thereafter. Plot ∆E/∆V against volume of K 2Cr2O7 and
note down the equivalence point.

17 | P a g e
BCHES202 Module-1

Molarity of K2Cr2O7 used for titrations= ------- N (A)

Equivalence point from graph= ------- cm3 (B)

Weight of iron/dm3 = NIron sample x Eq. weight of iron

= C x 55.85
= ------------
= ---------g/dm3

18 | P a g e
 BCHES202

19 | P a g e