Dr.

BALAJOTHI B
ASSISTANT PROFESSOR

Applied Chemistry for Computer Science & Engineering stream

BCHES202

MODULE 3: CORROSION CHEMISTRY AND ELECTRODE SYSTEM

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.

Corrosion Chemistry

Introduction

When the metal comes in contact with gaseous or liquid environment [or surrounding] they
undergo a spontaneous, but gradual destruction which starts at the surface of metals. In chemical
terminology destruction is known as corrosion. Corrosion is the chemical or electrochemical
reaction of a metal with its surroundings. Corrosion is the destructive attack of a material by
reaction with its environment. The serious consequences of the corrosion process have become
a problem of worldwide significance. In addition to our everyday encounters with this form of
degradation, corrosion causes plant shutdowns, waste of valuable resources, loss or
contamination of product, reduction in efficiency, costly maintenance,and expensive overdesign.
It can also jeopardize safety and inhibit technological progress.

Definition: Corrosion can be defined as the destruction or deterioration of metals or alloys

by surrounding environment through chemical or electrochemical changes.
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Corrosion can be a fast or slow process depending upon the metal, and the environment in which
it is undergoing corrosion. The familiar examples of corrosion are:

(i) Rusting of iron-a reddish brown scale formation on iron and steel objects. It is due to the
formation 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]

Harmful effects of corrosion:

Lose of efficiency
Contamination of product
Damage of metallic equipment’s
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.
Causes pollution due to escaping products from corrosion
Depletion of natural resource (Metals)

Global loss due to corrosion:

The natural phenomenon of infrastructural damage owing to corrosion costs up to 4% of
Global GDP per year.
In India, it could cost an estimated 5% of GDP per year.
This implies that the lack of protection against corrosion can lead to infrastructure getting
corroded much before reaching its design life.
Direct & Indirect losses
Direct loss: Material cost, maintenance cost, over-design, use of costly material
Indirect losses: Plant shutdown & loss of production, contamination of products, loss of
valuable products due to leakage etc, liability in accidents.

Corrosion of metal occurs either by direct chemical attack or by electrochemical attack on the
metal by the corrosive environment. Corrosion classified as;

(l) Dry corrosion (Chemical corrosion):

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Corrosion of metal occurs by direct chemical attack of atmospheric gases such as

oxygen, hydrogen sulfide, halogens and Sulphur dioxide in the absence of moisture to form a
metal oxide layer. As direct chemical attack takes place generally in the absence of moisture in
which the constituents of corrosion medium (H2O2, H2S, Halogens and SO2) directly attack on
the metal due to their chemical affinity towards the metal hence, this type of corrosion is known
as dry corrosion.
(2) Wet corrosion (Electrochemical corrosion):
Most of the corrosion cases are electrochemical in nature, taking place in the presence
of moisture or a conducting medium by the electrochemical (with the formation of a galvanic
cell on the metallic surface) attack on the metal such corrosion is known as wet corrosion.

Electrochemical theory of corrosion (Wet corrosion):

According to electrochemical theory, corrosion of metal take place due to the formation
of anodic and cathodic regions on the same metal surface or when two different metals are in
contact with each other in the presence of a conducting medium.
At the anodic region oxidation reaction takes place and the metal gets converted into its
ions, liberating electrons.
Consequently, metal undergoes corrosion at the anodic region. At the cathodic region
reduction reaction takes place.
Since the metal cannot be reduced further and hence metal does not undergo corrosion at
the cathodic region.
The electrons liberated at the anodic region migrate to the cathodic region constituting
corrosion current.
The metal ions liberated at the anode and anions at the cathode 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 anodic and cathodic reactions take place
simultaneously. There cannot be anodic reaction without cathodic reaction and vice versa
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Figure 1: Corrosion of Metal

Corrosion reaction:
Anodic reaction:
Oxidation of metal occurs
-
M → Mn+ + ne

Cathodic reaction:
Reduction occurs at the cathodic region and three reduction conditions are possible.
(i) Metal exposed to moisture (H2O) and air (O2); oxygen is reduced

O2 + 2H2O + 4e- → 4OH -

(ii) Metal exposed only to moisture; H2O is reduced

2 H2O + 2e- → H2 + 2OH-

(iii) Metal exposed to acidic medium with no air; H+ ions are reduced

2H+ + 2e- → H2

Rusting of iron based on electrochemical phenomenon

Anodic reaction: Anodic reaction is a simple oxidation reaction in which the metal atoms are
converted into their ions liberating electrons. For ex: When iron undergoes corrosion,
At the anodic area, oxidation take place, resulting in the corrosion of iron

Fe → Fe2+ + 2e -

Cathodic reaction: The electrons flow from the anodic to cathodic area and cause reduction.
There are three possible ways in which the reduction can take place.
In neutral or alkaline medium and the presence of oxygen, hydroxide ions
are formed
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O2 + 2H2O + 4e- → 4OH -

In neutral or alkaline medium and in the absence of oxygen.

2 H2O + 2e- →H2 + 2OH-

In acidic medium and in the absence of oxygen

2H+ + 2e- → H2

The metal ions produced at the anode combines with the OH- ions to form ferrous hydroxide,
whichundergoes aerial oxidation to form iron oxide
Products of anode & cathode:
Fe2+ + 2OH- → Fe(OH)2 (Ferrous hydroxide)

In the presence of oxygen:

4Fe(OH )2 + O2 + 2H2O → 2{Fe2O3.3H2O} (Iron oxide) (Rust)

Types of corrosion
According to electrochemical theory, corrosion occurs due to the formation of large number of
galvanic cells on the surface of the metal. A galvanic cell is formed, when there is a difference in
potential between t he regions across the metal surface. Metals undergo corrosion by different
types depending on the nature of metal, the nature of corrosion environment and the conditions.
Some of the important types of corrosion cases are discussed below.

1. Differential metal corrosion

2. Differential aeration Corrosion
1. Differential metal corrosion

When two dissimilar metals are in contact with each other in a corrosive conducting medium.
The two metals differ in their tendencies to undergo oxidation; the one with lower electrode
potential or the moreactive metal acts as anode and the one with higher electrode potential or the
less active metal act as cathode the potential difference between the two metals is the cause
corrosion. The anodic metal under goes corrosion and the cathodic metal is protected from
corrosion.
Examples
When two metals Fe and Cu are in contact: Since iron has lower reduction potential compared to
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Cu, ironundergoes corrosion and Cu is protected.

-0.44 V +0.34 V

Anodic reaction Cathodic reaction

Fe → Fe2+ + 2e- O2 + 2H2O + 4e- →4OH-

When two metals Zn and Fe are in contact: Since Zinc has lower reduction potential compared to
Fe, Znundergoes corrosion and Fe is protected.

-0.76 V -0.44 V

Anodic reaction Cathodic reaction

Zn → Zn2+ + 2e - O2 + 2H2O + 4e- →4OH-

Examples.

Steel pipe connected to copper.

Zinc coating on mild steel.
Tin coating on copper vessels.
Steel screws/reverts in copper sheet
Lead antimony solder around copper wire.

2.Differential aeration Corrosion

Corrosion of a metal due to difference in air or oxygen concentration on its surface is called
differentialaeration corrosion. When a metal is exposed to different oxygen concentration. The
part of the metal exposed to higher oxygen concentration acts as cathodic region and the part of
the metal exposed to lower oxygen concentration acts as an anodic region. Consequently, the
poor oxygenated region undergoes corrosion. The reactions may be represented as follows:
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Figure 2: Differential aeration Corrosion

Anodic reaction Fe → Fe2+ + 2e-

Cathodic reaction O2 + 2H2O + 4e- →4OH-

Example

1. Windows rods inside the frame suffer corrosion but not the exposed region.
2. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.
3. part of the nail inside the wall, being exposed to lower oxygen concentration than the exposed
part, undergoes corrosion.
4. Window rods inside the frame suffer corrosion but not the exposed region.
5. Paper pins inside the paper gets corroded, and the exposed part is free from corrosion.
6. Partially buried pipe line in soil or water undergoes corrosion whereas the exposed part is free
from corrosion.

2a. Water-line corrosion

It is the differential aeration corrosion observed in iron or steel partially in contact with
water. Usually observed in water storage tanks, ship water lifting pipes etc. The portion under
water will be exposed to less concentration of oxygen and will act as the anode and undergo
corrosion while the portion above water act as cathode and will remain unaffected. The extent
of corrosion will be maximum just below the waterline and hence is called waterline corrosion.
For example in water storage tank the metal tank part inside water level exposed only to dissolved
oxygen get corroded (anode) while the part above water line is exposed to higher oxygen
concentration is protected (cathode).
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Figure 3: Water line corrosion

2b. Pitting corrosion

It occurs when small particles of dust, water drop on metal surface or breakdown of
protective film. A typical pitting corrosion is illustrated as shown in figure. The metal portion
covered by dust act as anodedue to less oxygenated and undergoes corrosion beneath the dust
forming a pit. The metal part free fromdust exposed to higher oxygen concentration become
cathode and protected from corrosion. The corrosion rate is higher in this case due to small
anode area and large cathode area. All the electrons liberated at anode (pit) are absorbed by
large cathode area for reduction reaction.

Figure 4: Pitting Corrosion

Factors affecting rate of corrosion

The rate of corrosion depends on the following factors.
a) Nature of metal: In general, the metal with lower electrode potential values are more
reactive than the metal with higher electrode potential values. The more reactive metals are
more susceptible for corrosion, thus the tendency of metal to undergo corrosion decreases
with increase in electrode potential. For example, the active metals like k, Na, Mg, Zn etc,
with low electrode potential values are highly susceptible for corrosion. The noble metal
such as silver, gold, platinum etc, with higher electrode potential values are less susceptible
for corrosion. However, there are few exceptions for this general trend as some metal show
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the property of passivity.

b) Nature of corrosion product: The rate of corrosion depends on the nature of corrosion
product which is formed during corrosion. In the case of metal like iron, zinc and magnesium,
the oxides whichare formed during corrosion are, highly porous, Non-stoichiometric, highly
soluble and good ionic conductivities, As a result, corrosion is continued till the metal is
completely destroyed. On the other hand, in the case of metal like aluminum, titanium,
chromium etc, the oxides formed are non-porous, stoichiometric, and highly insoluble with
low ionic and electronic conductivities. As a result, the corrosion is stopped as soon as oxide
film is formed.
c) Relative areas of anode and cathode: Smaller the anodic area, larger the cathodic
area faster will bethe rate of corrosion because the demand of electrons for the reduction of
larger cathodic area will be more. Conversely larger the anodic area and smaller the cathodic
area slower will be the rate of corrosion.For example, if an iron sheet is coated with tin is not
properly coated, then tin is cathodic with respect to iron, i.e. iron is more reactive, the small
anodic area has to supply electrons to large cathodic area forcorrosion takes place, therefore
corrosion rate is faster. On the other hand, if iron sheet is coated with zinc is anodic with
respect to iron, even of the part of plated Zn peels off, intense corrosion is not observed
because it has small cathodic area, and large anodic area can supply electrons to small cathodic
area and therefore rate of corrosion is slow.

d) pH of the medium: In general, lower the pH of corrosion medium, higher is the corrosion
rate. (Exception: Metals like Al, Zn etc. undergo fast corrosion in media with high pH). Iron
does not undergocorrosion at pH greater than 10. This is due to the formation of protective
coating of hydrous oxides of iron. Between pH 10 and 3, the presence of oxygen is essential
for corrosion. If the pH is less than 3, severe corrosion occurs even in the absence of oxygen
due to continuous evolution of hydrogen gas.

e) Temperature: In general increase in temperature increase in corrosion rate. For

many metalsthe corrosion rate almost exponentially rises with increase in temperature.
This is attributed to
1. Increase in conductance of the medium- ions migrate fast at higher temperature.
2. Increase in the rate of chemical reaction
3. Increase in solubility of the corrosion products in the medium
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4. Decrease in the polarization effects at the anode and cathode sites. However, if
corrosion is dueto dissolved gases like O2, CO2 etc. The rate of corrosion decreases with
an increase in temperatureas the solubility of these gases in the medium decreases.
Corrosion control
According to electrochemical theory, corrosion occurs due to the oxidation and reductions
reactions at the anodic and cathodic areas. These reactions occur simultaneously and are
interdependent. So by decreasing the rate of any of these reactions or by preventing any one
reaction, the rate of corrosion canbe decreased. The methods used to control corrosion are:
1. Metal Coating
a) Anodic Metal Coating: Galvanisation
b) Cathodic Metal Coating: Tinning
2. Cathodic protection- Sacrificial Anode Method
3. Anodization
4. Corrosion inhibitors

1. Metal Coating

a) Anodic Metal Coating: Galvanisation:

Anodic metal coatings are coatings which are anodic to base metals. Example are Al,
Zn etc. These metals are above the Fe in the galvanic series and undergo corrosion thereby
protecting Fe. A characteristics feature of anodic coating is that the base metal on which the
coating is done will not get corroded even if the coating peels off. This is due to formation of
large anodic area and small cathodic areas.
Example: Galvanisation: It is a process of coating Zn over the surface of iron. The method is
carried
out by hot dipping process. It involves the following steps:
1. The iron sheet is washed with solvent to remove greasy & oily materials.
2. The iron sheet is washed with dil H2SO4 to remove oxide film.
3. The sheet is then treated with a mixture of aqueous solution of zinc chloride and
ammonium chloride& dried
4. The dried sheet is dipped in molten zinc at 430 – 450 0 C.
5. Excess Zn is removed by rolling, wiping or air blast.
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Figure 5: Galvanization process

Applications
1) Galvanized iron pipes are exclusively used for domestic purpose all over the world
2) Galvanized iron drum is used to preserve variety of chemicals, drugs & organic solvents.
3) Used in Roof sheets, fencing wires, barbed wire, buckets, pipes, etc.

2. Cathodic protection-

Cathodic protection is a method of protecting a metal or alloy from corrosion by converting it

completely into cathodic and no part of it is allowed to act as anode. Cathodic protection can be
achieved by the following methods: i. Sacrificial anode method and ii. Impressed current method.

Sacrificial anode method:

Corrosion of metal occurs at anodic area, where metals are oxidized to metal ions. In cathodic
protection,electrons are supplied from an external source to reverse and prevent oxidation of
metal at anodic area.Thus anodic are will be converted to cathodic. The process of protecting
a metal against corrosion by making the entire metal cathodic by providing electrons from an
external source is called cathodic protection.
Examples:
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1. Mg block connected to ships floating on water surface.

2. Mg block connected to underground buried pipe.
In this the metal structure to be protected is connected to a more anodic metal like Mg, Zn and
Al whichacts as anodic. In practice active metal Mg or Zn is connected to metal structure to
be protected. The more active metal Mg or Zn becomes anodic and corrodes but the metal
structure becomes cathodic is protected. Since the anode metal sacrifices to protect the metal
structure the method is known as sacrificial anode method.

` Figure 6: Sacrificial Protection

The metallic structure to be protected is connected to a more anodic metal using a metallic
wire. The more active metal gets corroded, while the parent structure is protected from the
corrosion. The more active metal so employed is called sacrificial anode. As the anodic metal
sacrifices its life to protect thebase metal from corrosion is called sacrificial anodic protection.
The commonly used sacrifical anodes are Mg, Zn, Al etc this method is generally used for
the protection of buried pipe lines ship hulls, watertanks.

Inorganic coatings: Inorganic coatings are generally chemical conversion coatings in which
a layer of the metal surface is converted into a compound, by chemical or electrochemical
reactions, which forms a barrier between the underlying metal surface and the corrosion
environment. They are the integral part of the metal itself. Inorganic coatings are applied by
chemical dip, spray or by electrolytic methods. Under this anodized coating and phosphate
coatings are employed.

Anodized coatings:
"Anodizing is an electrochemical process that converts the metal surface into a decorative,
durable, corrosion-resistant, anodic oxide finish"
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Principle: The components whose surfaces to be coated are made the anode in a dilute acid
solution. The oxygen liberated at the anode face results in the formation of a coherent oxide film
which is very adherent to the base metal.

Process: Process involves the following steps.

1. Pre-Treatment: Cleaning is done in a non-etching, alkaline detergent heated to

approximately 145o Fahrenheit. This process removes accumulated contaminants and light oils.

2. Rinsing: Multiple rinses, some using strictly de-ionized water follow each process
3. Etching (Chemical Milling): Etching in caustic soda (sodium hydroxide) prepares the
aluminum for anodizing by chemically removing a thin layer of aluminum. This alkaline bath
gives the aluminum surface a matte (even surface without shining) appearance.

4. Desmutting (Removing excess of Al): Rinsing in an acidic solution removes unwanted

surface alloy constituent particles not removed by the etching process.

5. Anodizing: Aluminum is immersed in a tank containing an electrolyte having a 15% sulfuric

acid concentration. Electric current is passed through the electrolyte solution by making
aluminum as anode and the tank as cathode. Voltage applied across the anode and cathode causes
negatively charged anions to migrate to the anode where the oxygen anions combine with the
aluminum to form aluminum oxide (A12O3).

6. Coloring: Anodic films are well suited to a variety of coloring methods including absorptive
dyeing, both organic and inorganic dyestuffs.
7. Sealing: The above coating is slightly porous and it is sealed by dipping in hot water. A12O3
gets hydrated to A12O3.H2O.

Anode —Al
Cathode — Lead or stainless steel
Bath — Chromic acid or sulfuric acid or phosphoric acid
Temperature — 35-40o C
The reactions involved in the anodization of Al are:
At anode: 2Al → 2A13+(aq) + 6e-
cathode: 6H+ + 6e- → 3H2
overall reaction: 2Al + 3H2O →Al2O3 +3H2
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Figure 7: Anodizing of Aluminum

Applications:

Anodized articles are used as soap boxes, tiffin carriers, window frames, etc.

The 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, K is constant.
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.
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The CPR is conveniently expressed in terms of either millis (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 cm2; Where, I mille
= 0.001 inch.

Electrode system
Electrochemistry: It is a branch of chemistry which deals with the study of transformation of
chemical energy into electrical energy and vice versa”

Electrochemical cells: An electrochemical cell is a device which converts chemical energy into
electrical energy or electrical energy into chemical energy”

Gibbs Free Energy (G): Gibbs energy is defined as maximum available energy in a system
that can be converted into useful work.
G =H -TS
The thermodynamic free energy is the amount of work that a thermodynamic system can
perform. The free energy is the internal energy of a system minus the amount of energy that
cannot be used to perform work.

EMF of a cell or Cell Potential: “Emf is the potential difference between the two electrodes of
a galvanic cell, which causes the flow of current from one electrode to other. It is also called as
cell potential or cell voltage. It is expressed in volts.

Mathematically, Ecell = Ecathode – Eanode

Ecell = Eright electrode – Eleft electrode

Single electrode potential or half cell potential [E]:

The potential that is developed due to the tendency of an element (metal or non-metal) to lose or
gain electrons, when it is in contact with the solution containing its own ions is known as single
electrode potential.

Standard electrode potential [Eo]:

The potential that is develop when an element is in equilibrium with the solution containing its
own ions of unit concentration (1 M) at 298 K is known as standard electrode potential. Electrodes
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are good conductors of electricity. Electrodes are used to make contact between non metallic parts
such as electrolytes, semiconductors. air. etc. of the circuit.
"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. Although inert electrodes also exist which don't take part in the reaction.
An electrode can be of gold, platinum, carbon, graphite, metal, etc. The electrode provides a
surface for oxidation-reduction reactions in the cells.

Types of electrodes:
Electrodes are mainly of two types - Reactive electrodes and Inert electrodes. Reactive electrodes
are those, which take part in the reaction taking place in the cell and can dissolve in the
electrolyte. Ex: Copper electrode, Silver electrode, zinc electrode etc. These are mainly used in
potentiometric work. Inert electrodes are those, which do not take part in the reaction. Ex:
Carbon electrode, Platinum electrode etc. Some of the types of electrodes are as
follows;
1. Metal-metal ion electrode: It consists ofa metal dipped in a solution containing its own ions.

Ex: Zn/Zn2+, Ag/Ag+; The electrode reaction is: Mn+ + ne -  M

2. Metal-metal insoluble salt electrode: It consists of a metal in contact with a sparingly soluble
salt of the same metal dipped in a solution containing anion of the salt. Ex: Calomel electrode (Hg/
Hg2Cl/ CI), silver-silver chloride electrode(Ag/AgCl/CI); The electrode

reactions are; Hg2Cl2 + 2e-  2 Hg + 2Cl and AgCl +e-  Ag + Cl respectively.

3. Gas electrode: It consists of a gas bubbling about an inert metal wire or foil, immersed in a
solution containing ions to which the gas is reversible. Ex: Hydrogen electrode (Pt/H2/H+),
Chlorine electrode (Pt/Cl2/Cl-): The electrode reactions are: H+ + e-  1/2 H2;

1/2Cl2 + e-  Cl
4. Oxidation-reduction electrode: It is an electrode in which the electrode potential arises due
to the presence of oxidized and reduced forms of. the same substance in the solution. The
potential developed is picked up by an inert electrode like platinum. Ex: Pt/Fe2+, Fe3+, Pt/Sn2+, Sn4+

The electrode reaction is Fe3+ + e-  Fe2+

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5. Ion selective electrode: It consists of a membrane in contact with a solution, with which it can
exchange ions. Ex: Glass electrode (exchanges H ions with the solution).
6. Amalgam electrode: It is similar to metal-metal ion electrode except for the fact that instead of
metal, a metal amalgam is in contact with solution of its own metal ions. Ex: lead amalgam
electrode (Pb-Hg /Pb2+).

Reference Electrodes
"Electrodes with a well-known and stable EO value are used as reference electrodes". The electrode
potential of any electrode can be measured with reference to these electrodes. Standard Hydrogen
Electrode (SHE) is a primary reference electrode as the electrode potential values of all other
electrodes are assigned with respect to it.
Role of reference electrodes:
1. The reference electrode provides a constant potential regardless of the composition of the
solution it is placed in.
2. The voltage difference between the reference and measuring electrodes is a function of the
pH value of a solution.
3. Common reference systems in use are Silver/Silver chloride (Ag/AgCl) and Mercury/
Calomel (Hg2Cl2) The Silver/Silver Chloride reference is far the most frequently employed because
it has universal applicability, a wide operating temperature range and is relatively non-toxic.
Limitations of standard hydrogen electrode:

1. Construction and working is difficult as it is difficult to maintain the concentration at unity

and pressure of gas uniformly at 1 atm.
2. Pt is highly susceptible to poisoning by the impurities present in the gas.
3. It cannot be used in the presence of oxidizing agents.

Secondary Reference Electrodes: Owing to the difficulties encountered with SHE, some
other electrodes with constant electrode potential were used as reference electrodes. These electrodes
are known as secondary reference electrodes. Eg: Calomel electrode and silver-silver chloride
electrode.

Calomel Electrode:
Construction: It is a metal-insoluble salt electrode consisting of mercury, mercurous chloride and a
solution of KCl. Mercury is placed at the bottom of a glass tube, having a side tube on each side.
Mercury is covered with a paste of mercurous chloride (calomel) with mercury and KCI soln. is
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introduced above the paste by the side tube. Pt wire sealed into glass tube is dipped into mercury
and used to provide the external contact; the conc. of KCI used is either decinormal, normal or
saturated solution.

Figure 8: Calomel electrode

The electrode representation is: Hg/ Hg2Cl2/Cl-
Electrode reactions (working): When it acts as anode the electrode reaction is,

2Hg → Hg22+ + 2e-

Hg2 2+ + 2Cl- → Hg2Cl2

Overall reaction: 2Hg + 2Cl- → Hg2Cl2 + 2e-

When it acts as cathode the electrode reactions are,

Hg22+ + 2e- → 2Hg

Hg2Cl2 → Hg22+ + 2Cl-

Overall reaction Hg2Cl2 + 2e- → 2Hg + 2Cl-

The net reversible electrode reaction is: Hg2Cl2 (S) + 2e- → 2Hg + 2Cl-

It is evident from the reaction that calomel electrode is reversible with respect to Cl- ions.

In other words, the potential of calomel electrode depends on concentration of KCI employed.

Acc. to Nernst eqn, the potential of calomel electrode at 298K is related to Cl- ions as,

Ecell = EOcell —0.0591/n log [Cl-]2 , where n=2

Ecell = EOcell —0.0591 log [Cl-]

Hence, the electrode potential of Calomel electrode dependent on the concentration of chloride ions
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Concentration of KCl 0.1N 1.0N Saturated

Potential of Calomel Electrode 0.338 V 0.281 V 0.244 V

Advantages:

It is very simple construction.

It can be used for long time without much attention.
Its electrode potential will not vary with temperature.
It is used as reference electrode.
Applications of calomel electrode:
The SCE is used in pH measurement.
Cyclic voltammetry and general aqueous electrochemistry.

Concentration Cells
"A concentration cell is a galvanic cell in which two electrodes of the same substance are in
contact with the same electrolyte of different concentrations".
Construction: The setup of a concentration cell consists of two electrodes made with the same
material dipped in the same electrolytic solutions of different concentrations. This type of cell Is
mainly used to determine the pH of the unknown acid-base solution. Let us consider a conc. cell
with respect to Nickel ions; the two electrodes of the cell are: Ni(s)/NiCl2(C1M) and
Ni(s)/NiCl2(C2M). When the electrodes are connected by a salt bridge, oxidation occurs at one
electrode and reduction occurs at the other electrode.

Anode
(Oxidation)

Discharge

[Ni2+] =0.5 M [Ni2+] =0.5 M

Figure 9: Concentration cell

The cell can be represented as: Ni(s)/NiCl2(C1M) // NiCl2(C2M) / Ni(s)

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Zn(s) / ZnS04 (C1M) // ZnS04 (C2M) / zn(s)

Working: The working of a concentration cell depends on maintaining the equilibrium between the
concentrations of two half cells. Thus it creates equilibrium between the two half-cells by transfer
of electrons. The electrons are transferred from half-cell having lower Concentration to half-cell
having higher concentration. The e.m.f of cell can be found by applying Nernst equation
The electrode reactions are given by:
Anode: Ni(s) → Ni2+ (C1) + 2e-
Cathode: Ni2+ (C2) + 2e- → Ni(s)
Net reaction: Ni2+ (C2) → Ni2+ (C1)

Applying Nernst equation for single electrode potential, we get

logC2  E Mn logC1
0.0591 0.0591
/ M  / M 
0 0
Ecell = E Mn
n n

logC2   logC1
0.0591 0.0591
Ecell =
n n

0.0591 [C 2]
Ecell = log
n C1

This is the expression of Nernst equation for

concentration cell at 25C.

Numerical Problems On Concentration Cells

1. A concentration cell is constructed by dipping copper rods in 0.001 M and 0.1 M CuSO4
solutions. write cell representation, cell reactions and calculate the emf of the Cell at 298 K.
2. consider a concentration cell of silver electrodes as represented; Ag(s)/
Ag+(0.00475M)//Ag+(0.043M)/Ag(s). Write the cell reactions and calculate the emf of the cell?
3. Two copper rods placed in CuS04 solutions of equal concentration are connected to form a
concentration cell. (a) What is cell potential? (b) Calculate the cell potential if one of the solutions
is diluted to 1/5th of its original concentration.
4. The spontaneous galvanic cell tin/tin(0.024)//tin(0.064)/tin, develops a potential of 0.0126 V
at 25o C. Calculate the valence of tin.
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5. The emf of the cell Cd/CdSO4 (0.0093M)// CdSO4 (X)/Cd is 0.015 V at 25o C. Find value of
x?
6. (a) write the half cell and net cell reactions, calculate the emf of the following concentration
cell, Cu/Cu2+(0.072M)// Cu2+(0.32M)/ Cu (b) Comment on the spontaneity of the cell reaction.
7. The emf of a concentration cell with 0.05 M and 0.025 M AgN03 solution is ?(Ans. 0.0177
V)
8. A concentration cell is constructed by dipping iron rods in 0.005M and 0.01M FeS04
solutions. Write the cell representation? Cell reaction and calculate the emf of the cell at 298K. (Ans.
0.0088 V)

Ion Selective Electrodes

"Certain electrodes are sensitive to only certain ions when they are in contact with different
kinds of ions. Electrodes with a specific ability to respond only certain ions present in the
solution and developing a potential with respect to that ions while ignoring Other ions are
called as ion selective electrodes".

Ion selective electrode possess the ability to respond only to a specific ion, there by developing
a potential w.r.t that species in a mixture and ignoring the other ions totally.

They are electrodes which can sensitively detect and quantitatively measure a particular chemical
species in a system. Since membrane is the most important component of an ion selective electrode
hence, it is also known as membrane electrode. Ex: Glass electrode is sensitive to only hydrogen
ions.
There are different types of ion selective electrodes, Some of them are:
Glass membrane electrode
Solid state electrode
Liquid state electrode

Construction of Glass Electrode:

Glass electrode is an ion selective electrode which is sensitive to the ions in the solution and hence
is widely used for pH determination. The glass electrode consists of a glass bulb made up of a
special type of glass (6%CaO, 22%Na2O and 72% SiO2) with high electrical conductance. The
glass bulb filled with a solution of constant pH (0.1M HCI) and has 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.
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The glass electrode system can be represented as:

Ag/AgCl/ 0.1M HCl/glass/HCl (pH=?)

Figure 10: Glass Electrode

Working: When the glass electrode is dipped in a solution of unknown pH, a potential developed
across the membrane. The potential developed is called the boundary potential and it is given by

Eb=E1 -E2 ……... (i)

where E1 is the potential developed at the outer surface of the membrane and E2 is the potential
developed at the inner surface of the membrane. Using Nernst equation (i) becomes

Eb = EO + 0.0591/n.log C1 - (EO + 0.0591/n.10g C2) …….(ii)

Eb = 0.0591 log C1 - 0.0591/n.log C2 at 298 K …………...(iii)
(n=l for H+ ions or glass electrode)

Where C1 is the conc. of the H+ ions in the solution whose pH is to be determined (unknown) and
C2 is the conc. of H+ ions of the internal reference solution. Since C2 is known, at 298K
Eb = L1 +0.0591 log C1 (where L1= 0.0591 log C2) ……….(iv)
Eb= L1- 0.0591 pH............................................... (v) (pH = -logC1)
The Glass electrode consists of Ag-AgCl electrode as the internal reference electrode. Therefore the
g1ass electrode potential has three components:

1. The boundary potential

2. The potential of the internal reference electrode

3. A small asymmetric potential

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(About Asymmetric potential: Asymmetric potential arises due to difference in responses of the
inner and outer surface of the glass bulb to changes in hydrogen ion activity. It may be due to
different conditions of strain in two glass surfaces. This asymmetric potential varies with time and
therefore, glass electrode must be standardized frequently by placing a solution of known ion
activity).

The potential of a glass electrode EG is given by;

EG=Eb+ Eref + Easy

Substituting for Eb from (iii); EG = L1 + 0.0591 log Cl + Eref + Easy

EG = EOG +0.0591 log Cl at 298K (where EOG = L1 + Eref + Easy

EG = EOG - 0.0591pH ... (vi)
Where, EOG = Standard emf of glass electrode, it is determined by combining the glass electrode
with a saturated calomel electrode and measuring the emf potentiometrically.

Applications:

l. Glass electrodes are commonly used for pH measurements.

2. Some of the specialized ion sensitive glass electrodes used for determination of the
concentration of lithium, sodium, ammonium, and other ions.

3. 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 and soil
acidity.

Determination of pH using glass electrode:

To determine pH of a given solution, the glass electrode is dipped in a solution where pH needs
to be determined. It is combined with a saturated calomel electrode. The cell notation is:
Hg/Hg2C12/Cl-//solution (pH=?)/glass/0.1M HCl/AgCl/Ag
 Dr. BALAJOTHI B
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Glass
Calomel

Solution of
unknownpH

Figure 11: Determination of pH using glass electrode

The emf of the cell so formed is determined potentiometrically. The emf of the cell should not be
measured using an ordinary voltmeter because the resistance offered by the glass is very high.
Hence high impedance voltmeter is used to record the emf of the cell.

Ecell = EG- Ecal

= EOG - 0.0591pH - Ecal (substituting from equation (vi))

Therefore; pH = (EOG - Ecal - Ecell )/0.0591

EOG value can be determined by dipping the glass electrode in a solution of known pH (buffer
solution) and measuring the emf of the cell formed when combined with a calomel electrode.

Introduction to Analyical Techniques

Analytical chemistry deals with the "qualitative and quantitative characterization of materials". It
embraces a wide variety of fields like environmental science, agriculture science, biomedical,
electronics, forensic research and space research. Analytical chemistry is an integral part of the R
& D Section of any industry. The two steps of chemical analysis in the characterization of matter
are identification and estimation of constituents of a substance. The identification step is called
the qualitative analysis, which gives information regarding the presence or absence of one or more
components of the sample. The estimation step is called the quantitative analysis, which
determines the exact quantity of the constituents present in a substance.
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The quantitative analysis can be classified into two types, depending upon the method of analysis.
1. Chemical methods of analysis (Classical)
2. 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 end etc.,

Types of instrumental methods of analysis

Instrumental methods of analysis can be classified into two types.

1. Electrical methods (electroanalytical methods)

2. Optical methods (spectroanalytical methods)
in
Electrical methods of analysis involve the measurement of current, voltage or resistance relation
to the concentration of a certain species in solution. Ex: Colorimetry, Conductometry and etc. The
optical methods are based on how the sample acts towards the electromagnetic radiation.
Advantages of instrumental methods over chemical methods:
The methods are much faster than the chemical methods

Applicable at lower concentrations

Find wide applications in industries

The analytical process can be automated

Disadvantages of instrumental methods:
The instruments are expensive

An initial or continuous calibration is required using a sample of material of known

composition.

The concentration range is limited

Specialized training is needed for the operation of certain sophisticated instruments.

 Dr. BALAJOTHI B
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Though instrumental methods are widely adopted, they have not rendered the classical
methods obsolete, because of their certain limitations. Instrumental methods and classical
methods are regarded as supplementary to each other.

Figure 12: Classification of analytical techniques

Principle, Instrumentation and Applications of Conductometry

Principle:
"During a titration process, one ion is replaced with another and the difference
in the ionic conductivities of these ions directly impacts the overall electrolytic
conductivity of the solution". Like a metallic conductor, electrolyte solutions also obey
Ohm's law,
E = IR …………(1)

Where, E is the applied potential, I is the current and R is the resistance,

The reciprocal of the resistance is called the conductance,
C=1/R ………..(2)
It is expressed in ohm-1, mhos or Siemen (S) in SI units
The resistance of any conductor is directly proportion to the length and inversely proportional to
the area of cross section of the conductor. Mathematically it is expressed as
R  l/a R = s(l/a)
where s is specific resistance or resistivity of the conductor
Therefore conductance from eq (1),
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C = 1/R = l/s(l/a) = l/s. a/l = k.a/l

C = k.a/l

K = C.l/a

Specific conductance = Observed conductance x Cell constant

Where 'K' is the specific conductance of the electrolyte solution for a given Conductivity cell. l/a is
called cell constant and given in cm-1 or m-1
Instrumentation: To measure the conductance of a solution, the solution is placed in a cell carrying
a pair of platinum electrodes. The measurements are made by connecting the Conductivity cell to
Conductivity Bridge as shown below.

Figure 13: Conductometry setup

Applications of conductometry:
1. Strong acid with a strong base: During the titration of HCI with NaOH, the reaction taking
place is, HCI + NaOH → NaC1 + H2O
The highly conducting H+ ions initially present in the solution are replaced by the Na+ ions having
a much smaller ionic conductance, while the concentration of chloride ions remains constant.
Therefore, the conductance first falls, and after the equivalence point has been reached, rapidly
rises with further additions of strong alkali which furnishes highly conducting OH- ions. The two
branches of the curve are straight lines provided the volume of the reagent added is small, and their
intersection gives the end point, as shown below. The unknown volume and weight of the HCI is
calculated from the end point.
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Figure 14: Strong acid versus a strong base

2. Mixture of a strong acid and a weak acid with a strong base: Upon adding a strong base
to a mixture of a strong acid and a weak acid (e.g. HCI + CH3COOH), the conductance falls until
the strong acid is neutralized completely, due to the removal of H+ ions. The weak acid remains
undissociated in the presence of a strong acid. Once the strong acid is completely neutralized, the
weak acid begins to dissociate and gets neutralized. This results in the increase in conductance of
the solution as the weak acid is consumed and converted into its salt. When the neutralization of
second acid is completed, there is a steep increase in conductance due to the ions furnished by the
strong base. The reactions as follows.

HCI + NaOH → NaC1 + H2O

CH3COOH + NaOH → CH3COONa + H2O

The three branches of the graph are straight lines as shown in the graph, the extrapolation of the
straight portions of three branches leads to definite location of the end points. The first point of
intersection gives the amount of base consumed by the strong acid and the difference between the
first and the second is the amount of base consumed by the weak acid.
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Volume of base added (ml)

Figure 15: Mixture of acids versus a strong base

3. Weak acid with a strong base: In the titration of a weak acid with a strong base, the shape of the
curve depends upon the concentration and the dissociation constant (Ka) of the acid. For ex: In the
neutralization of acetic acid with NaOH solution, the salt (CH3COONa), which is formed during the
titration tends to suppress the ionization of acetic acid still present so that its conductance decreases.
The increasing salt concentration; however tends to produce an increase in conductance. As a result
of these opposing changes, the titration curve may have a minimum and hence the difficulty arises
in locating the end point accurately. Thereafter, the conductance of the solution increases, and
somewhat an indefinite break occurs at the end point, and the graph becomes linear after all acid has
been neutralized.

CH3COOH + NaOH → CH3COONa + H2O

Figure 16: Weak acid versus a strong base

Advantages of Conductometric titrations:

In this method as conductance is measured by conductivity meter, indicator is not required.
Conductometric titration works for colored solution
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Accurate results can be obtained by conductometry

It is suitable for both weak base as well as weak acid
This method is also suitable for turbid solution
Limitations:

Can be employed only when there is appreciable change is conductance during the titration.
sometimes the salt level increases in the solution which masks the conductivity and do not
give accurate results
Sometimes high concentrations of ions mask the conductivity and hence do not give
accurate results.

Principle, Instrumentation and Applications of Potentiometry

Principle: "The potential difference between the two electrodes used to form the basis of
potentiometry. The addition of a titrant leads to a change in the ionic concentration, causing
changes in the potential difference".

The indicator electrode measures this potential difference. The reference electrode has a potential
value and remains stable when dipped into the sample solution.
The potential difference is calculated according to Nernst equation;

E=Eo + 2.303 RT log [Mn+ ]

E can be measured by combining the electrode with a reference electrode and measuring the
emf of the cell using potentiometer. The concentration can be calculated, provided Eo of the
electrode is known.

Location of end point: The titration curve can be obtained by plotting emf readings obtained
with the reference-indicator electrode pair against volume of the titrant added.

An approximate value of the end point can be obtained from the graph, as being midway
along the steep portion of the curve as shown below. Hence, the end point can be located
more precisely by employing derivative curves in which the first derivative curve (ΔE/ΔV)
against V or the Second derivative curve (Δ2E/ΔV2) against V are plotted as shown below.
 Dr. BALAJOTHI B
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Figure 17: Potentiometric titration curve

Figure 18: First derivative curve for potentiometric titration

Instrumentation: A potentiometer consists of

1. An indicator electrode Ex: Pt, ISE-glass electrode

2. A standard reference electrode Ex: calomel electrode, Ag/AgCl

3. Meter: To read the values directly with change in the potential due to the concentration
changes of the analyte.
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Burette

Saturated
Calomel
electrode

Figure 19:Potentiometer
setup
Applications of Potentiometry:

1. Acid base titrations: For an acid base titration, the indicator electrode has be a pH sensitive
Or H+ sensitive electrode as it has to respond to the change in pH during the titration. Therefore,
glass electrode is most commonly used as the indicator electrode. Saturated calomel electrode
is generally employed as the reference electrode. Since the pH changes very sharply near the end
point, the emf of the cell also changes rapidly near the end point. The accuracy of the method
depends upon the magnitude of the change in emf in the neighborhood of the equivalence point, and
this depends upon the concentration and strength of the acid and alkali. The method may be used to
titrate a mixture of acids which differ greatly in their strengths. For example, a mixture of acetic acid
and hydrochloric acid can be titrated.
2. Oxidation reduction titrations (Estimation of Mohr's salt): Oxidation reduction titrations
can conveniently be carried out as potentiometric titrations. For example, in the titration of Mohr’s
salt solution with potassium dichromate solution, calomel electrode is used as the reference
electrode and an inert platinum foil is used to pick up the potential of the indicator electrode,
which is actually the oxidation reduction electrode involving the redox species present in the
solution.

Before the titration is started, the solution contains only ferrous ions in the solution. When a small
volume of the dichromate solution is added, equivalent small quantities of Fe2+ ions are converted
into Fe3+ ions. In the process, the Cr6+ ions in dichromate are reduced to Cr3+ ions.

3Fe2+ + Cr6+ → 3Fe3+ + Cr3+

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The presence of Fe2+ and Fe3+ ions in the solution gives rise to an oxidation reduction electrode, the
potential of which can be picked up by the platinum electrode dipped in the solution (Pt/Fe3+ , Fe2+).
The electrode potential of the so formed electrode is given by,
E = EO + 0.05911og[Fe3+] / [Fe2+ ]
The electrode potential of the indicator electrode depends upon the ratio of the concentrations of
oxidized and reduced species in the solution. As the titration proceeds, the concentration of Fe3+
goes on increasing and that of Fe2+ goes on decreasing. As a result, the ratio in the expression for
electrode potential goes on increasing and the increase in the value of the ratio becomes very large
near the end point. This amounts in the large increase in the electrode potential and in turn, in the
measured emf of the cell.

At the equivalence point, all the Fe2+ ions are converted into Fe3+ ions, the Pt/Fe3+ , Fe2+ electrode
ceases to exist. But the addition of excess of dichromate introduces Cr6+ ions into the solution, which
along with the Cr3+ ions in the solution form a new oxidation reduction electrode Pt/Cr6+ , Cr3+. This
change over of indicator electrode at the end point also contributes to the large increase in potential
at the end point, as the EO values of the two electrodes differ by a large value.
3. Precipitation titrations: Precipitation reactions can also be carried out potentiometrically. In the
precipitation of an ion X, from solution by the addition of a suitable reagent, the concentration of X
in the solution will change most rapidly in the region of the end point. The potential of an indicator
electrode responsive to the concentration of X will undergo a like change, and hence can be followed
potentiometrically. In this case an indicator electrode comes in equilibrium with one of the ions of
the precipitate. For example, in the titration of silver ions with a halide ion, silver electrode can be
used as the indicator electrode.
AgNO3 + NaCl → AgC1 (ppt) + NaNO3

Advantages of Potentiometry:
colored solutions, dilute solutions or turbid suspensions can be titrated
Titration can be automated
Mixture of components can be titrated
Inexpensive and more accuracy
Reference electrode potential need not be known-constant
Limitations:

Mostly saturated solution of KCl is used and that is temperature dependent